diff --git a/docling/backend/xml/__init__.py b/docling/backend/xml/__init__.py new file mode 100644 index 00000000..e69de29b diff --git a/docling/backend/xml/uspto_backend.py b/docling/backend/xml/uspto_backend.py new file mode 100644 index 00000000..ef253b21 --- /dev/null +++ b/docling/backend/xml/uspto_backend.py @@ -0,0 +1,1888 @@ +"""Backend to parse patents from the United States Patent Office (USPTO). + +The parsers included in this module can handle patent grants pubished since 1976 and +patent applications since 2001. +The original files can be found in https://bulkdata.uspto.gov. +""" + +import html +import logging +import re +import xml.sax +import xml.sax.xmlreader +from abc import ABC, abstractmethod +from enum import Enum, unique +from io import BytesIO +from pathlib import Path +from typing import Any, Final, Optional, Union + +from bs4 import BeautifulSoup, Tag +from docling_core.types.doc import ( + DocItem, + DocItemLabel, + DoclingDocument, + DocumentOrigin, + TableCell, + TableData, + TextItem, +) +from docling_core.types.doc.document import LevelNumber +from pydantic import NonNegativeInt +from typing_extensions import Self, TypedDict, override + +from docling.backend.abstract_backend import DeclarativeDocumentBackend +from docling.datamodel.base_models import InputFormat +from docling.datamodel.document import InputDocument + +_log = logging.getLogger(__name__) + +XML_DECLARATION: Final = '' + + +@unique +class PatentHeading(Enum): + """Text of docling headings for tagged sections in USPTO patent documents.""" + + ABSTRACT = "ABSTRACT", 2 + CLAIMS = "CLAIMS", 2 + + @override + def __new__(cls, value: str, _) -> Self: + obj = object.__new__(cls) + obj._value_ = value + return obj + + @override + def __init__(self, _, level: LevelNumber) -> None: + self.level: LevelNumber = level + + +class PatentUsptoDocumentBackend(DeclarativeDocumentBackend): + @override + def __init__( + self, in_doc: InputDocument, path_or_stream: Union[BytesIO, Path] + ) -> None: + super().__init__(in_doc, path_or_stream) + + self.patent_content: str = "" + self.parser: Optional[PatentUspto] = None + + try: + if isinstance(self.path_or_stream, BytesIO): + while line := self.path_or_stream.readline().decode("utf-8"): + if line.startswith(" None: + doctype_line = doctype.lower() + if doctype == "PATN\n": + self.parser = PatentUsptoGrantAps() + elif "us-patent-application-v4" in doctype_line: + self.parser = PatentUsptoIce() + elif "us-patent-grant-v4" in doctype_line: + self.parser = PatentUsptoIce() + elif "us-grant-025" in doctype_line: + self.parser = PatentUsptoGrantV2() + elif all( + item in doctype_line + for item in ("patent-application-publication", "pap-v1") + ): + self.parser = PatentUsptoAppV1() + else: + self.parser = None + + @override + def is_valid(self) -> bool: + return bool(self.patent_content) and bool(self.parser) + + @classmethod + @override + def supports_pagination(cls) -> bool: + return False + + @override + def unload(self) -> None: + return + + @classmethod + @override + def supported_formats(cls) -> set[InputFormat]: + return {InputFormat.XML_USPTO} + + @override + def convert(self) -> DoclingDocument: + + if self.parser is not None: + doc = self.parser.parse(self.patent_content) + if doc is None: + raise RuntimeError( + f"Failed to convert doc (hash={self.document_hash}, " + f"name={self.file.name})." + ) + doc.name = self.file.name or "file" + mime_type = ( + "text/plain" + if isinstance(self.parser, PatentUsptoGrantAps) + else "application/xml" + ) + doc.origin = DocumentOrigin( + mimetype=mime_type, + binary_hash=self.document_hash, + filename=self.file.name or "file", + ) + + return doc + else: + raise RuntimeError( + f"Cannot convert doc (hash={self.document_hash}, " + f"name={self.file.name}) because the backend failed to init." + ) + + +class PatentUspto(ABC): + """Parser of patent documents from the US Patent Office.""" + + @abstractmethod + def parse(self, patent_content: str) -> Optional[DoclingDocument]: + """Parse a USPTO patent. + + Parameters: + patent_content: The content of a single patent in a USPTO file. + + Returns: + The patent parsed as a docling document. + """ + pass + + +class PatentUsptoIce(PatentUspto): + """Parser of patent documents from the US Patent Office (ICE). + + The compatible formats are: + - Patent Grant Full Text Data/XML Version 4.x ICE (from January 2005) + - Patent Application Full Text Data/XML Version 4.x ICE (from January 2005) + """ + + def __init__(self) -> None: + """Build an instance of PatentUsptoIce class.""" + self.handler = PatentUsptoIce.PatentHandler() + self.pattern = re.compile(r"^()", re.MULTILINE | re.DOTALL) + + def parse(self, patent_content: str) -> Optional[DoclingDocument]: + try: + xml.sax.parseString(patent_content, self.handler) + except xml.sax._exceptions.SAXParseException as exc_sax: + _log.error(f"Error in parsing USPTO document: {exc_sax}") + + return None + + doc = self.handler.doc + if doc: + raw_tables = re.findall(self.pattern, patent_content) + parsed_tables: list[TableData] = [] + _log.debug(f"Found {len(raw_tables)} tables to be parsed with XmlTable.") + for table in raw_tables: + table_parser = XmlTable(XML_DECLARATION + "\n" + table) + try: + table_data = table_parser.parse() + if table_data: + parsed_tables.append(table_data) + except Exception as exc_table: + _log.error(f"Error in parsing USPTO tables: {exc_table}") + if len(parsed_tables) != len(doc.tables): + _log.error( + f"Number of referenced ({len(doc.tables)}) and parsed " + f"({len(parsed_tables)}) tables differ." + ) + else: + for idx, item in enumerate(parsed_tables): + doc.tables[idx].data = item + + return doc + + class PatentHandler(xml.sax.handler.ContentHandler): + """SAX ContentHandler for patent documents.""" + + APP_DOC_ELEMENT: Final = "us-patent-application" + GRANT_DOC_ELEMENT: Final = "us-patent-grant" + + @unique + class Element(Enum): + """Represents an element of interest in the patent application document.""" + + ABSTRACT = "abstract", True + TITLE = "invention-title", True + CLAIMS = "claims", False + CLAIM = "claim", False + CLAIM_TEXT = "claim-text", True + PARAGRAPH = "p", True + HEADING = "heading", True + DESCRIPTION = "description", False + TABLE = "table", False # to track its position, without text + DRAWINGS = "description-of-drawings", True + STYLE_SUPERSCRIPT = "sup", True + STYLE_SUBSCRIPT = "sub", True + MATHS = "maths", False # to avoid keeping formulas + + @override + def __new__(cls, value: str, _) -> Self: + obj = object.__new__(cls) + obj._value_ = value + return obj + + @override + def __init__(self, _, is_text: bool) -> None: + self.is_text: bool = is_text + + @override + def __init__(self) -> None: + """Build an instance of the patent handler.""" + # Current patent being parsed + self.doc: Optional[DoclingDocument] = None + # Keep track of docling hierarchy level + self.level: LevelNumber = 1 + # Keep track of docling parents by level + self.parents: dict[LevelNumber, Optional[DocItem]] = {1: None} + # Content to retain for the current patent + self.property: list[str] + self.claim: str + self.claims: list[str] + self.abstract: str + self.text: str + self._clean_data() + # To handle mathematical styling + self.style_html = HtmlEntity() + + @override + def startElement(self, tag, attributes): # noqa: N802 + """Signal the start of an element. + + Args: + tag: The element tag. + attributes: The element attributes. + """ + if tag in ( + self.APP_DOC_ELEMENT, + self.GRANT_DOC_ELEMENT, + ): + self.doc = DoclingDocument(name="file") + self.text = "" + self._start_registered_elements(tag, attributes) + + @override + def skippedEntity(self, name): # noqa: N802 + """Receive notification of a skipped entity. + + HTML entities will be skipped by the parser. This method will unescape them + and add them to the text. + + Args: + name: Entity name. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + escaped = self.style_html.get_greek_from_iso8879(f"&{name};") + unescaped = html.unescape(escaped) + if unescaped == escaped: + _log.debug(f"Unrecognized HTML entity: {name}") + return + + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(unescaped, elm_val) + else: + self.text += unescaped + + @override + def endElement(self, tag): # noqa: N802 + """Signal the end of an element. + + Args: + tag: The element tag. + """ + if tag in ( + self.APP_DOC_ELEMENT, + self.GRANT_DOC_ELEMENT, + ): + self._clean_data() + self._end_registered_element(tag) + + @override + def characters(self, content): + """Receive notification of character data. + + Args: + content: Data reported by the handler. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(content, elm_val) + else: + self.text += content + + def _start_registered_elements( + self, tag: str, attributes: xml.sax.xmlreader.AttributesImpl + ) -> None: + if tag in [member.value for member in self.Element]: + # special case for claims: claim lines may start before the + # previous one is closed + if ( + tag == self.Element.CLAIM_TEXT.value + and self.property + and self.property[-1] == tag + and self.text.strip() + ): + self.claim += " " + self.text.strip() + self.text = "" + elif tag == self.Element.HEADING.value: + level_attr: str = attributes.get("level", "") + new_level: int = int(level_attr) if level_attr.isnumeric() else 1 + max_level = min(self.parents.keys()) + # increase heading level with 1 for title, if any + self.level = ( + new_level + 1 if (new_level + 1) in self.parents else max_level + ) + self.property.append(tag) + + def _end_registered_element(self, tag: str) -> None: + if tag in [item.value for item in self.Element] and self.property: + current_tag = self.property.pop() + self._add_property(current_tag, self.text.strip()) + + def _add_property(self, name: str, text: str) -> None: + if not name or not self.doc: + return + + if name == self.Element.TITLE.value: + if text: + self.parents[self.level + 1] = self.doc.add_title( + parent=self.parents[self.level], # type: ignore[arg-type] + text=text, + ) + self.level += 1 + self.text = "" + + elif name == self.Element.ABSTRACT.value: + if self.abstract: + heading_text = PatentHeading.ABSTRACT.value + heading_level = ( + PatentHeading.ABSTRACT.level + if PatentHeading.ABSTRACT.level in self.parents + else 1 + ) + abstract_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=self.abstract, + parent=abstract_item, + ) + + elif name == self.Element.CLAIM_TEXT.value: + text = re.sub("\\s+", " ", text).strip() + if text: + self.claim += " " + text + self.text = "" + + elif name == self.Element.CLAIM.value and self.claim: + self.claims.append(self.claim.strip()) + self.claim = "" + + elif name == self.Element.CLAIMS.value and self.claims: + heading_text = PatentHeading.CLAIMS.value + heading_level = ( + PatentHeading.CLAIMS.level + if PatentHeading.CLAIMS.level in self.parents + else 1 + ) + claims_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + for text in self.claims: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, text=text, parent=claims_item + ) + + elif name == self.Element.PARAGRAPH.value and text: + # remmove blank spaces added in paragraphs + text = re.sub("\\s+", " ", text) + if self.Element.ABSTRACT.value in self.property: + self.abstract = ( + (self.abstract + " " + text) if self.abstract else text + ) + else: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=text, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.text = "" + + elif name == self.Element.HEADING.value and text: + self.parents[self.level + 1] = self.doc.add_heading( + text=text, + level=self.level, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.level += 1 + self.text = "" + + elif name == self.Element.TABLE.value: + # set an empty table as placeholder + empty_table = TableData(num_rows=0, num_cols=0, table_cells=[]) + self.doc.add_table( + data=empty_table, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + def _apply_style(self, text: str, style_tag: str) -> str: + """Apply an HTML style to text. + + Args: + text: A string containing plain text. + style_tag: An HTML tag name for styling text. If the tag name is not + recognized as one of the supported styles, the method will return + the original `text`. + + Returns: + A string after applying the style. + """ + formatted = text + + if style_tag == self.Element.STYLE_SUPERSCRIPT.value: + formatted = html.unescape(self.style_html.get_superscript(text)) + elif style_tag == self.Element.STYLE_SUBSCRIPT.value: + formatted = html.unescape(self.style_html.get_subscript(text)) + + return formatted + + def _clean_data(self) -> None: + """Reset the variables from stream data.""" + self.property = [] + self.claim = "" + self.claims = [] + self.abstract = "" + + +class PatentUsptoGrantV2(PatentUspto): + """Parser of patent documents from the US Patent Office (grants v2.5). + + The compatible format is: + - Patent Grant Full Text Data/XML Version 2.5 (from January 2002 till December 2004) + """ + + @override + def __init__(self) -> None: + """Build an instance of PatentUsptoGrantV2 class.""" + self.handler = PatentUsptoGrantV2.PatentHandler() + self.pattern = re.compile(r"^(
)", re.MULTILINE | re.DOTALL) + + @override + def parse(self, patent_content: str) -> Optional[DoclingDocument]: + try: + xml.sax.parseString(patent_content, self.handler) + except xml.sax._exceptions.SAXParseException as exc_sax: + _log.error(f"Error in parsing USPTO document: {exc_sax}") + + return None + + doc = self.handler.doc + if doc: + raw_tables = re.findall(self.pattern, patent_content) + parsed_tables: list[TableData] = [] + _log.debug(f"Found {len(raw_tables)} tables to be parsed with XmlTable.") + for table in raw_tables: + table_parser = XmlTable(XML_DECLARATION + "\n" + table) + try: + table_data = table_parser.parse() + if table_data: + parsed_tables.append(table_data) + except Exception as exc_table: + _log.error(f"Error in parsing USPTO tables: {exc_table}") + if len(parsed_tables) != len(doc.tables): + _log.error( + f"Number of referenced ({len(doc.tables)}) and parsed " + f"({len(parsed_tables)}) tables differ." + ) + else: + for idx, item in enumerate(parsed_tables): + doc.tables[idx].data = item + + return doc + + class PatentHandler(xml.sax.handler.ContentHandler): + """SAX ContentHandler for patent documents.""" + + GRANT_DOC_ELEMENT: Final = "PATDOC" + CLAIM_STATEMENT: Final = "What is claimed is:" + + @unique + class Element(Enum): + """Represents an element of interest in the patent application document.""" + + PDAT = "PDAT", True # any type of data + ABSTRACT = ("SDOAB", False) + SDOCL = ("SDOCL", False) + TITLE = ("B540", False) + CLAIMS = ("CL", False) + CLAIM = ("CLM", False) + PARAGRAPH = ("PARA", True) + HEADING = ("H", True) + DRAWINGS = ("DRWDESC", False) + STYLE_SUPERSCRIPT = ("SP", False) + STYLE_SUBSCRIPT = ("SB", False) + STYLE_ITALIC = ("ITALIC", False) + CWU = ("CWU", False) # avoid tables, chemicals, formulas + TABLE = ("table", False) # to keep track of table positions + + @override + def __new__(cls, value: str, _) -> Self: + obj = object.__new__(cls) + obj._value_ = value + return obj + + @override + def __init__(self, _, is_text: bool) -> None: + self.is_text: bool = is_text + + @override + def __init__(self) -> None: + """Build an instance of the patent handler.""" + # Current patent being parsed + self.doc: Optional[DoclingDocument] = None + # Keep track of docling hierarchy level + self.level: LevelNumber = 1 + # Keep track of docling parents by level + self.parents: dict[LevelNumber, Optional[DocItem]] = {1: None} + # Content to retain for the current patent + self.property: list[str] + self.claim: str + self.claims: list[str] + self.paragraph: str + self.abstract: str + self._clean_data() + # To handle mathematical styling + self.style_html = HtmlEntity() + + @override + def startElement(self, tag, attributes): # noqa: N802 + """Signal the start of an element. + + Args: + tag: The element tag. + attributes: The element attributes. + """ + if tag == self.GRANT_DOC_ELEMENT: + self.doc = DoclingDocument(name="file") + self.text = "" + self._start_registered_elements(tag, attributes) + + @override + def skippedEntity(self, name): # noqa: N802 + """Receive notification of a skipped entity. + + HTML entities will be skipped by the parser. This method will unescape them + and add them to the text. + + Args: + name: Entity name. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + escaped = self.style_html.get_greek_from_iso8879(f"&{name};") + unescaped = html.unescape(escaped) + if unescaped == escaped: + logging.debug("Unrecognized HTML entity: " + name) + return + + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(unescaped, elm_val) + else: + self.text += unescaped + + @override + def endElement(self, tag): # noqa: N802 + """Signal the end of an element. + + Args: + tag: The element tag. + """ + if tag == self.GRANT_DOC_ELEMENT: + self._clean_data() + self._end_registered_element(tag) + + @override + def characters(self, content): + """Receive notification of character data. + + Args: + content: Data reported by the handler. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(content, elm_val) + else: + self.text += content + + def _start_registered_elements( + self, tag: str, attributes: xml.sax.xmlreader.AttributesImpl + ) -> None: + if tag in [member.value for member in self.Element]: + if ( + tag == self.Element.HEADING.value + and not self.Element.SDOCL.value in self.property + ): + level_attr: str = attributes.get("LVL", "") + new_level: int = int(level_attr) if level_attr.isnumeric() else 1 + max_level = min(self.parents.keys()) + # increase heading level with 1 for title, if any + self.level = ( + new_level + 1 if (new_level + 1) in self.parents else max_level + ) + self.property.append(tag) + + def _end_registered_element(self, tag: str) -> None: + if tag in [elm.value for elm in self.Element] and self.property: + current_tag = self.property.pop() + self._add_property(current_tag, self.text) + + def _add_property(self, name: str, text: str) -> None: + if not name or not self.doc: + return + if name == self.Element.PDAT.value and text: + if not self.property: + self.text = "" + return + + wrapper = self.property[-1] + text = self._apply_style(text, wrapper) + + if self.Element.TITLE.value in self.property and text.strip(): + title = text.strip() + self.parents[self.level + 1] = self.doc.add_title( + parent=self.parents[self.level], # type: ignore[arg-type] + text=title, + ) + self.level += 1 + + elif self.Element.ABSTRACT.value in self.property: + self.abstract += text + + elif self.Element.CLAIM.value in self.property: + self.claim += text + + # Paragraph text not in claims or abstract + elif ( + self.Element.PARAGRAPH.value in self.property + and self.Element.CLAIM.value not in self.property + and self.Element.ABSTRACT.value not in self.property + ): + self.paragraph += text + + # headers except claims statement + elif ( + self.Element.HEADING.value in self.property + and not self.Element.SDOCL.value in self.property + and text.strip() + ): + self.parents[self.level + 1] = self.doc.add_heading( + text=text.strip(), + level=self.level, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.level += 1 + + self.text = "" + + elif name == self.Element.CLAIM.value and self.claim.strip(): + self.claims.append(self.claim.strip()) + self.claim = "" + + elif name == self.Element.CLAIMS.value and self.claims: + heading_text = PatentHeading.CLAIMS.value + heading_level = ( + PatentHeading.CLAIMS.level + if PatentHeading.CLAIMS.level in self.parents + else 1 + ) + claims_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + for text in self.claims: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, text=text, parent=claims_item + ) + + elif name == self.Element.ABSTRACT.value and self.abstract.strip(): + abstract = self.abstract.strip() + heading_text = PatentHeading.ABSTRACT.value + heading_level = ( + PatentHeading.ABSTRACT.level + if PatentHeading.ABSTRACT.level in self.parents + else 1 + ) + abstract_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, text=abstract, parent=abstract_item + ) + + elif name == self.Element.PARAGRAPH.value: + paragraph = self.paragraph.strip() + if paragraph and self.Element.CLAIM.value not in self.property: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=paragraph, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + elif self.Element.CLAIM.value in self.property: + # we may need a space after a paragraph in claim text + self.claim += " " + self.paragraph = "" + + elif name == self.Element.TABLE.value: + # set an empty table as placeholder + empty_table = TableData(num_rows=0, num_cols=0, table_cells=[]) + self.doc.add_table( + data=empty_table, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + def _apply_style(self, text: str, style_tag: str) -> str: + """Apply an HTML style to text. + + Args: + text: A string containing plain text. + style_tag: An HTML tag name for styling text. If the tag name is not + recognized as one of the supported styles, the method will return + the original `text`. + + Returns: + A string after applying the style. + """ + formatted = text + + if style_tag == self.Element.STYLE_SUPERSCRIPT.value: + formatted = html.unescape(self.style_html.get_superscript(text)) + elif style_tag == self.Element.STYLE_SUBSCRIPT.value: + formatted = html.unescape(self.style_html.get_subscript(text)) + elif style_tag == self.Element.STYLE_ITALIC.value: + formatted = html.unescape(self.style_html.get_math_italic(text)) + + return formatted + + def _clean_data(self) -> None: + """Reset the variables from stream data.""" + self.text = "" + self.property = [] + self.claim = "" + self.claims = [] + self.paragraph = "" + self.abstract = "" + + +class PatentUsptoGrantAps(PatentUspto): + """Parser of patents documents from the US Patent Office (grants APS). + + The compatible format is: + - Patent Grant Full Text Data/APS (from January 1976 till December 2001) + """ + + @unique + class Section(Enum): + """Represent a section in a patent APS document.""" + + ABSTRACT = "ABST" + SUMMARY = "BSUM" + DETAILS = "DETD" + CLAIMS = "CLMS" + DRAWINGS = "DRWD" + + @unique + class Field(Enum): + """Represent a field in a patent APS document.""" + + DOC_NUMBER = "WKU" + TITLE = "TTL" + PARAGRAPH = "PAR" + PARAGRAPH_1 = "PA1" + PARAGRAPH_2 = "PA2" + PARAGRAPH_3 = "PA3" + TEXT = "PAL" + CAPTION = "PAC" + NUMBER = "NUM" + NAME = "NAM" + IPC = "ICL" + ISSUED = "ISD" + FILED = "APD" + PATENT_NUMBER = "PNO" + APPLICATION_NUMBER = "APN" + APPLICATION_TYPE = "APT" + COUNTRY = "CNT" + + @override + def __init__(self) -> None: + """Build an instance of PatentUsptoGrantAps class.""" + self.doc: Optional[DoclingDocument] = None + # Keep track of docling hierarchy level + self.level: LevelNumber = 1 + # Keep track of docling parents by level + self.parents: dict[LevelNumber, Optional[DocItem]] = {1: None} + + def get_last_text_item(self) -> Optional[TextItem]: + """Get the last text item at the current document level. + + Returns: + The text item or None, if the current level parent has no children.""" + if self.doc: + parent = self.parents[self.level] + children = parent.children if parent is not None else [] + else: + return None + text_list: list[TextItem] = [ + item + for item in self.doc.texts + if isinstance(item, TextItem) and item.get_ref() in children + ] + + if text_list: + return text_list[-1] + else: + return None + + def store_section(self, section: str) -> None: + """Store the section heading in the docling document. + + Only the predefined sections from PatentHeading will be handled. + The other sections are created by the Field.CAPTION field. + + Args: + section: A patent section name.""" + heading: PatentHeading + if self.doc is None: + return + elif section == self.Section.ABSTRACT.value: + heading = PatentHeading.ABSTRACT + elif section == self.Section.CLAIMS.value: + heading = PatentHeading.CLAIMS + else: + return None + + self.level = heading.level if heading.level in self.parents else 1 + self.parents[self.level + 1] = self.doc.add_heading( + heading.value, + level=self.level, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.level += 1 + + def store_content(self, section: str, field: str, value: str) -> None: + """Store the key value within a document section in the docling document. + + Args: + section: A patent section name. + field: A field name. + value: A field value name. + """ + if ( + not self.doc + or not field + or field not in [item.value for item in PatentUsptoGrantAps.Field] + ): + return + + if field == self.Field.TITLE.value: + self.parents[self.level + 1] = self.doc.add_title( + parent=self.parents[self.level], text=value # type: ignore[arg-type] + ) + self.level += 1 + + elif field == self.Field.TEXT.value and section == self.Section.ABSTRACT.value: + abst_item = self.get_last_text_item() + if abst_item: + abst_item.text += " " + value + else: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=value, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + elif field == self.Field.NUMBER.value and section == self.Section.CLAIMS.value: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text="", + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + elif ( + field + in ( + self.Field.PARAGRAPH.value, + self.Field.PARAGRAPH_1.value, + self.Field.PARAGRAPH_2.value, + self.Field.PARAGRAPH_3.value, + ) + and section == self.Section.CLAIMS.value + ): + last_claim = self.get_last_text_item() + if last_claim is None: + last_claim = self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text="", + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + last_claim.text += f" {value}" if last_claim.text else value + + elif field == self.Field.CAPTION.value and section in ( + self.Section.SUMMARY.value, + self.Section.DETAILS.value, + self.Section.DRAWINGS.value, + ): + # captions are siblings of abstract since no level info is provided + head_item = PatentHeading.ABSTRACT + self.level = head_item.level if head_item.level in self.parents else 1 + self.parents[self.level + 1] = self.doc.add_heading( + value, + level=self.level, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.level += 1 + + elif field in ( + self.Field.PARAGRAPH.value, + self.Field.PARAGRAPH_1.value, + self.Field.PARAGRAPH_2.value, + self.Field.PARAGRAPH_3.value, + ) and section in ( + self.Section.SUMMARY.value, + self.Section.DETAILS.value, + self.Section.DRAWINGS.value, + ): + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=value, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + def parse(self, patent_content: str) -> Optional[DoclingDocument]: + self.doc = self.doc = DoclingDocument(name="file") + section: str = "" + key: str = "" + value: str = "" + line_num = 0 + for line in patent_content.splitlines(): + cols = re.split("\\s{2,}", line, maxsplit=1) + if key and value and (len(cols) == 1 or (len(cols) == 2 and cols[0])): + self.store_content(section, key, value) + key = "" + value = "" + if len(cols) == 1: # section title + section = cols[0] + self.store_section(section) + _log.debug(f"Parsing section {section}") + elif len(cols) == 2: # key value + if cols[0]: # key present + key = cols[0] + value = cols[1] + elif not re.match(r"^##STR\d+##$", cols[1]): # line continues + value += " " + cols[1] + line_num += 1 + if key and value: + self.store_content(section, key, value) + + # TODO: parse tables + return self.doc + + +class PatentUsptoAppV1(PatentUspto): + """Parser of patent documents from the US Patent Office (applications v1.x) + + The compatible format is: + - Patent Application Full Text Data/XML Version 1.x (from March 2001 till December + 2004) + """ + + @override + def __init__(self) -> None: + """Build an instance of PatentUsptoAppV1 class.""" + self.handler = PatentUsptoAppV1.PatentHandler() + self.pattern = re.compile(r"^(
)", re.MULTILINE | re.DOTALL) + + @override + def parse(self, patent_content: str) -> Optional[DoclingDocument]: + try: + xml.sax.parseString(patent_content, self.handler) + except xml.sax._exceptions.SAXParseException as exc_sax: + _log.error(f"Error in parsing USPTO document: {exc_sax}") + + return None + + doc = self.handler.doc + if doc: + raw_tables = re.findall(self.pattern, patent_content) + parsed_tables: list[TableData] = [] + _log.debug(f"Found {len(raw_tables)} tables to be parsed with XmlTable.") + for table in raw_tables: + table_parser = XmlTable(XML_DECLARATION + "\n" + table) + try: + table_data = table_parser.parse() + if table_data: + parsed_tables.append(table_data) + except Exception as exc_table: + _log.error(f"Error in parsing USPTO tables: {exc_table}") + if len(parsed_tables) != len(doc.tables): + _log.error( + f"Number of referenced ({len(doc.tables)}) and parsed " + f"({len(parsed_tables)}) tables differ." + ) + else: + for idx, item in enumerate(parsed_tables): + doc.tables[idx].data = item + + return doc + + class PatentHandler(xml.sax.handler.ContentHandler): + """SAX ContentHandler for patent documents.""" + + APP_DOC_ELEMENT: Final = "patent-application-publication" + + @unique + class Element(Enum): + """Represents an element of interest in the patent application document.""" + + DRAWINGS = "brief-description-of-drawings", False + ABSTRACT = "subdoc-abstract", False + TITLE = "title-of-invention", True + CLAIMS = "subdoc-claims", False + CLAIM = "claim", False + CLAIM_TEXT = "claim-text", True + NUMBER = ("number", False) + PARAGRAPH = "paragraph", True + HEADING = "heading", True + STYLE_SUPERSCRIPT = "superscript", True + STYLE_SUBSCRIPT = "subscript", True + # do not store text of a table, since it can be within paragraph + TABLE = "table", False + # do not store text of a formula, since it can be within paragraph + MATH = "math-cwu", False + + @override + def __new__(cls, value: str, _) -> Self: + obj = object.__new__(cls) + obj._value_ = value + return obj + + @override + def __init__(self, _, is_text: bool) -> None: + self.is_text: bool = is_text + + @override + def __init__(self) -> None: + """Build an instance of the patent handler.""" + # Current patent being parsed + self.doc: Optional[DoclingDocument] = None + # Keep track of docling hierarchy level + self.level: LevelNumber = 1 + # Keep track of docling parents by level + self.parents: dict[LevelNumber, Optional[DocItem]] = {1: None} + # Content to retain for the current patent + self.property: list[str] + self.claim: str + self.claims: list[str] + self.abstract: str + self.text: str + self._clean_data() + # To handle mathematical styling + self.style_html = HtmlEntity() + + @override + def startElement(self, tag, attributes): # noqa: N802 + """Signal the start of an element. + + Args: + tag: The element tag. + attributes: The element attributes. + """ + if tag == self.APP_DOC_ELEMENT: + self.doc = DoclingDocument(name="file") + self.text = "" + self._start_registered_elements(tag, attributes) + + @override + def skippedEntity(self, name): # noqa: N802 + """Receive notification of a skipped entity. + + HTML entities will be skipped by the parser. This method will unescape them + and add them to the text. + + Args: + name: Entity name. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + escaped = self.style_html.get_greek_from_iso8879(f"&{name};") + unescaped = html.unescape(escaped) + if unescaped == escaped: + logging.debug("Unrecognized HTML entity: " + name) + return + + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(unescaped, elm_val) + else: + self.text += unescaped + + @override + def endElement(self, tag): # noqa: N802 + """Signal the end of an element. + + Args: + tag: The element tag. + """ + if tag == self.APP_DOC_ELEMENT: + self._clean_data() + self._end_registered_element(tag) + + @override + def characters(self, content): + """Receive notification of character data. + + Args: + content: Data reported by the handler. + """ + if self.property: + elm_val = self.property[-1] + element = self.Element(elm_val) + if element.is_text: + if element in ( + self.Element.STYLE_SUPERSCRIPT, + self.Element.STYLE_SUBSCRIPT, + ): + # superscripts and subscripts need to be under text elements + if len(self.property) < 2: + return + parent_val = self.property[-2] + parent = self.Element(parent_val) + if parent.is_text: + self.text += self._apply_style(content, elm_val) + else: + self.text += content + + def _start_registered_elements( + self, tag: str, attributes: xml.sax.xmlreader.AttributesImpl + ) -> None: + if tag in [member.value for member in self.Element]: + # special case for claims: claim lines may start before the + # previous one is closed + if ( + tag == self.Element.CLAIM_TEXT.value + and self.property + and self.property[-1] == tag + and self.text.strip() + ): + self.claim += " " + self.text.strip("\n") + self.text = "" + elif tag == self.Element.HEADING.value: + level_attr: str = attributes.get("lvl", "") + new_level: int = int(level_attr) if level_attr.isnumeric() else 1 + max_level = min(self.parents.keys()) + # increase heading level with 1 for title, if any + self.level = ( + new_level + 1 if (new_level + 1) in self.parents else max_level + ) + self.property.append(tag) + + def _end_registered_element(self, tag: str) -> None: + if tag in [elm.value for elm in self.Element] and self.property: + current_tag = self.property.pop() + self._add_property(current_tag, self.text) + + def _add_property(self, name: str, text: str) -> None: + if not name or not self.doc: + return + + if name == self.Element.TITLE.value: + title = text.strip() + if title: + self.parents[self.level + 1] = self.doc.add_text( + parent=self.parents[self.level], # type: ignore[arg-type] + label=DocItemLabel.TITLE, + text=title, + ) + self.level += 1 + self.text = "" + elif name == self.Element.ABSTRACT.value: + abstract = self.abstract.strip() + if abstract: + heading_text = PatentHeading.ABSTRACT.value + heading_level = ( + PatentHeading.ABSTRACT.level + if PatentHeading.ABSTRACT.level in self.parents + else 1 + ) + abstract_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=self.abstract, + parent=abstract_item, + ) + self.abstract = "" + self.text = "" + elif name == self.Element.CLAIM_TEXT.value: + if text: + self.claim += self.text.strip("\n") + self.text = "" + + elif name == self.Element.CLAIM.value: + claim = self.claim.strip() + if claim: + self.claims.append(claim) + self.claim = "" + + elif name == self.Element.CLAIMS.value and self.claims: + heading_text = PatentHeading.CLAIMS.value + heading_level = ( + PatentHeading.CLAIMS.level + if PatentHeading.CLAIMS.level in self.parents + else 1 + ) + claims_item = self.doc.add_heading( + heading_text, + level=heading_level, + parent=self.parents[heading_level], # type: ignore[arg-type] + ) + for text in self.claims: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, text=text, parent=claims_item + ) + + elif name in ( + self.Element.PARAGRAPH.value, + self.Element.HEADING.value, + ): + if text and self.Element.ABSTRACT.value in self.property: + self.abstract = (self.abstract + text) if self.abstract else text + elif text.strip(): + text = re.sub("\\s+", " ", text).strip() + if name == self.Element.HEADING.value: + self.parents[self.level + 1] = self.doc.add_heading( + text=text, + level=self.level, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.level += 1 + else: + self.doc.add_text( + label=DocItemLabel.PARAGRAPH, + text=text, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + self.text = "" + + elif name == self.Element.TABLE.value: + # set an empty table as placeholder + empty_table = TableData(num_rows=0, num_cols=0, table_cells=[]) + self.doc.add_table( + data=empty_table, + parent=self.parents[self.level], # type: ignore[arg-type] + ) + + def _apply_style(self, text: str, style_tag: str) -> str: + """Apply an HTML style to text. + + Args: + text: A string containing plain text. + style_tag: An HTML tag name for styling text. If the tag name is not + recognized as one of the supported styles, the method will return + the original `text`. + + Returns: + A string after applying the style. + """ + formatted = html.unescape(text) + + if style_tag == self.Element.STYLE_SUPERSCRIPT.value: + formatted = html.unescape(self.style_html.get_superscript(formatted)) + elif style_tag == self.Element.STYLE_SUBSCRIPT.value: + formatted = html.unescape(self.style_html.get_subscript(formatted)) + + return formatted + + def _clean_data(self): + """Reset the variables from stream data.""" + self.property = [] + self.abstract = "" + self.claim = "" + self.claims = [] + self.text = "" + + +class XmlTable: + """Provide a table parser for xml tables in USPTO patent documents. + + The OASIS Open XML Exchange Table Model can be downloaded from: + http://oasis-open.org/specs/soextblx.dtd + """ + + class MinColInfoType(TypedDict): + offset: list[int] + colwidth: list[int] + + class ColInfoType(MinColInfoType): + cell_range: list[int] + cell_offst: list[int] + + def __init__(self, input: str) -> None: + """Initialize the table parser with the xml content. + + Args: + input: The xml content. + """ + self.max_nbr_messages = 2 + self.nbr_messages = 0 + self.empty_text = "" + self._soup = BeautifulSoup(input, features="xml") + + def _create_tg_range(self, tgs: list[dict[str, Any]]) -> dict[int, ColInfoType]: + """Create a unified range along the table groups. + + Args: + tgs: Table group column specifications. + + Returns: + Unified group column specifications. + """ + colinfo: dict[int, XmlTable.ColInfoType] = {} + + if len(tgs) == 0: + return colinfo + + for itg, tg in enumerate(tgs): + colinfo[itg] = { + "offset": [], + "colwidth": [], + "cell_range": [], + "cell_offst": [0], + } + offst = 0 + for info in tg["colinfo"]: + cw = info["colwidth"] + cw = re.sub("pt", "", cw, flags=re.I) + cw = re.sub("mm", "", cw, flags=re.I) + try: + cw = int(cw) + except BaseException: + cw = float(cw) + colinfo[itg]["colwidth"].append(cw) + colinfo[itg]["offset"].append(offst) + offst += cw + colinfo[itg]["offset"].append(offst) + + min_colinfo: XmlTable.MinColInfoType = {"offset": [], "colwidth": []} + + min_colinfo["offset"] = colinfo[0]["offset"] + offset_w0 = [] + for itg, col in colinfo.items(): + # keep track of col with 0 width + for ic, cw in enumerate(col["colwidth"]): + if cw == 0: + offset_w0.append(col["offset"][ic]) + + min_colinfo["offset"] = sorted( + list(set(col["offset"] + min_colinfo["offset"])) + ) + + # add back the 0 width cols to offset list + offset_w0 = list(set(offset_w0)) + min_colinfo["offset"] = sorted(min_colinfo["offset"] + offset_w0) + + for i in range(len(min_colinfo["offset"]) - 1): + min_colinfo["colwidth"].append( + min_colinfo["offset"][i + 1] - min_colinfo["offset"][i] + ) + + for itg, col in colinfo.items(): + i = 1 + range_ = 1 + for min_i in range(1, len(min_colinfo["offset"])): + min_offst = min_colinfo["offset"][min_i] + offst = col["offset"][i] + if min_offst == offst: + if ( + len(col["offset"]) == i + 1 + and len(min_colinfo["offset"]) > min_i + 1 + ): + range_ += 1 + else: + col["cell_range"].append(range_) + col["cell_offst"].append(col["cell_offst"][-1] + range_) + range_ = 1 + i += 1 + elif min_offst < offst: + range_ += 1 + else: + _log.debug("A USPTO XML table has wrong offsets.") + return {} + + return colinfo + + def _get_max_ncols(self, tgs_info: dict[int, ColInfoType]) -> NonNegativeInt: + """Get the maximum number of columns across table groups. + + Args: + tgs_info: Unified group column specifications. + + Return: + The maximum number of columns. + """ + ncols_max = 0 + for rowinfo in tgs_info.values(): + ncols_max = max(ncols_max, len(rowinfo["colwidth"])) + + return ncols_max + + def _parse_table(self, table: Tag) -> TableData: + """Parse the content of a table tag. + + Args: + The table element. + + Returns: + A docling table object. + """ + tgs_align = [] + tg_secs = table.find_all("tgroup") + if tg_secs: + for tg_sec in tg_secs: + ncols = tg_sec.get("cols", None) + if ncols: + ncols = int(ncols) + tg_align = {"ncols": ncols, "colinfo": []} + cs_secs = tg_sec.find_all("colspec") + if cs_secs: + for cs_sec in cs_secs: + colname = cs_sec.get("colname", None) + colwidth = cs_sec.get("colwidth", None) + tg_align["colinfo"].append( + {"colname": colname, "colwidth": colwidth} + ) + + tgs_align.append(tg_align) + + # create unified range along the table groups + tgs_range = self._create_tg_range(tgs_align) + + # if the structure is broken, return an empty table + if not tgs_range: + dl_table = TableData(num_rows=0, num_cols=0, table_cells=[]) + return dl_table + + ncols_max = self._get_max_ncols(tgs_range) + + # extract table data + table_data: list[TableCell] = [] + i_row_global = 0 + is_row_empty: bool = True + tg_secs = table.find_all("tgroup") + if tg_secs: + for itg, tg_sec in enumerate(tg_secs): + tg_range = tgs_range[itg] + row_secs = tg_sec.find_all(["row", "tr"]) + + if row_secs: + for row_sec in row_secs: + entry_secs = row_sec.find_all(["entry", "td"]) + is_header: bool = row_sec.parent.name in ["thead"] + + ncols = 0 + local_row: list[TableCell] = [] + is_row_empty = True + if entry_secs: + wrong_nbr_cols = False + for ientry, entry_sec in enumerate(entry_secs): + text = entry_sec.get_text().strip() + + # start-end + namest = entry_sec.attrs.get("namest", None) + nameend = entry_sec.attrs.get("nameend", None) + if isinstance(namest, str) and namest.isnumeric(): + namest = int(namest) + else: + namest = ientry + 1 + if isinstance(nameend, str) and nameend.isnumeric(): + nameend = int(nameend) + shift = 0 + else: + nameend = ientry + 2 + shift = 1 + + if nameend > len(tg_range["cell_offst"]): + wrong_nbr_cols = True + self.nbr_messages += 1 + if self.nbr_messages <= self.max_nbr_messages: + _log.debug( + "USPTO table has # entries != # columns" + ) + break + + range_ = [ + tg_range["cell_offst"][namest - 1], + tg_range["cell_offst"][nameend - 1] - shift, + ] + + # add row and replicate cell if needed + cell_text = text if text else self.empty_text + if cell_text != self.empty_text: + is_row_empty = False + for irep in range(range_[0], range_[1] + 1): + ncols += 1 + local_row.append( + TableCell( + column_header=is_header, + text=cell_text, + start_row_offset_idx=i_row_global, + end_row_offset_idx=i_row_global + 1, + row_span=1, + start_col_offset_idx=range_[0], + end_col_offset_idx=range_[1] + 1, + col_span=range_[1] - range_[0] + 1, + ) + ) + + if wrong_nbr_cols: + # keep empty text, not to introduce noise + local_row = [] + ncols = 0 + + # add empty cell up to ncols_max + for irep in range(ncols, ncols_max): + local_row.append( + TableCell( + column_header=is_header, + text=self.empty_text, + start_row_offset_idx=i_row_global, + end_row_offset_idx=i_row_global + 1, + row_span=1, + start_col_offset_idx=irep, + end_col_offset_idx=irep + 1, + col_span=1, + ) + ) + # do not add empty rows + if not is_row_empty: + table_data.extend(local_row) + i_row_global += 1 + + dl_table = TableData( + num_rows=i_row_global, num_cols=ncols_max, table_cells=table_data + ) + + return dl_table + + def parse(self) -> Optional[TableData]: + """Parse the first table from an xml content. + + Returns: + A docling table data. + """ + section = self._soup.find("table") + if section is not None: + table = self._parse_table(section) + if table.num_rows == 0 or table.num_cols == 0: + _log.warning("The parsed USPTO table is empty") + return table + else: + return None + + +class HtmlEntity: + """Provide utility functions to get the HTML entities of styled characters. + + This class has been developped from: + https://unicode-table.com/en/html-entities/ + https://www.w3.org/TR/WD-math-970515/table03.html + """ + + def __init__(self): + """Initialize this class by loading the HTML entity dictionaries.""" + self.superscript = str.maketrans( + { + "1": "¹", + "2": "²", + "3": "³", + "4": "⁴", + "5": "⁵", + "6": "⁶", + "7": "⁷", + "8": "⁸", + "9": "⁹", + "0": "⁰", + "+": "⁺", + "-": "⁻", + "−": "⁻", + "=": "⁼", + "(": "⁽", + ")": "⁾", + "a": "ª", + "o": "º", + "i": "ⁱ", + "n": "ⁿ", + } + ) + self.subscript = str.maketrans( + { + "1": "₁", + "2": "₂", + "3": "₃", + "4": "₄", + "5": "₅", + "6": "₆", + "7": "₇", + "8": "₈", + "9": "₉", + "0": "₀", + "+": "₊", + "-": "₋", + "−": "₋", + "=": "₌", + "(": "₍", + ")": "₎", + "a": "ₐ", + "e": "ₑ", + "o": "ₒ", + "x": "ₓ", + } + ) + self.mathematical_italic = str.maketrans( + { + "A": "𝐴", + "B": "𝐵", + "C": "𝐶", + "D": "𝐷", + "E": "𝐸", + "F": "𝐹", + "G": "𝐺", + "H": "𝐻", + "I": "𝐼", + "J": "𝐽", + "K": "𝐾", + "L": "𝐿", + "M": "𝑀", + "N": "𝑁", + "O": "𝑂", + "P": "𝑃", + "Q": "𝑄", + "R": "𝑅", + "S": "𝑆", + "T": "𝑇", + "U": "𝑈", + "V": "𝑉", + "W": "𝑊", + "Y": "𝑌", + "Z": "𝑍", + "a": "𝑎", + "b": "𝑏", + "c": "𝑐", + "d": "𝑑", + "e": "𝑒", + "f": "𝑓", + "g": "𝑔", + "h": "𝑕", + "i": "𝑖", + "j": "𝑗", + "k": "𝑘", + "l": "𝑙", + "m": "𝑚", + "n": "𝑛", + "o": "𝑜", + "p": "𝑝", + "q": "𝑞", + "r": "𝑟", + "s": "𝑠", + "t": "𝑡", + "u": "𝑢", + "v": "𝑣", + "w": "𝑤", + "x": "𝑥", + "y": "𝑦", + "z": "𝑧", + } + ) + + self.lookup_iso8879 = { + "&Agr;": "Α", + "&Bgr;": "Β", + "&Ggr;": "Γ", + "&Dgr;": "Δ", + "&Egr;": "Ε", + "&Zgr;": "Ζ", + "&EEgr;": "Η", + "&THgr;": "Θ", + "&Igr;": "Ι", + "&Kgr;": "Κ", + "&Lgr;": "Λ", + "&Mgr;": "Μ", + "&Ngr;": "Ν", + "&Xgr;": "Ξ", + "&Ogr;": "Ο", + "&Pgr;": "Π", + "&Rgr;": "Ρ", + "&Sgr;": "Σ", + "&Tgr;": "Τ", + "&Ugr;": "Υ", + "&PHgr;": "Φ", + "&KHgr;": "Χ", + "&PSgr;": "Ψ", + "&OHgr;": "Ω", + "&agr;": "α", + "&bgr;": "β", + "&ggr;": "γ", + "&dgr;": "δ", + "&egr;": "ε", + "&zgr;": "ζ", + "&eegr;": "η", + "&thgr;": "θ", + "&igr;": "ι", + "&kgr;": "κ", + "&lgr;": "λ", + "&mgr;": "μ", + "&ngr;": "ν", + "&xgr;": "ξ", + "&ogr;": "ο", + "&pgr;": "π", + "&rgr;": "ρ", + "&sgr;": "ς", + "&tgr;": "τ", + "&ugr;": "υ", + "&phgr;": "φ", + "&khgr;": "χ", + "&psgr;": "ψ", + "&ohgr;": "ω", + } + + def get_superscript(self, text: str) -> str: + """Get a text in superscript as HTML entities. + + Args: + text: The text to transform. + + Returns: + The text in superscript as HTML entities. + """ + return text.translate(self.superscript) + + def get_subscript(self, text: str) -> str: + """Get a text in subscript as HTML entities. + + Args: + The text to transform. + + Returns: + The text in subscript as HTML entities. + """ + return text.translate(self.subscript) + + def get_math_italic(self, text: str) -> str: + """Get a text in italic as HTML entities. + + Args: + The text to transform. + + Returns: + The text in italics as HTML entities. + """ + return text.translate(self.mathematical_italic) + + def get_greek_from_iso8879(self, text: str) -> str: + """Get an HTML entity of a greek letter in ISO 8879. + + Args: + The text to transform, as an ISO 8879 entitiy. + + Returns: + The HTML entity representing a greek letter. If the input text is not + supported, the original text is returned. + """ + return self.lookup_iso8879.get(text, text) diff --git a/docling/datamodel/base_models.py b/docling/datamodel/base_models.py index dd6291ab..bbd1a3ed 100644 --- a/docling/datamodel/base_models.py +++ b/docling/datamodel/base_models.py @@ -1,4 +1,4 @@ -from enum import Enum, auto +from enum import Enum from typing import TYPE_CHECKING, Dict, List, Optional, Union from docling_core.types.doc import ( @@ -28,6 +28,8 @@ class ConversionStatus(str, Enum): class InputFormat(str, Enum): + """A document format supported by document backend parsers.""" + DOCX = "docx" PPTX = "pptx" HTML = "html" @@ -36,6 +38,7 @@ class InputFormat(str, Enum): ASCIIDOC = "asciidoc" MD = "md" XLSX = "xlsx" + XML_USPTO = "xml_uspto" class OutputFormat(str, Enum): @@ -55,6 +58,7 @@ class OutputFormat(str, Enum): InputFormat.IMAGE: ["jpg", "jpeg", "png", "tif", "tiff", "bmp"], InputFormat.ASCIIDOC: ["adoc", "asciidoc", "asc"], InputFormat.XLSX: ["xlsx"], + InputFormat.XML_USPTO: ["xml", "txt"], } FormatToMimeType: Dict[InputFormat, List[str]] = { @@ -81,10 +85,13 @@ class OutputFormat(str, Enum): InputFormat.XLSX: [ "application/vnd.openxmlformats-officedocument.spreadsheetml.sheet" ], + InputFormat.XML_USPTO: ["application/xml", "text/plain"], } -MimeTypeToFormat = { - mime: fmt for fmt, mimes in FormatToMimeType.items() for mime in mimes +MimeTypeToFormat: dict[str, list[InputFormat]] = { + mime: [fmt for fmt in FormatToMimeType if mime in FormatToMimeType[fmt]] + for value in FormatToMimeType.values() + for mime in value } diff --git a/docling/datamodel/document.py b/docling/datamodel/document.py index f8dec5cb..5f6e5ec3 100644 --- a/docling/datamodel/document.py +++ b/docling/datamodel/document.py @@ -3,7 +3,17 @@ from enum import Enum from io import BytesIO from pathlib import Path, PurePath -from typing import TYPE_CHECKING, Dict, Iterable, List, Optional, Set, Type, Union +from typing import ( + TYPE_CHECKING, + Dict, + Iterable, + List, + Literal, + Optional, + Set, + Type, + Union, +) import filetype from docling_core.types.doc import ( @@ -235,7 +245,7 @@ def docs( if isinstance(obj, Path): yield InputDocument( path_or_stream=obj, - format=format, + format=format, # type: ignore[arg-type] filename=obj.name, limits=self.limits, backend=backend, @@ -243,7 +253,7 @@ def docs( elif isinstance(obj, DocumentStream): yield InputDocument( path_or_stream=obj.stream, - format=format, + format=format, # type: ignore[arg-type] filename=obj.name, limits=self.limits, backend=backend, @@ -251,15 +261,15 @@ def docs( else: raise RuntimeError(f"Unexpected obj type in iterator: {type(obj)}") - def _guess_format(self, obj: Union[Path, DocumentStream]): + def _guess_format(self, obj: Union[Path, DocumentStream]) -> Optional[InputFormat]: content = b"" # empty binary blob - format = None + formats: list[InputFormat] = [] if isinstance(obj, Path): mime = filetype.guess_mime(str(obj)) if mime is None: ext = obj.suffix[1:] - mime = self._mime_from_extension(ext) + mime = _DocumentConversionInput._mime_from_extension(ext) if mime is None: # must guess from with obj.open("rb") as f: content = f.read(1024) # Read first 1KB @@ -274,15 +284,53 @@ def _guess_format(self, obj: Union[Path, DocumentStream]): if ("." in obj.name and not obj.name.startswith(".")) else "" ) - mime = self._mime_from_extension(ext) + mime = _DocumentConversionInput._mime_from_extension(ext) - mime = mime or self._detect_html_xhtml(content) + mime = mime or _DocumentConversionInput._detect_html_xhtml(content) mime = mime or "text/plain" + formats = MimeTypeToFormat.get(mime, []) + if formats: + # TODO: remove application/xml case after adding another XML parse + if len(formats) == 1 and mime not in ("text/plain", "application/xml"): + return formats[0] + else: # ambiguity in formats + return _DocumentConversionInput._guess_from_content( + content, mime, formats + ) + else: + return None + + @staticmethod + def _guess_from_content( + content: bytes, mime: str, formats: list[InputFormat] + ) -> Optional[InputFormat]: + """Guess the input format of a document by checking part of its content.""" + input_format: Optional[InputFormat] = None + content_str = content.decode("utf-8") + + if mime == "application/xml": + match_doctype = re.search(r"]+>", content_str) + if match_doctype: + xml_doctype = match_doctype.group() + if InputFormat.XML_USPTO in formats and any( + item in xml_doctype + for item in ( + "us-patent-application-v4", + "us-patent-grant-v4", + "us-grant-025", + "patent-application-publication", + ) + ): + input_format = InputFormat.XML_USPTO + + elif mime == "text/plain": + if InputFormat.XML_USPTO in formats and content_str.startswith("PATN\r\n"): + input_format = InputFormat.XML_USPTO - format = MimeTypeToFormat.get(mime) - return format + return input_format - def _mime_from_extension(self, ext): + @staticmethod + def _mime_from_extension(ext): mime = None if ext in FormatToExtensions[InputFormat.ASCIIDOC]: mime = FormatToMimeType[InputFormat.ASCIIDOC][0] @@ -293,7 +341,19 @@ def _mime_from_extension(self, ext): return mime - def _detect_html_xhtml(self, content): + @staticmethod + def _detect_html_xhtml( + content: bytes, + ) -> Optional[Literal["application/xhtml+xml", "application/xml", "text/html"]]: + """Guess the mime type of an XHTML, HTML, or XML file from its content. + + Args: + content: A short piece of a document from its beginning. + + Returns: + The mime type of an XHTML, HTML, or XML file, or None if the content does + not match any of these formats. + """ content_str = content.decode("ascii", errors="ignore").lower() # Remove XML comments content_str = re.sub(r"", "", content_str, flags=re.DOTALL) @@ -302,6 +362,8 @@ def _detect_html_xhtml(self, content): if re.match(r"<\?xml", content_str): if "xhtml" in content_str[:1000]: return "application/xhtml+xml" + else: + return "application/xml" if re.match(r" FormatOption: InputFormat.HTML: FormatOption( pipeline_cls=SimplePipeline, backend=HTMLDocumentBackend ), + InputFormat.XML_USPTO: FormatOption( + pipeline_cls=SimplePipeline, backend=PatentUsptoDocumentBackend + ), InputFormat.IMAGE: FormatOption( pipeline_cls=StandardPdfPipeline, backend=DoclingParseV2DocumentBackend ), diff --git a/tests/data/groundtruth/docling_v2/ipa20180000016.itxt b/tests/data/groundtruth/docling_v2/ipa20180000016.itxt new file mode 100644 index 00000000..725205db --- /dev/null +++ b/tests/data/groundtruth/docling_v2/ipa20180000016.itxt @@ -0,0 +1,185 @@ +item-0 at level 0: unspecified: group _root_ + item-1 at level 1: title: LIGHT EMITTING DEVICE AND PLANT CULTIVATION METHOD + item-2 at level 2: section_header: ABSTRACT + item-3 at level 3: paragraph: Provided is a light emitting device that includes a light emitting element having a light emission peak wavelength ranging from 380 nm to 490 nm, and a fluorescent material excited by light from the light emitting element and emitting light having at a light emission peak wavelength ranging from 580 nm or more to less than 680 nm. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B ranging from 2.0 to 4.0 and a ratio R/FR of the photon flux density R to a photon flux density FR ranging from 0.7 to 13.0, the photon flux density R being in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B being in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR being in a wavelength range of 700 nm or more and 780 nm or less. + item-4 at level 2: section_header: CROSS-REFERENCE TO RELATED APPLICATION + item-5 at level 3: paragraph: The application claims benefit of Japanese Patent Application No. 2016-128835 filed on Jun. 29, 2016, the entire disclosure of which is hereby incorporated by reference in its entirety. + item-6 at level 2: section_header: BACKGROUND + item-7 at level 2: section_header: Technical Field + item-8 at level 3: paragraph: The present disclosure relates to a light emitting device and a plant cultivation method. + item-9 at level 2: section_header: Description of Related Art + item-10 at level 3: paragraph: With environmental changes due to climate change and other artificial disruptions, plant factories are expected to increase production efficiency of vegetables and be capable of adjusting production in order to make it possible to stably supply vegetables. Plant factories that are capable of artificial management can stably supply clean and safe vegetables to markets, and therefore are expected to be the next-generation industries. + item-11 at level 3: paragraph: Plant factories that are completely isolated from external environment make it possible to artificially control and collect various data such as growth method, growth rate data, yield data, depending on classification of plants. Based on those data, plant factories are able to plan production according to the balance between supply and demand in markets, and supply plants such as vegetables without depending on surrounding conditions such as climatic environment. Particularly, an increase in food production is indispensable with world population growth. If plants can be systematically produced without the influence by surrounding conditions such as climatic environment, vegetables produced in plant factories can be stably supplied within a country, and additionally can be exported abroad as viable products. + item-12 at level 3: paragraph: In general, vegetables that are grown outdoors get sunlight, grow while conducting photosynthesis, and are gathered. On the other hand, vegetables that are grown in plant factories are required to be harvested in a short period of time, or are required to grow in larger than normal sizes even in an ordinary growth period. + item-13 at level 3: paragraph: In plant factories, the light source used in place of sunlight affect a growth period, growth of plants. LED lighting is being used in place of conventional fluorescent lamps, from a standpoint of power consumption reduction. + item-14 at level 3: paragraph: For example, Japanese Unexamined Patent Publication No. 2009-125007 discloses a plant growth method. In this method, the plants is irradiated with light emitted from a first LED light emitting element and/or a second LED light emitting element at predetermined timings using a lighting apparatus including the first LED light emitting element emitting light having a wavelength region of 625 to 690 nm and the second LED light emitting element emitting light having a wavelength region of 420 to 490 nm in order to emit lights having sufficient intensities and different wavelengths from each other. + item-15 at level 2: section_header: SUMMARY + item-16 at level 3: paragraph: However, even though plants are merely irradiated with lights having different wavelengths as in the plant growth method disclosed in Japanese Unexamined Patent Publication No. 2009-125007, the effect of promoting plant growth is not sufficient. Further improvement is required in promotion of plant growth. + item-17 at level 3: paragraph: Accordingly, an object of the present disclosure is to provide a light emitting device capable of promoting growth of plants and a plant cultivation method. + item-18 at level 3: paragraph: Means for solving the above problems are as follows, and the present disclosure includes the following embodiments. + item-19 at level 3: paragraph: A first embodiment of the present disclosure is a light emitting device including a light emitting element having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less, and a fluorescent material that is excited by light from the light emitting element and emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of a photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less. + item-20 at level 3: paragraph: A second embodiment of the present disclosure is a plant cultivation method including irradiating plants with light from the light emitting device. + item-21 at level 3: paragraph: According to embodiments of the present disclosure, a light emitting device capable of promoting growth of plants and a plant cultivation method can be provided. + item-22 at level 2: section_header: BRIEF DESCRIPTION OF THE DRAWINGS + item-23 at level 3: paragraph: FIG. 1 is a schematic cross sectional view of a light emitting device according to an embodiment of the present disclosure. + item-24 at level 3: paragraph: FIG. 2 is a diagram showing spectra of wavelengths and relative photon flux densities of exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting devices. + item-25 at level 3: paragraph: FIG. 3 is a graph showing fresh weight (edible part) at the harvest time of each plant grown by irradiating the plant with light from exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting device. + item-26 at level 3: paragraph: FIG. 4 is a graph showing nitrate nitrogen content in each plant grown by irradiating the plant with light from exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting device. + item-27 at level 2: section_header: DETAILED DESCRIPTION + item-28 at level 3: paragraph: A light emitting device and a plant cultivation method according to the present invention will be described below based on an embodiment. However, the embodiment described below only exemplifies the technical concept of the present invention, and the present invention is not limited to the light emitting device and plant cultivation method described below. In the present specification, the relationship between the color name and the chromaticity coordinate, the relationship between the wavelength range of light and the color name of monochromatic light follows JIS Z8110. + item-29 at level 3: section_header: Light Emitting Device + item-30 at level 4: paragraph: An embodiment of the present disclosure is a light emitting device including a light emitting element having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less (hereinafter sometimes referred to as a “region of from near ultraviolet to blue color”), and a first fluorescent material emitting light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by being excited by light from the light emitting element. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of the photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less. + item-31 at level 4: paragraph: An example of the light emitting device according to one embodiment of the present disclosure is described below based on the drawings. FIG. 1 is a schematic cross sectional view showing a light emitting device 100 according to an embodiment of the present disclosure. + item-32 at level 4: paragraph: The light emitting device 100 includes a molded article 40, a light emitting element 10 and a fluorescent member 50, as shown in FIG. 1. The molded article 40 includes a first lead 20 and a second lead 30 that are integrally molded with a resin portion 42 containing a thermoplastic resin or a thermosetting resin. The molded article 40 forms a depression having a bottom and sides, and the light emitting element 10 is placed on the bottom of the depression. The light emitting element 10 has a pair of an anode and a cathode, and the anode and the cathode are electrically connected to the first lead 20 and the second lead 30 respectively through the respective wires 60. The light emitting element 10 is covered with the fluorescent member 50. The fluorescent member 50 includes, for example, a fluorescent material 70 performing wavelength conversion of light from the light emitting element 10, and a resin. The fluorescent material 70 includes a first fluorescent material 71 and a second fluorescent material 72. A part of the first lead 20 and the second lead 30 that are connected to a pair of the anode and the cathode of the light emitting element 10 is exposed toward outside a package constituting the light emitting element 100. The light emitting device 100 can emit light by receiving electric power supply from the outside through the first lead 20 and the second lead 30. + item-33 at level 4: paragraph: The fluorescent member 50 not only performs wavelength conversion of light emitted from the light emitting element 10, but functions as a member for protecting the light emitting element 10 from the external environment. In FIG. 1, the fluorescent material 70 is localized in the fluorescent member 50 in the state that the first fluorescent material 71 and the second fluorescent material 72 are mixed with each other, and is arranged adjacent to the light emitting element 10. This constitution can efficiently perform the wavelength conversion of light from the light emitting element 10 in the fluorescent material 70, and as a result, can provide a light emitting device having excellent light emission efficiency. The arrangement of the fluorescent member 50 containing the fluorescent material 70, and the light emitting element 10 is not limited to the embodiment that the fluorescent material 70 is arranged adjacent to the light emitting element 10 as shown in FIG. 1, and considering the influence of heat generated from the light emitting element 10, the fluorescent material 70 can be arranged separated from the light emitting element 10 in the fluorescent member 50. Furthermore, light having suppressed color unevenness can be emitted from the light emitting device 100 by arranging the fluorescent material 70 almost evenly in the fluorescent member 50. In FIG. 1, the fluorescent material 70 is arranged in the state that the first fluorescent material 71 and the second fluorescent material 72 are mixed with each other. However, for example, the first fluorescent material 71 may be arranged in a layer state and the second fluorescent material 72 may be arranged thereon in another layer state. Alternatively, the second fluorescent material 72 may be arranged in a layer state and the first fluorescent material 71 may be arranged thereon in another layer state. + item-34 at level 4: paragraph: The light emitting device 100 includes the first fluorescent material 71 having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by being excited by light from the light emitting element 10, and preferably further includes the second fluorescent material 72 having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by being excited by light from the light emitting element 10. + item-35 at level 4: paragraph: The first fluorescent material 71 and the second fluorescent material 72 are contained in, for example, the fluorescent member 50 covering the light emitting element 10. The light emitting device 100 in which the light emitting element 10 has been covered with the fluorescent member 50 containing the first fluorescent material 71 and the second fluorescent material 72 emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by a part of light emission of the light emitting element 10 that is absorbed in the first fluorescent material 71. Furthermore, the light emitting device 100 emits light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by a part of light emission of the light emitting element 10 that is absorbed in the second fluorescent material 72. + item-36 at level 4: paragraph: Plants grow when a pigment (chlorophyll a and chlorophyll b) present in chlorophyll thereof absorbs light and additionally takes carbon dioxide gas and water therein, and these are converted to carbohydrates (saccharides) by photosynthesis. Chlorophyll a and chlorophyll b used in growth promotion of plants particularly have absorption peaks in a red region of 625 nm or more and 675 nm or less and a blue region of 425 nm or more and 475 nm or less. The action of photosynthesis by chlorophylls of plants mainly occurs in a wavelength range of 400 nm or more and 700 nm or less, but chlorophyll a and chlorophyll b further have local absorption peaks in a region of 700 nm or more and 800 nm or less. + item-37 at level 4: paragraph: For example, when plants are irradiated with light having longer wavelength than and absorption peak (in the vicinity of 680 nm) in a red region of chlorophyll a, a phenomenon called red drop, in which activity of photosynthesis rapidly decreases, occurs. However, it is known that when plants are irradiated with light containing near infrared region together with light of red region, photosynthesis is accelerated by a synergistic effect of those two kinds of lights. This phenomenon is called the Emerson effect. + item-38 at level 4: paragraph: Intensity of light with which plants are irradiated is represented by photon flux density. The photon flux density (μmol·m⁻²·s⁻¹) is the number of photons reaching a unit area per unit time. The amount of photosynthesis depends on the number of photons, and therefore does not depend on other optical characteristics if the photon flux density is the same. However, wavelength dependency activating photosynthesis differs depending on photosynthetic pigment. Intensity of light necessary for photosynthesis of plants is sometimes represented by Photosynthetic Photon Flux Density (PPFD). + item-39 at level 4: paragraph: The light emitting device 100 emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of the photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m⁻²·g⁻¹) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less. + item-40 at level 4: paragraph: It is estimated that in plants, which are irradiated with light containing the photon flux density FR from the light emitting device 100, photosynthesis is activated by Emerson effect, and as a result, growth of plants can be promoted. Furthermore, when plants are irradiated with light containing the photon flux density FR, growth of the plants can be promoted by a reversible reaction between red light irradiation, to which chlorophyll as chromoprotein contained in plants has participated, and far infrared light irradiation. + item-41 at level 4: paragraph: Examples of nutrients necessary for growth of plants include nitrogen, phosphoric acid, and potassium. Of those nutrients, nitrogen is absorbed in plants as nitrate nitrogen (nitrate ion: NO₃⁻). The nitrate nitrogen changes into nitrite ion (NO₂⁻) by a reduction reaction, and when the nitrite ion is further reacted with fatty acid amine, nitrosoamine is formed. It is known that nitrite ion acts to hemoglobin in blood, and it is known that a nitroso compound sometimes affects health of a human body. Mechanism of converting nitrate nitrogen into nitrite ion in vivo is complicated, and the relationship between the amount of intake of nitrate nitrogen and the influence to health of a human body is not clarified. However, it is desired that the content of nitrate nitrogen having a possibility of affecting health of a human body is smaller. + item-42 at level 4: paragraph: For the above reasons, nitrogen is one of nutrients necessary for growth of plants, but it is preferred that the content of nitrate nitrogen in food plants be reduced to a range that does not disturb the growth of plants. + item-43 at level 4: paragraph: It is preferred that the light emitting device 100 further include the second fluorescent material 72 having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by being excited by light from the light emitting element 10, wherein the R/FR ratio is within a range of 0.7 or more and 5.0 or less. The R/FR ratio is more preferably within a range of 0.7 or more and 2.0 or less. + item-44 at level 3: section_header: Light Emitting Element + item-45 at level 4: paragraph: The light emitting element 10 is used as an excitation light source, and is a light emitting element emitting light having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less. As a result, a stable light emitting device having high efficiency, high linearity of output to input and strong mechanical impacts can be obtained. + item-46 at level 4: paragraph: The range of the light emission peak wavelength of the light emitting element 10 is preferably in a range of 390 nm or more and 480 nm or less, more preferably in a range of 420 nm or more and 470 nm or less, and still more preferably in a range of 440 nm or more and 460 nm or less, and particularly preferably in a range of 445 nm or more and 455 nm or less. A light emitting element including a nitride semiconductor (InₓAlyGa₁₋ₓ₋yN, 0≦X, 0≦Y and X+Y≦1) is preferably used as the light emitting element 10. + item-47 at level 4: paragraph: The half value width of emission spectrum of the light emitting element 10 can be, for example, 30 nm or less. + item-48 at level 3: section_header: Fluorescent Member + item-49 at level 4: paragraph: The fluorescent member 50 used in the light emitting device 100 preferably includes the first fluorescent material 71 and a sealing material, and more preferably further includes the second fluorescent material 72. A thermoplastic resin and a thermosetting resin can be used as the sealing material. The fluorescent member 50 may contain other components such as a filler, a light stabilizer and a colorant, in addition to the fluorescent material and the sealing material. Examples of the filler include silica, barium titanate, titanium oxide and aluminum oxide. + item-50 at level 4: paragraph: The content of other components other than the fluorescent material 70 and the sealing material in the fluorescent member 50 is preferably in a range of 0.01 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the sealing material. + item-51 at level 4: paragraph: The total content of the fluorescent material 70 in the fluorescent member 50 can be, for example, 5 parts by mass or more and 300 parts by mass or less, per 100 parts by mass of the sealing material. The total content is preferably 10 parts by mass or more and 250 parts by mass or less, more preferably 15 parts by mass or more and 230 parts by mass or less, and still more preferably 15 parts by mass or more and 200 parts by mass or less. When the total content of the fluorescent material 70 in the fluorescent member 50 is within the above range, the light emitted from the light emitting element 10 can be efficiently subjected to wavelength conversion in the fluorescent material 70. + item-52 at level 3: section_header: First Fluorescent Material + item-53 at level 4: paragraph: The first fluorescent material 71 is a fluorescent material that is excited by light from the light emitting element 10 and emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm. Examples of the first fluorescent material 71 include an Mn⁴⁺-activated fluorogermanate fluorescent material, an Eu²⁺-activated nitride fluorescent material, an Eu²⁺-activated alkaline earth sulfide fluorescent material and an Mn⁴⁺-activated halide fluorescent material. The first fluorescent material 71 may use one selected from those fluorescent materials and may use a combination of two or more thereof. The first fluorescent material preferably contains an Eu²⁺-activated nitride fluorescent material and an Mn⁴⁺-activated fluorogermanate fluorescent material. + item-54 at level 4: paragraph: The Eu²⁺-activated nitride fluorescent material is preferably a fluorescent material that has a composition including at least one element selected from Sr and Ca, and Al and contains silicon nitride that is activated by Eu²⁺, or a fluorescent material that has a composition including at least one element selected from the group consisting of alkaline earth metal elements and at least one element selected from the group consisting of alkali metal elements and contains aluminum nitride that is activated by Eu²⁺. + item-55 at level 4: paragraph: The halide fluorescent material that is activated by Mn⁴⁺ is preferably a fluorescent material that has a composition including at least one element or ion selected from the group consisting of alkali metal elements and an ammonium ion (NH⁴⁺) and at least one element selected from the group consisting of Group 4 elements and Group 14 elements and contains a fluoride that is activated by Mn⁴⁺. + item-56 at level 4: paragraph: Examples of the first fluorescent material 71 specifically include fluorescent materials having any one composition of the following formulae (I) to (VI). + item-57 at level 4: paragraph: (i−j)MgO.(j/2)Sc₂O₃.kMgF₂.mCaF₂.(1−n)GeO₂.(n/2)Mt₂O₃:zMn⁴⁺ (I) + item-58 at level 4: paragraph: wherein Mt is at least one selected from the group consisting of Al, Ga, and In, and j, k, m, n, and z are numbers satisfying 2≦i≦4, 0≦j<0.5, 0 + + + + + +US +20110039701 +A1 +20110217 + + + + +US +12750336 +20100330 + + +12 + + +EP +08166352.8 +20081010 + + + + +20060101 +A +
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+ + + + + + +Bayer CropScience AG +03 +
+Monheim +DE +
+ + + + + +

The invention relates to novel compounds of the formula (I)

+

+embedded image + +

+

in which X, Y, Z, A, B and G have the meanings given above, +
+to a plurality of processes and intermediates for their preparation and to their use as pesticides and/or herbicides. +

+

Moreover, the invention relates to selective herbicidal compositions comprising, firstly, the phenyl-substituted bicyclooctane-1,3-dione derivates 33 and, secondly, a crop plant compatibility-improving compound.

+

The present invention furthermore relates to increasing the activity of crop protection compositions comprising in particular phenyl-substituted bicyclooctane-1,3-dione derivates by adding ammonium salts or phosphonium salts and, if appropriate, penetrants, to the corresponding compositions, to processes for their preparation and to their use in crop protection as insecticides and/or acaricides and/or for preventing unwanted plant growth.

+ + + +

The present invention relates to novel phenyl-substituted bicyclooctane-1,3-dione derivatives, to a plurality of processes for their preparation and to their use as pesticides and/or herbicides.

+

Moreover, the invention relates to novel selective herbicidal active compound combinations comprising, firstly, phenyl-substituted bicyclooctane-1,3-dione derivates and, secondly, at least one crop plant compatibility-improving compound, which combinations can be used with particularly good results for the selective control of weeds and various crops of useful plants.

+

The present invention furthermore relates to increasing the activity of crop protection compositions comprising in particular phenyl-substituted bicyclooctane-1,3-dione derivates by adding ammonium salts or phosphonium salts and, if appropriate, penetrants, to the corresponding compositions, to processes for their preparation and to their use in crop protection as insecticides and/or for preventing unwanted plant growth.

+

It is known that certain substituted 2-arylcyclopentanediones have herbicidal, insecticidal and acaricidal properties (cf., for example, U.S. Pat. Nos. 4,283,348; 4,338,122; 4,436,666; 4,526,723; 4,551,547; 4,632,698; WO 96/01 798; WO 96/03 366, WO 97/14 667 and also WO 98/39281, WO 99/43649, WO99/48869, WO 99/55673, WO 01/17972, WO 01/74770, WO 03/062244, WO 04/080962, WO04/111042, WO05/092897, WO06/029799, WO07/080,066, WO07/096,058, WO 09/019,005 and WO 09/019,015). Also known are compounds which are substituted in a similar way: 3-hydroxy-5,5-dimethyl-2-phenylcyclopent-2-en-1-one from the publication Micklefield et. al., Tetrahedron, (1992), 7519-26 and the natural product Involution (−)-cis-5-(3,4-dihydroxyphenyl)-3,4-dihydroxy-2-(4-hydroxyphenyl)-cyclopent-2-enone from the publication Edwards et al., J. Chem. Soc. S, (1967), 405-9. An insecticidal or acaricidal action is not described. Moreover, 2-(2,4,6-trimethylphenyl)-1,3-indanedione is known from the publication J. Economic Entomology, 66 (1973), 584 and the laid-open publication DE-A 2 361 084, with herbicidal and acaricidal actions being stated.

+

However, in particular at low application rates and concentrations, the activity and activity spectrum of these compounds is not always fully satisfactory. Furthermore, the compatibility of these compounds with plants is not always sufficient.

+

This invention now provides novel compounds of the formula (I)

+

+embedded image + +

+

in which +

    +
  • X represents alkyl, cycloalkyl or alkoxy,
    • +
  • Y represents hydrogen, alkyl or alkoxy,
    • +
  • Z represents hydrogen, alkyl or cycloalkyl,
    • +
  • where
    • +
  • A and B together with the carbon atom to which they are attached represent a saturated or unsaturated unsubstituted or substituted cycle which optionally contains at least one heteroatom,
    • +
  • or
    • +
  • A and B together with the carbon atom to which they are attached represent a carbonyl group, a C1-C4-alkylene group or a ═N—OR9 group,
    • +
  • G represents hydrogen (a) or represents one of the groups
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • E represents a metal ion equivalent or an ammonium ion,
      • +
    • L represents oxygen or sulphur,
      • +
    • M represents oxygen or sulphur,
      • +
    +
    • +
  • R1 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl which may be interrupted by at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl,
    • +
  • R2 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl,
    • +
  • R3, R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio,
    • +
  • R6 and R7 independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted phenyl, represent optionally substituted benzyl, or together with the nitrogen atom to which they are attached represent a cycle which is optionally interrupted by oxygen or sulphur,
    • +
  • R9 represents hydrogen, represents in each case optionally substituted alkyl, cycloalkyl, CH2-cycloalkyl, alkenyl, alkinyl, arylalkyl or hetarylalkyl.
    • +
+

+

Depending inter alia on the nature of the substituents, the compounds of the formula (I) may be present as geometric and/or optical isomers or isomer mixtures of varying composition which, if appropriate, may be separated in a customary manner. The present invention provides both the pure isomers and the isomer mixtures, their preparation and use and compositions comprising them. However, for the sake of simplicity, hereinbelow only compounds of the formula (I) are referred to, although what is meant is both the pure compounds and, if appropriate, mixtures having various proportions of isomeric compounds.

+

Depending on the position of the substituent G, the compounds of the formula (I) can be present in the two isomeric forms of the formulae (I-A) and (I-B)

+

+embedded image + +

+

which is meant to be indicated by the broken line in formula (I).

+

The compounds of the formulae (I-A) and (I-B) can be present both as mixtures and in the form of their pure isomers. If appropriate, mixtures of the compounds of the formulae (I-A) and (I-B) can be separated by physical methods, for example by way of chromatographic methods.

+

For reasons of clarity, hereinbelow only one of the possible isomers is shown in each case. This does not exclude that, if appropriate, the compounds may be present in the form of the isomer mixtures or in the respective other isomeric form.

+

Including the different meanings (a), (b), (c), (d), (e), (f) and (g) of group G, the following principle structures (I-a) to (I-g) result:

+

+embedded image + + +embedded image + +

+

in which +
+A, B, E, L, M, X, Y, Z, R1, R2, R3, R4, R5, R6 and R7 have the meanings given above. +

+

A further form of stereoisomerism results from the cis-attachment of the two carbacyclic five-membered rings, namely in the case where specifically the two substituents A and B in formula (Ia) are not identical.

+

+embedded image + +

+

Hereinbelow, the isomers encountered in this case are referred to as “syn” and “anti”, respectively, depending on whether the substituent A or B to be prioritized according to the Cahn-Ingold-Prelog rules is in the anti- or syn-position to the cyclopentanedione ring. Two examples of such forms of isomerism in the compounds of the formula (I-a) are mentioned below:

+

+embedded image + +

+

Furthermore, it has been found that the novel compounds of the formula (I) are obtained by one of the processes described below: +

    +
  • (A) Compounds of the formula (I-a)
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • A, B, X, Y and Z have the meaning given above
      • +
    • are obtained when
      • +
    • ketocarboxylic esters of the formula (II)
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • A, B, X, Y and Z have the meaning given above and
      • +
    • R8 represents alkyl (in particular C1-C8-alkyl)
      • +
    • are cyclized intramolecularly, if appropriate in the presence of a diluent and in the presence of a base.
      • +
    +
    • +
+

+

Moreover, it has been found +

    +
  • (B) that the compounds of the formula (I-b) shown above in which A, B, R1, X, Y and Z have the meanings given above are obtained when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted
    • +
  • (α) with acid halides of the formula (III)
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • R1 has the meaning given above and
      • +
    • Hal represents halogen (in particular chlorine or bromine)
      • +
    • or
      • +
    +
    • +
  • (β) with carboxylic anhydrides of the formula (IV)
    • +
+

+

+
+R1—CO—O—CO—R1  (IV) +

    +
  • +
      +
    • in which
      • +
    • R1 has the meaning given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
      • +
    +
    • +
  • (C) that the compounds of the formula (I-c) shown above in which A, B, R2, M, X, Y and Z have the meanings given above and L represents oxygen are obtained when the compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted +
      +
    • with chloroformic esters or chloroformic thio esters of the formula (V)
      • +
    +
    • +
+

+

+
+R2-M-CO—Cl  (V) +

    +
  • +
      +
    • in which
      • +
    • R2 and M have the meanings given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
      • +
    +
    • +
  • (D) that compounds of the formula (I-c) shown above in which A, B, R2, M, X, Y and Z have the meanings given above and L represents sulphur are obtained when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted +
      +
    • with chloromonothioformic esters or chlordithioformic esters of the formula (VI)
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • M and R2 have the meanings given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder;
      • +
    +
    • +
  • (E) that compounds of the formula (I-d) shown above in which A, B, R3, X, Y and Z have the meanings given above are obtained when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted +
      +
    • with sulphonyl chlorides of the formula (VII)
      • +
    +
    • +
+

+

+
+R3—SO2—Cl  (VII) +

    +
  • +
      +
    • in which
      • +
    • R3 has the meaning given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
      • +
    +
    • +
  • (F) that compounds of the formula (I-e) shown above in which A, B, L, R4, R5, X, Y and Z have the meanings given above are obtained when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted +
      +
    • with phosphorus compounds of the formula (VIII)
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • L, R4 and R5 have the meanings given above and
      • +
    • Hal represents halogen (in particular chlorine or bromine),
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
      • +
    +
    • +
  • (G) that compounds of the formula (I-f) shown above in which A, B, E, X, Y and Z have the meanings given above are obtained when compounds of the formula (I-a) in which A, B, X, Y and Z have the meanings given above are in each case reacted +
      +
    • with metal compounds or amines of the formulae (IX) or (X), respectively
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • Me represents a mono- or divalent metal (preferably an alkali metal or alkaline earth metal, such as lithium, sodium, potassium, magnesium or calcium),
      • +
    • t represents the number 1 or 2 and
      • +
    • R10, R11, R12 independently of one another represent hydrogen or alkyl (preferably C1-C8-alkyl),
      • +
    • if appropriate in the presence of a diluent,
      • +
    +
    • +
  • (H) that compounds of the formula (I-g) shown above in which A, B, L, R6, R7, X, Y and Z have the meanings given above are obtained +
      +
    • when compounds of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given above are in each case reacted
      • +
    +
    • +
  • (α) with isocyanates or isothiocyanates of the formula (XI)
    • +
+

+

+
+R6—N═C=L  (XI) +

    +
  • +
      +
    • in which
      • +
    • R6 and L have the meanings given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or
      • +
    +
    • +
  • (β) with carbamoyl chlorides or thiocarbamoyl chlorides of the formula (XII)
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • L, R6 and R7 have the meanings given above,
      • +
    • if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.
      • +
    +
    • +
+

+

Furthermore, it has been found that the novel compounds of the formula (I) are very effective as pesticides, preferably as insecticides, acaricides and herbicides.

+

Surprisingly, it has now also been found that certain substituted cyclic ketoenoles, when used together with the crop plant compatibility-improving compounds (safener/antidotes) described below, efficiently prevent damage to the crop plants and can be used in a particularly advantageous manner as broad-spectrum combination preparations for the selective control of unwanted plants in crops of useful plants, such as, for example, in cereals, but also in maize, potatoes, soya beans and rice.

+

The invention also provides selective herbicidal compositions comprising an effective amount of an active compound combination comprising, as components, +

    +
  • a′) at least one compound of the formula (I), in which A, B, G, X, Y and Z have the meaning given above
    • +
  • and
    • +
  • (b′) at least one crop plant compatibility-improving compound (safener). +
      +
    • The safeners are preferably selected from the group consisting of:
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • S1) Compounds of the formula (S1)
      • +
    • where the symbols and indices have the following meanings:
      • +
    • nA is a natural number from 0 to 5, preferably from 0 to 3;
      • +
    • RA1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl;
      • +
    • WA is an unsubstituted or substituted divalent heterocyclic radical from the group consisting of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms from the group consisting of N and O, where at least one nitrogen atom and at most one oxygen atom is present in the ring, preferably a radical from the group consisting of (WA1) to (WA4),
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • mA is 0 or 1;
      • +
    • RA2 is ORA3, SRA3 or NRA3RA4 or a saturated or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is attached via the nitrogen atom to the carbonyl group in (S1) and which is unsubstituted or substituted by radicals from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy and optionally substituted phenyl, preferably a radical of the formula ORA3, NHRA4 or N(CH3)2, in particular of the formula ORA3;
      • +
    • RA3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical having preferably a total of 1 to 18 carbon atoms;
      • +
    • RA4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl;
      • +
    • RA5 is H, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C8)-alkyl, cyano or COORA9 where RA9 is hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C6)-hydroxyalkyl, (C3-C12)-cycloalkyl or tri-(C1-C4)-alkylsilyl;
      • +
    • RA6, RA7, RA8 are identical or different and are hydrogen, (C1-C8)-alkyl, (C1-C8)-haloalkyl, (C3-C12)-cycloalkyl or substituted or unsubstituted phenyl;
      • +
    • preferably:
      • +
    • a) compounds of the type of the dichlorophenylpyrazoline-3-carboxylic acid (S1a), preferably compounds such as 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylic acid, ethyl 1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate (S1-1) (“mefenpyr-diethyl”), and related compounds, as described in WO-A-91/07874;
      • +
    • b) derivatives of dichlorophenylpyrazolecarboxylic acid (S1b), preferably compounds such as ethyl 1-(2,4-dichloiophenyl)-5-methylpyrazole-3-carboxylate (S1-2), ethyl 1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (S1-3), ethyl 1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate (S1-4) and related compounds, as described in EP-A-333 131 and EP-A-269 806;
      • +
    • c) derivatives of 1,5-diphenylpyrazole-3-carboxylic acid (S1c), preferably compounds such as ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-5), methyl 1-(2-chlorophenyl)-5-phenylpyrazole-3-carboxylate (S1-6) and related compounds, as described, for example, in EP-A-268554;
      • +
    • d) compounds of the type of the triazolecarboxylic acids (S1d), preferably compounds such as fenchlorazole(-ethyl), i.e. ethyl 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate (S1-7), and related compounds, as described in EP-A-174 562 and EP-A-346 620;
      • +
    • e) compounds of the type of the 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or the 5,5-diphenyl-2-isoxazoline-3-carboxylic acid (S1c), preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (S1-8) or ethyl 5-phenyl-2-isoxazoline-3-carboxylate (S1-9) and related compounds, as described in WO-A-91/08202, or 5,5-diphenyl-2-isoxazolinecarboxylic acid (S1-10) or ethyl 5,5-diphenyl-2-isoxazolinecarboxylate (S1-11) (“isoxadifen-ethyl”) or n-propyl 5,5-diphenyl-2-isoxazolinecarboxylate (S1-12) or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (S1-13), as described in the patent application WO-A-95/07897.
      • +
    • S2) Quinoline derivatives of the formula (S2)
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • where the symbols and indices have the following meanings:
      • +
    • RB1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl;
      • +
    • nB is a natural number from 0 to 5, preferably from 0 to 3;
      • +
    • RB2 is ORB3, SRB3 or NRB3RB4 or a saturated +
        +
      • or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, preferably from the group consisting of O and S, which is attached via the nitrogen atom to the carbonyl group in (S2) and which is unsubstituted or substituted by radicals from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy and optionally substituted phenyl, preferably a radical of the formula ORB3, NHRB4 or N(CH3)2, in particular of the formula ORB3;
        • +
      +
      • +
    • RB3 is hydrogen or an unsubstituted or substituted aliphatic hydrocarbon radical having preferably a total of 1 to 18 carbon atoms;
      • +
    • RB4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl;
      • +
    • TB is a (C1- or C2)-alkanediyl chain which is unsubstituted or substituted by one or two (C1-C4)-alkyl radicals or by [(C1-C3)-alkoxy]carbonyl;
      • +
    • preferably:
      • +
    • a) compounds of the type of the 8-quinolinoxyacetic acid (S2a), preferably 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (“cloquintocet-mexyl”) (S2-1), 1,3-dimethyl-but-1-yl (5-chloro-8-quinolinoxy)acetate (S2-2), 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (S2-3), 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (S2-4), ethyl (5-chloro-8-quinolinoxy)acetate (S2-5), methyl (5-chloro-8-quinolinoxy)acetate (S2-6), allyl (5-chloro-8-quinolinoxy)acetate (S2-7), 2-(2-propylideneiminoxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate (S2-8), 2-oxo-prop-1-yl (5-chloro-8-quinolinoxy)acetate (S2-9) and related compounds, as described in EP-A-86 750, EP-A-94 349 and EP-A-191 736 or EP-A-0 492 366, and also (5-chloro-8-quinolinoxy)acetic acid (S2-10), its hydrates and salts, for example its lithium, sodium, potassium, calcium, magnesium, aluminium, iron, ammonium, quaternary ammonium, sulphonium or phosphonium salts, as described in WO-A-2002/34048;
      • +
    • b) compounds of the type of the (5-chloro-8-quinolinoxy)malonic acid (S2b), preferably compounds such as diethyl (5-chloro-8-quinolinoxy)malonate, diallyl (5-chloro-8-quinolinoxy)malonate, methyl ethyl (5-chloro-8-quinolinoxy)malonate and related compounds, as described in EP-A-0 582 198.
      • +
    • S3) Compounds of the formula (S3)
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • where the symbols and indices have the following meanings:
      • +
    • RC1 is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, (C3-C7)-cycloalkyl, preferably dichloromethyl;
      • +
    • RC2, RC3 are identical or different and are hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkylcarbamoyl-(C1-C4)-alkyl, (C2-C4)-alkenylcarbamoyl-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, dioxolanyl-(C1-C4)-alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or RC2 and RC3 together form a substituted or unsubstituted heterocyclic ring, preferably an oxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidine or benzoxazine ring;
      • +
    • preferably: +
        +
      • active compounds of the type of the dichloroacetamides which are frequently used as pre-emergence safeners (soil-acting safeners), such as, for example,
        • +
      • “dichlormid” (N,N-diallyl-2,2-dichloroacetamide) (S3-1),
        • +
      • “R-29148” (3-dichloroacetyl-2,2,5-trimethyl-1,3-oxazolidine) from Stauffer (S3-2),
        • +
      • “R-28725” (3-dichloroacetyl-2,2-dimethyl-1,3-oxazolidine) from Stauffer (S3-3),
        • +
      • “benoxacor” (4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine) (S3-4),
        • +
      • “PPG-1292” (N-allyl-N-[(1,3-dioxolan-2-yl)methyl]dichloroacetamide) from PPG Industries (S3-5),
        • +
      • “DKA-24” (N-allyl-N-[(allylaminocarbonyl)methyl]dichloroacetamide) from Sagro-Chem (S3-6),
        • +
      • “AD-67” or “MON 4660” (3-dichloroacetyl-1-oxa-3-azaspiro[4,5]decane) from Nitrokemia or Monsanto (S3-7),
        • +
      • “TI-35” (1-dichloroacetylazepane) from TRI-Chemical RT (S3-8)
        • +
      • “diclonon” (dicyclonon) or “BAS145138” or “LAB145138” (S3-9) (3-dichloroacetyl-2,5,5-trimethyl-1,3-diazabicyclo[4.3.0]nonane) from BASF,
        • +
      • “furilazole” or “MON 13900” ((RS)-3-dichloroacetyl-5-(2-furyl)-2,2-dimethyloxazolidine) (S3-10) and also its (R)-isomer (S3-11).
        • +
      +
      • +
    • S4) N-Acylsulphonamides of the formula (S4) and their salts
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • where the symbols and indices have the following meanings:
      • +
    • XD is CH or N;
      • +
    • RD1 is CO—NRD5RD6 or NHCO—RD7;
      • +
    • RD2 is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl;
      • +
    • RD3 is hydrogen, (C1-C4)-alkyl, (C1-C4)-alkenyl or (C2-C4)-alkynyl;
      • +
    • RD4 is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkyl-sulphinyl, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl;
      • +
    • RD5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl which contains vD heteroatoms from the group consisting of nitrogen, oxygen and sulphur, where the seven last-mentioned radicals are substituted by vD substituents from the group consisting of halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulphinyl, (C1-C2)-alkylsulphonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl and phenyl and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)-haloalkyl;
      • +
    • RD6 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, where the three last-mentioned radicals are substituted by vD radicals from the group consisting of halogen, hydroxy, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio, or
      • +
    • RD7 and RD6 together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical;
      • +
    • RD7 is hydrogen, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, where the 2 last-mentioned radicals are substituted by vD substituents from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy and (C1-C4)-alkylthio and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)-haloalkyl;
      • +
    • nD is 0, 1 or 2;
      • +
    • mD is 1 or 2;
      • +
    • vD is 0, 1, 2 or 3; +
      +from among these, preference is given to compounds of the type of the N-acylsulphonamides, for example of the formula (S4a) below, which are known, for example, from WO-A-97/4subchamber16 +
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • RD7 is (C1-C6)-alkyl, (C3-C6)-cycloalkyl, where the 2 last-mentioned radicals are substituted by vD substituents from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy and (C1-C4)-alkylthio and, in the case of cyclic radicals, also (C1-C4)-alkyl and (C1-C4)-haloalkyl;
      • +
    • RD4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3,
      • +
    • mD 1 or 2;
      • +
    • vD iso, 1, 2 or 3;
      • +
    • and also
      • +
    • acylsulphamoylbenzamides, for example of the formula (S4b) below, which are known, for example, from WO-A-99/16744,
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • for example those in which
      • +
    • RD5=cyclopropyl and (RD4)=2-OMe (“cyprosulfamide”, S4-1),
      • +
    • RD5=cyclopropyl and (RD4)=5-Cl-2-OMe (S4-2),
      • +
    • RD5=ethyl and (RD4)=2-OMe (S4-3),
      • +
    • RD5=isopropyl and (RD4)=5-Cl-2-OMe (S4-4) and
      • +
    • RD5=isopropyl and (RD4)=2-OMe (S4-5) +
      +and also +
      • +
    • compounds of the type of the N-acylsulphamoylphenylureas of the formula (S4c), which are known, for example, from EP-A-365484,
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • RD8 and RD9 independently of one another are hydrogen, (C1-C8)-alkyl, (C3-C8)-cycloalkyl, (C3-C6)-alkenyl, (C3-C6)-alkynyl,
      • +
    • RD4 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, CF3,
      • +
    • mD is 1 or 2;
      • +
    • for example
      • +
    +
    • +
  • 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3-methylurea,
    • +
  • 1-[4-(N-2-methoxybenzoylsulphamoyl)phenyl]-3,3-dimethylurea,
    • +
  • 1-[4-(N-4,5-dimethylbenzoyl sulphamoyl)phenyl]-3-methylurea +
      +
    • S5) Active compounds from the class of the hydroxyaromatics and aromatic-aliphatic carboxylic acid derivatives (S5), for example ethyl 3,4,5-triacetoxybenzoate, 3,5-dimethoxy-4-hydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 4-hydroxysalicylic acid, 4-fluorosalicyclic acid, 2-hydroxycinnamic acid, 1,2-dihydro-2-oxo-6-trifluoromethylpyridine-3-carboxamide, 2,4-dichlorocinnamic acid, as described in WO-A-2004/084631, WO-A-2005/015994, WO-A-2005/016001.
      • +
    • S6) Active compounds from the class of the 1,2-dihydroquinoxalin-2-ones (S6), for example 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, 1-methyl-3-(2-thienyl)-1,2-dihydroquinoxaline-2-thione, 1-(2-aminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one hydrochloride, 1-[2-(diethylamino)ethyl]-6,7-dimethyl-3-thiophen-2-ylquinoxalin-2(1H)-one, 1-(2-methylsulphonylaminoethyl)-3-(2-thienyl)-1,2-dihydroquinoxalin-2-one, as described in WO-A-2005/112630.
      • +
    • S7) Compounds of the formula (S7), as described in WO-A-1998/38856,
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • where the symbols and indices have the following meanings:
      • +
    • RE1, RE2 independently of one another are halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, nitro;
      • +
    • AE is COORE3 or COSRE4
      • +
    • RE3, RE4 independently of one another are hydrogen, (C1-C4)-alkyl, (C2-C6)-alkenyl, (C2-C4)-alkynyl, cyanoalkyl, (C1-C4)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or alkylammonium,
      • +
    • nE1 is 0 or 1;
      • +
    • nE2, nE3 independently of one another are 0, l or 2,
      • +
    • preferably: +
        +
      • diphenylmethoxyacetic acid,
        • +
      • ethyl diphenylmethoxyacetate,
        • +
      • methyl diphenylmethoxyacetate (CAS Reg. No.: 41858-19-9) (S7-1).
        • +
      +
      • +
    • S8) Compounds of the formula (S8), as described in WO-A-98/27049,
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • XF is CH or N,
      • +
    • nF is, if XF═N, an integer from 0 to 4 and
      • +
    • nF is, if XF═CH, an integer from 0 to 5,
      • +
    • RE1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkylthio, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl, optionally substituted phenyl, optionally substituted phenoxy,
      • +
    • RF2 is hydrogen or (C1-C4)-alkyl,
      • +
    • RF3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C1-C4)-alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; or salts thereof,
      • +
    • preferably compounds in which
      • +
    • XF is CH,
      • +
    • nF is an integer from 0 to 2,
      • +
    • RF1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy,
      • +
    • RF2 is hydrogen or (C1-C4)-alkyl,
      • +
    • RF3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, preferably by up to three, identical or different radicals from the group consisting of halogen and alkoxy; +
        +
      • or salts thereof,
        • +
      +
      • +
    • S9) Active compounds from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones (S9), for example 1,2-dihydro-4-hydroxy-1-ethyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.: 219479-18-2), 1,2-dihydro-4-hydroxy-1-methyl-3-(5-tetrazolylcarbonyl)-2-quinolone (CAS Reg. No.: 95855-00-8), as described in WO-A-1999/000020.
      • +
    • S10) Compounds of the formula (S10a) or (S10b) +
        +
      • as described in WO-A-2007/023719 and WO-A-2007/023764
        • +
      +
      • +
    +
    • +
+

+

+embedded image + +

    +
  • +
      +
    • in which
      • +
    • RG1 is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3
      • +
    • YG, ZG independently of one another are O or S,
      • +
    • nG is an integer from 0 to 4,
      • +
    • RG2 is (C1-C16)-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl, halobenzyl,
      • +
    • RG3 is hydrogen or (C1-C6)-alkyl.
      • +
    • S11) Active compounds of the type of the oxyimino compounds (S11), which are known as seed dressings, such as, for example, “oxabetrinil” ((Z)-1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile) (S11-1), which is known as seed dressing safener for millet against metolachlor damage, +
        +
      • “fluxofenim” (1-(4-chlorophenyl)-2,2,2-trifluoro-1-ethanone O-(1,3-dioxolan-2-ylmethyl)oxime) (S11-2), which is known as seed dressing safener for millet against metolachlor damage, and
        • +
      • “cyometrinil” or “CGA-43089” ((Z)-cyanomethoxyimino(phenyl)acetonitrile) (S11-3), which is known as seed dressing safener for millet against metolachlor damage.
        • +
      +
      • +
    • S12) Active compounds from the class of the isothiochromanones (S12), such as, for example, methyl [(3-oxo-1H-2-benzothiopyran-4(3H)-ylidene)methoxy]acetate (CAS Reg. No.: 205121-04-6) (S12-1) and related compounds from WO-A-1998/13361.
      • +
    • S13) One or more compounds from group (S13): +
        +
      • “naphthalic anhydride” (1,8-naphthalenedicarboxylic anhydride) (S13-1), which is known as seed dressing safener for corn against thiocarbamate herbicide damage,
        • +
      • “fenclorim” (4,6-dichloro-2-phenylpyrimidine) (S13-2), which is known as safener for pretilachlor in sown rice,
        • +
      • “flurazole” (benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate) (S13-3), which is known as seed dressing safener for millet against alachlor and metolachlor damage,
        • +
      • “CL-304415” (CAS Reg. No.: 31541-57-8) (4-carboxy-3,4-dihydro-2H-1-benzopyran-4-acetic acid) (S13-4) from American Cyanamid, which is known as safener for corn against imidazolinone damage,
        • +
      • “MG-191” (CAS Reg. No.: 96420-72-3) (2-dichloromethyl-2-methyl-1,3-dioxolane) (S13-5) from Nitrokemia, which is known as safener for corn,
        • +
      • “MG-838” (CAS Reg. No.: 133993-74-5) (2-propenyl 1-oxa-4-azaspiro[4.5]decane-4-carbodithioate) (S13-6) from Nitrokemia,
        • +
      • “disulfoton” (O,O-diethyl S-2-ethylthioethyl phosphorodithioate) (S13-7),
        • +
      • “dietholate” (O,O-diethyl O-phenyl phosphorothioate) (S13-8),
        • +
      • “mephenate” (4-chlorophenyl methylcarbamate) (S13-9).
        • +
      +
      • +
    • S14) Active compounds which, besides a herbicidal effect against harmful plants, also have a safener effect on crop plants such as rice, such as, for example; “dimepiperate” or “MY-93” (S-1-methyl-1-phenylethyl piperidine-1-carbothioate), which is known as safener for rice against molinate herbicide damage, +
        +
      • “daimuron” or “SK 23” (1-(1-methyl-1-phenylethyl)-3-p-tolylurea), which is known as safener for rice against imazosulphuron herbicide damage,
        • +
      • “cumyluron”=“JC-940” (3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenyl-ethyl)urea, see JP-A-60087254), which is known as safener for rice against some herbicide damage,
        • +
      • “methoxyphenone” or “NK 049” (3,3′-dimethyl-4-methoxybenzophenone), which is known as safener for rice against some herbicide damage,
        • +
      • “CSB” (1-bromo-4-(chloromethylsulphonyl)benzene) from Kumiai, (CAS Reg. No. 54091-06-4), which is known as safener against some herbicide damage in rice.
        • +
      +
      • +
    • S15) Active compounds which are primarily used as herbicides, but also have safener effect on crop plants, for example
      • +
    +
    • +
  • (2,4-dichlorophenoxy)acetic acid (2,4-D),
    • +
  • (4-chlorophenoxy)acetic acid,
    • +
  • (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),
    • +
  • 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),
    • +
  • (4-chloro-o-tolyloxy)acetic acid (MCPA),
    • +
  • 4-(4-chloro-o-tolyloxy)butyric acid,
    • +
  • 4-(4-chlorophenoxy)butyric acid,
    • +
  • 3,6-dichloro-2-methoxybenzoic acid (dicamba),
    • +
  • 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate (lactidichlor-ethyl).
    • +
+

+

Most preferred crop plant compatibility-improving compounds [component (b′)] are cloquintocet-mexyl, fenchlorazole-ethyl, isoxadifen-ethyl, mefenpyr-diethyl, fenclorim, cumyluron, S4-1 and S4-5, and particular emphasis is given to cloquintocet-mexyl and mefenpyr-diethyl. Emphasis is also given to cyprosulphamide (S4-1).

+

Examples of the selective herbicidal combinations according to the invention comprising in each case one active compound of the formula (I) and in each case one of the safeners defined above are listed below:

+

+ +

+ + + + + + + + + + + +Active compound + + + + +of the formula +Safener + + + + + + + + + +I-a-1 +cloquintocet-mexyl + + + +I-a-1 +fenchlorazole-ethyl + + + +I-a-1 +isoxadifen-ethyl + + + +I-a-1 +mefenpyr-diethyl + + + +I-a-1 +fenclorim + + + +I-a-1 +cumyluron + + + +I-a-1 +S4-1 + + + +I-a-1 +S4-5 + + + +I-a-2 +cloquintocet-mexyl + + + +I-a-2 +fenchlorazole-ethyl + + + +I-a-2 +isoxadifen-ethyl + + + +I-a-2 +mefenpyr-diethyl + + + +I-a-2 +fenclorim + + + +I-a-2 +cumyluron + + + +I-a-2 +S4-1 + + + +I-a-2 +S4-5 + + + +I-a-3 +cloquintocet-mexyl + + + +I-a-3 +fenchlorazole-ethyl + + + +I-a-3 +isoxadifen-ethyl + + + +I-a-3 +mefenpyr-diethyl + + + +I-a-3 +fenclorim + + + +I-a-3 +cumyluron + + + +I-a-3 +S4-1 + + + +I-a-3 +S4-5 + + + +I-a-4 +cloquintocet-mexyl + + + +I-a-4 +fenchlorazole-ethyl + + + +I-a-4 +isoxadifen-ethyl + + + +I-a-4 +mefenpyr-diethyl + + + +I-a-4 +fenclorim + + + +I-a-4 +cumyluron + + + +I-a-4 +S4-1 + + + +I-a-4 +S4-5 + + + +I-a-5 +cloquintocet-mexyl + + + +I-a-5 +fenchlorazole-ethyl + + + +I-a-5 +isoxadifen-ethyl + + + +I-a-5 +mefenpyr-diethyl + + + +I-a-5 +fenclorim + + + +I-a-5 +cumyluron + + + +I-a-5 +S4-1 + + + +I-a-5 +S4-5 + + + +I-a-6 +cloquintocet-mexyl + + + +I-a-6 +fenchlorazole-ethyl + + + +I-a-6 +isoxadifen-ethyl + + + +I-a-6 +mefenpyr-diethyl + + + +I-a-6 +fenclorim + + + +I-a-6 +cumyluron + + + +I-a-6 +S4-1 + + + +I-a-6 +S4-5 + + + +I-a-7 +cloquintocet-mexyl + + + +I-a-7 +fenchlorazole-ethyl + + + +I-a-7 +isoxadifen-ethyl + + + +I-a-7 +mefenpyr-diethyl + + + +I-a-7 +fenclorim + + + +I-a-7 +cumyluron + + + +I-a-7 +S4-1 + + + +I-a-7 +S4-5 + + + +I-a-8 +cloquintocet-mexyl + + + +I-a-8 +fenchlorazole-ethyl + + + +I-a-8 +isoxadifen-ethyl + + + +I-a-8 +mefenpyr-diethyl + + + +I-a-8 +fenclorim + + + +I-a-8 +cumyluron + + + +I-a-8 +S4-1 + + + +I-a-8 +S4-5 + + + +I-a-9 +cloquintocet-mexyl + + + +I-a-9 +fenchlorazole-ethyl + + + +I-a-9 +isoxadifen-ethyl + + + +I-a-9 +mefenpyr-diethyl + + + +I-a-9 +fenclorim + + + +I-a-9 +cumyluron + + + +I-a-9 +S4-1 + + + +I-a-9 +S4-5 + + + +I-a-10 +cloquintocet-mexyl + + + +I-a-10 +fenchlorazole-ethyl + + + +I-a-10 +isoxadifen-ethyl + + + +I-a-10 +mefenpyr-diethyl + + + +I-a-10 +fenclorim + + + +I-a-10 +cumyluron + + + +I-a-10 +S4-1 + + + +I-a-10 +S4-5 + + + +I-a-11 +cloquintocet-mexyl + + + +I-a-11 +fenchlorazole-ethyl + + + +I-a-11 +isoxadifen-ethyl + + + +I-a-11 +mefenpyr-diethyl + + + +I-a-11 +fenclorim + + + +I-a-11 +cumyluron + + + +I-a-11 +S4-1 + + + +I-a-11 +S4-5 + + + +I-a-12 +cloquintocet-mexyl + + + +I-a-12 +fenchlorazole-ethyl + + + +I-a-12 +isoxadifen-ethyl + + + +I-a-12 +mefenpyr-diethyl + + + +I-a-12 +fenclorim + + + +I-a-12 +cumyluron + + + +I-a-12 +S4-1 + + + +I-a-12 +S4-5 + + + +I-a-13 +cloquintocet-mexyl + + + +I-a-13 +fenchlorazole-ethyl + + + +I-a-13 +isoxadifen-ethyl + + + +I-a-13 +mefenpyr-diethyl + + + +I-a-13 +fenclorim + + + +I-a-13 +cumyluron + + + +I-a-13 +S4-1 + + + +I-a-13 +S4-5 + + + +I-a-14 +cloquintocet-mexyl + + + +I-a-14 +fenchlorazole-ethyl + + + +I-a-14 +isoxadifen-ethyl + + + +I-a-14 +mefenpyr-diethyl + + + +I-a-14 +fenclorim + + + +I-a-14 +cumyluron + + + +I-a-14 +S4-1 + + + +I-a-14 +S4-5 + + + +I-a-15 +cloquintocet-mexyl + + + +I-a-15 +fenchlorazole-ethyl + + + +I-a-15 +isoxadifen-ethyl + + + +I-a-15 +mefenpyr-diethyl + + + +I-a-15 +fenclorim + + + +I-a-15 +cumyluron + + + +I-a-15 +S4-1 + + + +I-a-15 +S4-5 + + + +I-a-16 +cloquintocet-mexyl + + + +I-a-16 +fenchlorazole-ethyl + + + +I-a-16 +isoxadifen-ethyl + + + +I-a-16 +mefenpyr-diethyl + + + +I-a-16 +fenclorim + + + +I-a-16 +cumyluron + + + +I-a-16 +S4-1 + + + +I-a-16 +S4-5 + + + +I-a-17 +cloquintocet-mexyl + + + +I-a-17 +fenchlorazole-ethyl + + + +I-a-17 +isoxadifen-ethyl + + + +I-a-17 +mefenpyr-diethyl + + + +I-a-17 +fenclorim + + + +I-a-17 +cumyluron + + + +I-a-17 +S4-1 + + + +I-a-17 +S4-5 + + + +I-a-18 +cloquintocet-mexyl + + + +I-a-18 +fenchlorazole-ethyl + + + +I-a-18 +isoxadifen-ethyl + + + +I-a-18 +mefenpyr-diethyl + + + +I-a-18 +fenclorim + + + +I-a-18 +cumyluron + + + +I-a-18 +S4-1 + + + +I-a-18 +S4-5 + + + +I-a-19 +cloquintocet-mexyl + + + +I-a-19 +fenchlorazole-ethyl + + + +I-a-19 +isoxadifen-ethyl + + + +I-a-19 +mefenpyr-diethyl + + + +I-a-19 +fenclorim + + + +I-a-19 +cumyluron + + + +I-a-19 +S4-1 + + + +I-a-19 +S4-5 + + + +I-a-20 +cloquintocet-mexyl + + + +I-a-20 +fenchlorazole-ethyl + + + +I-a-20 +isoxadifen-ethyl + + + +I-a-20 +mefenpyr-diethyl + + + +I-a-20 +fenclorim + + + +I-a-20 +cumyluron + + + +I-a-20 +S4-1 + + + +I-a-20 +S4-5 + + + +I-a-21 +cloquintocet-mexyl + + + +I-a-21 +fenchlorazole-ethyl + + + +I-a-21 +isoxadifen-ethyl + + + +I-a-21 +mefenpyr-diethyl + + + +I-a-21 +fenclorim + + + +I-a-21 +cumyluron + + + +I-a-21 +S4-1 + + + +I-a-21 +S4-5 + + + +I-a-22 +cloquintocet-mexyl + + + +I-a-22 +fenchlorazole-ethyl + + + +I-a-22 +isoxadifen-ethyl + + + +I-a-22 +mefenpyr-diethyl + + + +I-a-22 +fenclorim + + + +I-a-22 +cumyluron + + + +I-a-22 +S4-1 + + + +I-a-22 +S4-5 + + + +I-a-23 +cloquintocet-mexyl + + + +I-a-23 +fenchlorazole-ethyl + + + +I-a-23 +isoxadifen-ethyl + + + +I-a-23 +mefenpyr-diethyl + + + +I-a-23 +fenclorim + + + +I-a-23 +cumyluron + + + +I-a-23 +S4-1 + + + +I-a-23 +S4-5 + + + +I-a-24 +cloquintocet-mexyl + + + +I-a-24 +fenchlorazole-ethyl + + + +I-a-24 +isoxadifen-ethyl + + + +I-a-24 +mefenpyr-diethyl + + + +I-a-24 +fenclorim + + + +I-a-24 +cumyluron + + + +I-a-24 +S4-1 + + + +I-a-24 +S4-5 + + + +I-a-25 +cloquintocet-mexyl + + + +I-a-25 +fenchlorazole-ethyl + + + +I-a-25 +isoxadifen-ethyl + + + +I-a-25 +mefenpyr-diethyl + + + +I-a-25 +fenclorim + + + +I-a-25 +cumyluron + + + +I-a-25 +S4-1 + + + +I-a-25 +S4-5 + + + +I-a-26 +cloquintocet-mexyl + + + +I-a-26 +fenchlorazole-ethyl + + + +I-a-26 +isoxadifen-ethyl + + + +I-a-26 +mefenpyr-diethyl + + + +I-a-26 +fenclorim + + + +I-a-26 +cumyluron + + + +I-a-26 +S4-1 + + + +I-a-26 +S4-5 + + + +I-a-27 +cloquintocet-mexyl + + + +I-a-27 +fenchlorazole-ethyl + + + +I-a-27 +isoxadifen-ethyl + + + +I-a-27 +mefenpyr-diethyl + + + +I-a-27 +fenclorim + + + +I-a-27 +cumyluron + + + +I-a-27 +S4-1 + + + +I-a-27 +S4-5 + + + +I-a-28 +cloquintocet-mexyl + + + +I-a-28 +fenchlorazole-ethyl + + + +I-a-28 +isoxadifen-ethyl + + + +I-a-28 +mefenpyr-diethyl + + + +I-a-28 +fenclorim + + + +I-a-28 +cumyluron + + + +I-a-28 +S4-1 + + + +I-a-28 +S4-5 + + + +I-a-29 +cloquintocet-mexyl + + + +I-a-29 +fenchlorazole-ethyl + + + +I-a-29 +isoxadifen-ethyl + + + +I-a-29 +mefenpyr-diethyl + + + +I-a-29 +fenclorim + + + +I-a-29 +cumyluron + + + +I-a-29 +S4-1 + + + +I-a-29 +S4-5 + + + +I-a-30 +cloquintocet-mexyl + + + +I-a-30 +fenchlorazole-ethyl + + + +I-a-30 +isoxadifen-ethyl + + + +I-a-30 +mefenpyr-diethyl + + + +I-a-30 +fenclorim + + + +I-a-30 +cumyluron + + + +I-a-30 +S4-1 + + + +I-a-30 +S4-5 + + + +I-a-31 +cloquintocet-mexyl + + + +I-a-31 +fenchlorazole-ethyl + + + +I-a-31 +isoxadifen-ethyl + + + +I-a-31 +mefenpyr-diethyl + + + +I-a-31 +fenclorim + + + +I-a-31 +cumyluron + + + +I-a-31 +S4-1 + + + +I-a-31 +S4-5 + + + +I-a-32 +cloquintocet-mexyl + + + +I-a-32 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+fenchlorazole-ethyl + + + +I-d-13 +isoxadifen-ethyl + + + +I-d-13 +mefenpyr-diethyl + + + +I-d-13 +fenclorim + + + +I-d-13 +cumyluron + + + +I-d-13 +S4-1 + + + +I-d-13 +S4-5 + + + +I-d-14 +cloquintocet-mexyl + + + +I-d-14 +fenchlorazole-ethyl + + + +I-d-14 +isoxadifen-ethyl + + + +I-d-14 +mefenpyr-diethyl + + + +I-d-14 +fenclorim + + + +I-d-14 +cumyluron + + + +I-d-14 +S4-1 + + + +I-d-14 +S4-5 + + + +I-d-15 +cloquintocet-mexyl + + + +I-d-15 +fenchlorazole-ethyl + + + +I-d-15 +isoxadifen-ethyl + + + +I-d-15 +mefenpyr-diethyl + + + +I-d-15 +fenclorim + + + +I-d-15 +cumyluron + + + +I-d-15 +S4-1 + + + +I-d-15 +S4-5 + + + +I-f-1 +cloquintocet-mexyl + + + +I-f-1 +fenchlorazole-ethyl + + + +I-f-1 +isoxadifen-ethyl + + + +I-f-1 +mefenpyr-diethyl + + + +I-f-1 +fenclorim + + + +I-f-1 +cumyluron + + + +I-f-1 +S4-1 + + + +I-f-1 +S4-5 + + + +I-f-2 +cloquintocet-mexyl + + + +I-f-2 +fenchlorazole-ethyl + + + +I-f-2 +isoxadifen-ethyl + + + +I-f-2 +mefenpyr-diethyl + + + +I-f-2 +fenclorim + + + +I-f-2 +cumyluron + + + +I-f-2 +S4-1 + + + +I-f-2 +S4-5 + + + +I-f-3 +cloquintocet-mexyl + + + +I-f-3 +fenchlorazole-ethyl + + + +I-f-3 +isoxadifen-ethyl + + + +I-f-3 +mefenpyr-diethyl + + + +I-f-3 +fenclorim + + + +I-f-3 +cumyluron + + + +I-f-3 +S4-1 + + + +I-f-3 +S4-5 + + + +I-f-4 +cloquintocet-mexyl + + + +I-f-4 +fenchlorazole-ethyl + + + +I-f-4 +isoxadifen-ethyl + + + +I-f-4 +mefenpyr-diethyl + + + +I-f-4 +fenclorim + + + +I-f-4 +cumyluron + + + +I-f-4 +S4-1 + + + +I-f-4 +S4-5 + + + +I-f-5 +cloquintocet-mexyl + + + +I-f-5 +fenchlorazole-ethyl + + + +I-f-5 +isoxadifen-ethyl + + + +I-f-5 +mefenpyr-diethyl + + + +I-f-5 +fenclorim + + + +I-f-5 +cumyluron + + + +I-f-5 +S4-1 + + + +I-f-5 +S4-5 + + + +I-f-6 +cloquintocet-mexyl + + + +I-f-6 +fenchlorazole-ethyl + + + +I-f-6 +isoxadifen-ethyl + + + +I-f-6 +mefenpyr-diethyl + + + +I-f-6 +fenclorim + + + +I-f-6 +cumyluron + + + +I-f-6 +S4-1 + + + +I-f-6 +S4-5 + + + +I-f-7 +cloquintocet-mexyl + + + +I-f-7 +fenchlorazole-ethyl + + + +I-f-7 +isoxadifen-ethyl + + + +I-f-7 +mefenpyr-diethyl + + + +I-f-7 +fenclorim + + + +I-f-7 +cumyluron + + + +I-f-7 +S4-1 + + + +I-f-7 +S4-5 + + + +I-f-8 +cloquintocet-mexyl + + + +I-f-8 +fenchlorazole-ethyl + + + +I-f-8 +isoxadifen-ethyl + + + +I-f-8 +mefenpyr-diethyl + + + +I-f-8 +fenclorim + + + +I-f-8 +cumyluron + + + +I-f-8 +S4-1 + + + +I-f-8 +S4-5 + + + +I-f-9 +cloquintocet-mexyl + + + +I-f-9 +fenchlorazole-ethyl + + + +I-f-9 +isoxadifen-ethyl + + + +I-f-9 +mefenpyr-diethyl + + + +I-f-9 +fenclorim + + + +I-f-9 +cumyluron + + + +I-f-9 +S4-1 + + + +I-f-9 +S4-5 + + + +I-f-10 +cloquintocet-mexyl + + + +I-f-10 +fenchlorazole-ethyl + + + +I-f-10 +isoxadifen-ethyl + + + +I-f-10 +mefenpyr-diethyl + + + +I-f-10 +fenclorim + + + +I-f-10 +cumyluron + + + +I-f-10 +S4-1 + + + +I-f-10 +S4-5 + + + +I-f-11 +cloquintocet-mexyl + + + +I-f-11 +fenchlorazole-ethyl + + + +I-f-11 +isoxadifen-ethyl + + + +I-f-11 +mefenpyr-diethyl + + + +I-f-11 +fenclorim + + + +I-f-11 +cumyluron + + + +I-f-11 +S4-1 + + + +I-f-11 +S4-5 + + + +I-f-12 +cloquintocet-mexyl + + + +I-f-12 +fenchlorazole-ethyl + + + +I-f-12 +isoxadifen-ethyl + + + +I-f-12 +mefenpyr-diethyl + + + +I-f-12 +fenclorim + + + +I-f-12 +cumyluron + + + +I-f-12 +S4-1 + + + +I-f-12 +S4-5 + + + +I-f-13 +cloquintocet-mexyl + + + +I-f-13 +fenchlorazole-ethyl + + + +I-f-13 +isoxadifen-ethyl + + + +I-f-13 +mefenpyr-diethyl + + + +I-f-13 +fenclorim + + + +I-f-13 +cumyluron + + + +I-f-13 +S4-1 + + + +I-f-13 +S4-5 + + + +I-f-14 +cloquintocet-mexyl + + + +I-f-14 +fenchlorazole-ethyl + + + +I-f-14 +isoxadifen-ethyl + + + +I-f-14 +mefenpyr-diethyl + + + +I-f-14 +fenclorim + + + +I-f-14 +cumyluron + + + +I-f-14 +S4-1 + + + +I-f-14 +S4-5 + + + +I-f-15 +cloquintocet-mexyl + + + +I-f-15 +fenchlorazole-ethyl + + + +I-f-15 +isoxadifen-ethyl + + + +I-f-15 +mefenpyr-diethyl + + + +I-f-15 +fenclorim + + + +I-f-15 +cumyluron + + + +I-f-15 +S4-1 + + + +I-f-15 +S4-5 + + + +I-f-16 +cloquintocet-mexyl + + + +I-f-16 +fenchlorazole-ethyl + + + +I-f-16 +isoxadifen-ethyl + + + +I-f-16 +mefenpyr-diethyl + + + +I-f-16 +fenclorim + + + +I-f-16 +cumyluron + + + +I-f-16 +S4-1 + + + +I-f-16 +S4-5 + + + +I-f-17 +cloquintocet-mexyl + + + +I-f-17 +fenchlorazole-ethyl + + + +I-f-17 +isoxadifen-ethyl + + + +I-f-17 +mefenpyr-diethyl + + + +I-f-17 +fenclorim + + + +I-f-17 +cumyluron + + + +I-f-17 +S4-1 + + + +I-f-17 +S4-5 + + + +I-f-18 +cloquintocet-mexyl + + + +I-f-18 +fenchlorazole-ethyl + + + +I-f-18 +isoxadifen-ethyl + + + +I-f-18 +mefenpyr-diethyl + + + +I-f-18 +fenclorim + + + +I-f-18 +cumyluron + + + +I-f-18 +S4-1 + + + +I-f-18 +S4-5 + + + +I-f-19 +cloquintocet-mexyl + + + +I-f-19 +fenchlorazole-ethyl + + + +I-f-19 +isoxadifen-ethyl + + + +I-f-19 +mefenpyr-diethyl + + + +I-f-19 +fenclorim + + + +I-f-19 +cumyluron + + + +I-f-19 +S4-1 + + + +I-f-19 +S4-5 + + + +I-f-20 +cloquintocet-mexyl + + + +I-f-20 +fenchlorazole-ethyl + + + +I-f-20 +isoxadifen-ethyl + + + +I-f-20 +mefenpyr-diethyl + + + +I-f-20 +fenclorim + + + +I-f-20 +cumyluron + + + +I-f-20 +S4-1 + + + +I-f-20 +S4-5 + + + +I-f-21 +cloquintocet-mexyl + + + +I-f-21 +fenchlorazole-ethyl + + + +I-f-21 +isoxadifen-ethyl + + + +I-f-21 +mefenpyr-diethyl + + + +I-f-21 +fenclorim + + + +I-f-21 +cumyluron + + + +I-f-21 +S4-1 + + + +I-f-21 +S4-5 + + + +I-f-22 +cloquintocet-mexyl + + + +I-f-22 +fenchlorazole-ethyl + + + +I-f-22 +isoxadifen-ethyl + + + +I-f-22 +mefenpyr-diethyl + + + +I-f-22 +fenclorim + + + +I-f-22 +cumyluron + + + +I-f-22 +S4-1 + + + +I-f-22 +S4-5 + + + +I-f-23 +cloquintocet-mexyl + + + +I-f-23 +fenchlorazole-ethyl + + + +I-f-23 +isoxadifen-ethyl + + + +I-f-23 +mefenpyr-diethyl + + + +I-f-23 +fenclorim + + + +I-f-23 +cumyluron + + + +I-f-23 +S4-1 + + + +I-f-23 +S4-5 + + + +I-f-24 +cloquintocet-mexyl + + + +I-f-24 +fenchlorazole-ethyl + + + +I-f-24 +isoxadifen-ethyl + + + +I-f-24 +mefenpyr-diethyl + + + +I-f-24 +fenclorim + + + +I-f-24 +cumyluron + + + +I-f-24 +S4-1 + + + +I-f-24 +S4-5 + + + +I-f-25 +cloquintocet-mexyl + + + +I-f-25 +fenchlorazole-ethyl + + + +I-f-25 +isoxadifen-ethyl + + + +I-f-25 +mefenpyr-diethyl + + + +I-f-25 +fenclorim + + + +I-f-25 +cumyluron + + + +I-f-25 +S4-1 + + + +I-f-25 +S4-5 + + + + + + + +
+ +

+

It has now surprisingly been found that the above-defined active compound combinations of compounds of the general formula (I) and safeners (antidotes) from group (b′) set out above combine very good compatibility with useful plants with a particularly high herbicidal activity and can be used in various crops, in particular in cereals (especially wheat), but also in soya beans, potatoes, maize and rice, for the selective control of weeds.

+

In this context, it is considered surprising that, from a multiplicity of known safeners or antidotes capable of antagonizing the damaging effect of a herbicidal crop plant, it is specifically the compounds of group (b′) set out above which are suitable for compensating—almost completely—the damaging effect of compounds of the formula (I) on the crop plants, without at the same time having any substantial adverse effect on the herbicidal activity against the weeds.

+

Emphasis may be given here to the particularly advantageous effect of the preferred and most preferred combination partners from group (b′), particularly with regard to the sparing of cereal plants, such as, for example, wheat, barley and rye, but also maize and rice, as crop plants.

+

The formula (I) provides a general definition of the compounds according to the invention. Preferred substituents or ranges of the radicals given in the formulae mentioned above and below are illustrated below: +

+

+

+embedded image + +

+

+

In the radical definitions mentioned as being preferred, halogen represents fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine. The terms alkyl, alkylidene and alkenyl refer both to straight-chain and to branched hydrocarbon radicals. +

+

+

+embedded image + +

+

+

+embedded image + +

+

+

In the radical definitions mentioned as being particularly preferred, halogen represents fluorine, chlorine and bromine, in particular fluorine and chlorine. The terms alkyl, alkylidene and alkenyl are referred both to straight-chain and to branched hydrocarbon radicals. +

+

+

+embedded image + +

+

+

+embedded image + +

+

+

The general or preferred radical definitions or illustrations listed above can be combined with one another as desired, i.e. including combinations between the respective ranges and preferred ranges. They apply both to the end products and, correspondingly, to the precursors and intermediates.

+

Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred (preferable).

+

Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.

+

Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.

+

Emphasis according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as emphasized.

+

Special preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being especially preferred.

+

Saturated or unsaturated hydrocarbon radicals, such as alkyl, alkanediyl or alkenyl, can in each case be straight-chain or branched as far as this is possible, including in combination with heteroatoms, such as, for example, in alkoxy.

+

Optionally substituted radicals may be mono- or polysubstituted unless indicated otherwise, and in the case of multiple substitutions the substituents can be identical or different.

+

With particular emphasis, G represents hydrogen.

+

In addition to the compounds mentioned in the Preparation Examples, the following compounds of the formula (I-1-a) may be specifically mentioned:

+

+embedded image + +

+

+ + + + + + + + +TABLE 1 + + + + + +  +A +B + + + + + + + + + + + + + + + + + +—O—(CH2)2—O— + + + +—O—(CH2)4—O— + + + +—O—CHCH3—CH2—O— + + + +—O—CHCH3—CHCH3—O— + + + +—O—(CH2)3—O— + + + +—O—CHCH3—(CH2)2—O— + + + +—O—CHCH3—CH2—CHCH3—O— + + + +—O—CH2—CH(CH3)—CH2—O— + + + +—O—CH2—CH(OCH3)—CH2—O— + + + +—O—CH2—C(CH3)2—CH2—O— + + + + + + + +embedded image + + + + + + + + +—O—CH2—CH═CH—CH2—O— + + + +—S—(CH2)2—S— + + + +—S—(CH2)3—S— + + + +—O—CH2—O—CH2— + + + +—O—C(CH3)2—O—CH2— + + + + + +X = CH3, Y = CH3, Z = CH3 + + + +
+ +
+Table 2: A and B as mentioned in Table 1 and +

+

+

In the literature it has already been described how the action of various active compounds can be boosted by addition of ammonium salts. The salts in question, however, are detersive salts (for example WO 95/017817) or salts which have relatively long alkyl substituents and/or aryl substituents and which have a permeabilizing action or which increase the active compound's solubility (for example EP-A 0 453 086, EP-A 0 664 081, FR-A 2 600 494, U.S. Pat. No. 4,844,734, U.S. Pat. No. 5,462,912, U.S. Pat. No. 5,538,937, US-A 03/0224939, US-A 05/0009880, US-A 05/0096386). Moreover, the prior art describes the action only for particular active compounds and/or particular applications of the corresponding compositions. In other cases, in turn, the salts in question are those of sulphonic acids, where the acids themselves have a paralytic action on insects (U.S. Pat. No. 2,842,476). A boost to action by ammonium sulphate, for example, is described by way of example for the herbicides glyphosate, phosphinothricin and for phenyl-substituted cyclic ketoenols (U.S. Pat. No. 6,645,914, EP-A2 0 036 106, WO 07/068,427). A corresponding boost of action in the case of insecticides has already been described in WO 07/068,428.

+

The use of ammonium sulphate as a formulating assistant has also been described for certain active compounds and applications (WO 92/16108), but its purpose therein is to stabilize the formulation, not to boost the action.

+

It has now been found, surprisingly, that the action of insecticides and/or acaricides and/or herbicides from the class of the phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I) can be boosted significantly through the addition of ammonium salts or phosphonium salts to the application solution or through the incorporation of these salts into a formulation comprising phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I). The present invention therefore provides for the use of ammonium salts or phosphonium salts for boosting the action of crop protection compositions which comprise as their active compound herbicidal and/or insecticidal and/or acaricidal phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I). The invention likewise provides compositions which comprise herbicidal and/or acaricidal and/or insecticidal phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I) and action-boosting ammonium salts or phosphonium salts, including not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention further provides, finally, for the use of these compositions for controlling insect pests and/or spider mites and/or unwanted vegetation.

+

The active compounds can be used in the compositions according to the invention in a broad concentration range. The concentration of the active compounds in the formulation is typically 0.1%-50% by weight.

+

Formula (III′) provides a definition of the ammonium salts and phosphonium salts which, according to the invention, boost the activity of crop protection compositions comprising fatty acid biosynthesis inhibitors

+

+embedded image + +

+

in which +
+D represents nitrogen or phosphorus, +
+D preferably represents nitrogen, +
+R26, R27, R28 and R29 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene, the substituents being selectable from halogen, nitro and cyano, +
+R26, R27, R28 and R29 independently of one another preferably represent hydrogen or in each case optionally substituted C1-C4-alkyl, the substituents being selectable from halogen, nitro and cyano, +
+R26, R27, R28 and R29 independently of one another particularly preferably represent hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, +
+R26, R27, R28 and R29 very particularly preferably represent hydrogen, +
+n represents 1, 2, 3 or 4, +
+n preferably represents 1 or 2, +
+R30 represents an organic or inorganic anion, +
+R30 preferably represents hydrogencarbonate, tetraborate, fluoride, bromide, iodide, chloride, monohydrogenphosphate, dihydrogenphosphate, hydrogensulphate, tartrate, sulphate, nitrate, thiosulphate, thiocyanate, formate, lactate, acetate, propionate, butyrate, pentanoate or oxalate, +
+R30 particularly preferably represents lactate, sulphate, nitrate, thiosulphate, thiocyanate, oxalate or formate. +
+R30 very particularly preferably represents sulphate. +

+

The ammonium salts and phosphonium salts of the formula (III′) can be used in a broad concentration range to boost the activity of crop protection compositions comprising phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I). In general the ammonium salts or phosphonium salts are used in the ready-to-use crop protection composition in a concentration of 0.5 to 80 mmol/l, preferably 0.75 to 37.5 mmol/l, more preferably 1.5 to 25 mmol/l. In the case of a formulated product the ammonium salt and/or phosphonium salt concentration in the formulation is chosen such that it is within these stated general, preferred or particularly preferred ranges after the formulation has been diluted to the desired active compound concentration. The concentration of the salt in the formulation is typically 1%-50% by weight.

+

In one preferred embodiment of the invention the activity is boosted by adding to the crop protection compositions not only an ammonium salt and/or phosphonium salt but also, additionally, a penetrant. It is considered entirely surprising that even in these cases an even greater boost to activity is observed. The present invention therefore likewise provides for the use of a combination of penetrant and ammonium salts and/or phosphonium salts to boost the activity of crop protection compositions which comprise insecticidal and/or acaricidal and/or herbicidal phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I) as active compound. The invention likewise provides compositions which comprise herbicidal and/or acaricidal and/or insecticidal phenyl-substituted bicyclooctane-1,3-dione derivatives of the formula (I), penetrants and ammonium salts and/or phosphonium salts, including specifically not only formulated active compounds but also ready-to-use compositions (spray liquors). The invention additionally provides, finally, for the use of these compositions for controlling harmful insects and/or spider mites and/or unwanted vegetation.

+

In the present context, suitable penetrants are all those substances which are usually employed to improve penetration of agrochemically active compounds into plants. In this context, penetrants are defined in that they penetrate from the aqueous spray liquor and/or the spray coating into the cuticles of the plant, thus increasing the mobility of active compounds in the cuticles. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used for determining this property.

+

Examples of suitable penetrants include alkanol alkoxylates. Penetrants of the invention are alkanol alkoxylates of the formula (IV′)

+

+
+R—O-(-AO)v—R′  (IV′) +

+

in which +

+

+

One preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+R—O-(-EO—)n—R′  (IV′-a) +

+

in which +
+R is as defined above, +
+R′ is as defined above, +
+EO represents —CH2—CH2—O—, and +
+n represents a number from 2 to 20. +

+

A further preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+R—O-(-EO—)p—(—PO—)q—R′  (IV′-b) +

+

in which +
+R is as defined above, +
+R′ is as defined above, +
+EO represents —CH2—CH2—O—, +
+PO represents +

+

+embedded image + +

+

p represents a number from 1 to 10, and +
+q represents a number from 1 to 10. +

+

A further preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+R—O—(—PO-)r-(EO—)s—R′  (IV′-c) +

+

in which +
+R is as defined above, +
+R′ is as defined above, +
+EO represents —CH2—CH2—O—, +
+PO represents +

+

+embedded image + +

+

r is a number from 1 to 10, and +
+s is a number from 1 to 10. +

+

A further preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+R—O-(-EO—)p—(—BO—)q—R′  (IV′-d) +

+

in which +
+R and R′ are as defined above, +
+EO represents —CH2—CH2—O—, +
+BO represents +

+

+embedded image + +

+

p is a number from 1 to 10 and +
+q. is a number from 1 to 10. +

+

A further preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+R—O—(—BO-)r-(-EO—)s—R′  (IV′-e) +

+

in which +
+R and R′ are as defined above, +
+BO represents +

+

+embedded image + +

+

EO represents —CH, —CH2—O—, +
+r represents a number from 1 to 10 and +
+s represents a number from 1 to 10. +

+

A further preferred group of penetrants are alkanol alkoxylates of the formula

+

+
+CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—R′  (IV′-f) +

+

in which +
+R′ is as defined above, +
+t represents a number from 8 to 13, +
+u represents a number from 6 to 17. +

+

In the formulae indicated above, +

+

+

As an example of an alkanol alkoxylate of the formula (IV′-c) mention may be made of 2-ethylhexyl alkoxylate of the formula

+

+embedded image + +

+

in which +
+EO represents —CH2—CH2—O—, +
+PO represents +

+

+embedded image + +

+

and +
+the numbers 8 and 6 represent average values. +

+

As an example of an alkanol alkoxylate of the formula (IV′-d) mention may be made of the formula

+

+
+CH3—(CH2)10—O-(-EO—)6—(—BO—)2—CH3  (IV′-d-1) +

+

in which +
+EO represents —CH2—CH2—O—, +
+BO represents +

+

+embedded image + +

+

and +
+the numbers 10, 6 and 2 represent average values. +

+

Particularly preferred alkanol alkoxylates of the formula (IV′-f) are compounds of this formula in which

+

t represents a number from 9 to 12 and +
+u represents a number from 7 to 9. +

+

Mention may be made with very particular preference of alkanol alkoxylate of the formula (IV′-f-1)

+

+
+CH3—(CH2)t—CH2—O—(—CH2—CH2—O—)u—H  (IV′-f-1) +

+

in which +
+t represents the average value 10.5 and +
+u represents the average value 8.4. +

+

A general definition of the alkanol alkoxylates is given by the formulae above. These substances are mixtures of compounds of the stated type with different chain lengths. The indices therefore have average values which may also deviate from whole numbers.

+

The alkanol alkoxylates of the formulae stated are known and in some cases are available commercially or can be prepared by known methods (cf. WO 98/35 553, WO 00/35 278 and EP-A 0 681 865).

+

Suitable penetrants also include, for example, substances which promote the availability of the compounds of the formula (I) in the spray coating. These include, for example, mineral or vegetable oils. Suitable oils are all mineral or vegetable oils—modified or otherwise—which can typically be used in agrochemical compositions. Mention may be made by way of example of sunflower oil, rapeseed oil, olive oil, castor oil, colza oil, maize seed oil, cotton seed oil and soya bean oil, or the esters of said oils. Preference is given to rapeseed oil, sunflower oil and their methyl or ethyl esters.

+

The concentration of penetrant in the compositions of the invention can be varied within a wide range. In the case of a formulated crop protection composition it is in general 1% to 95%, preferably 1% to 55%, more preferably 15%-40% by weight. In the ready-to-use compositions (spray liquors) the concentrations are generally between 0.1 and 10 g/l, preferably between 0.5 and 5 g/l.

+

Crop protection compositions of the invention may also comprise further components, examples being surfactants and/or dispersing assistants or emulsifiers.

+

Suitable nonionic surfactants and/or dispersing assistants include all substances of this type that can typically be used in agrochemical compositions. Preferably mention may be made of polyethylene oxide-polypropylene oxide block copolymers, polyethylene glycol ethers of linear alcohols, reaction products of fatty acids with ethylene oxide and/or propylene oxide, and also polyvinyl alcohol, polyvinylpyrrolidone, copolymers of polyvinyl alcohol and polyvinylpyrrolidone, and copolymers of (meth)acrylic acid and (meth)acrylic esters, and additionally alkyl ethoxylates and alkylaryl ethoxylates, which optionally may be phosphated and optionally may be neutralized with bases, mention being made, by way of example, of sorbitol ethoxylates, and, as well, polyoxyalkylenamine derivatives.

+

Suitable anionic surfactants include all substances of this type that can typically be used in agrochemical compositions. Preference is given to alkali metal salts and alkaline earth metal salts of alkylsulphonic acids or alkylarykulphonic acids.

+

A further preferred group of anionic surfactants and/or dispersing assistants are the following salts that are of low solubility in plant oil: salts of polystyrenesulphonic acids, salts of polyvinylsulphonic acids, salts of naphthalenesulphonic acid-formaldehyde condensation products, salts of condensation products of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde, and salts of lignosulphonic acid.

+

Suitable additives which may be included in the formulations of the invention are emulsifiers, foam inhibitors, preservatives, antioxidants, colorants and inert filling materials.

+

Preferred emulsifiers are ethoxylated nonylphenols, reaction products of alkylphenols with ethylene oxide and/or propylene oxide, ethoxylated arylalkylphenols, and also ethoxylated and propoxylated arylalkylphenols, and also sulphated or phosphated arylalkyl ethoxylates and/or arylalkyl ethoxypropoxylates, mention being made by way of example of sorbitan derivatives, such as polyethylene oxide-sorbitan fatty acid esters, and sorbitan fatty acid esters.

+

The active compounds of the invention, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as crop protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:

+

From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.

+

From the class of the Arachnida, for example, Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Nuphersa spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.

+

From the class of the Bivalva, for example, Dreissena spp.

+

From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.

+

From the order of the Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Hellula undalis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus holo-leucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllotreta spp., Popillia japonica, Premnotrypes spp., Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.

+

From the order of the Collembola, for example, Onychiurus armatus.

+

From the order of the Diplopoda, for example, Blaniulus guttulatus.

+

From the order of the Diptera, for example, Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp., Gastrophilus spp., Hydrellia spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia spp., Phorbia spp., Prodiplosis spp., Psila rosae, Rhagoletis spp., Stomoxys spp., Tabanus spp., Tannia spp., Tetanops spp., Tipula spp.

+

From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.

+

From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp, Strongyloides fuellebomi, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.

+

It is furthermore possible to control protozoans, such as Eimeria.

+

From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monalonion atratum, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.

+

From the order of the Homoptera, for example, Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Hieroglyphus spp., Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes spp., Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.

+

From the order of the Hymenoptera, for example, Athalia spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

+

From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.

+

From the order of the Isoptera, for example, Acromyrmex spp., Atta spp., Cornitermes cumulans, Microtermes obeli, Odontotermes spp., Reticulitermes spp.

+

From the order of the Lepidoptera, for example, Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Chematobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria, Maruca testulalis, Mamestra brassicae, Mocis spp., Mythimna separata, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scotia segetum, Sesamia spp., Sparganothis spp., Spodoptera spp., Stathmopoda spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichoplusia spp., Tuta absoluta, Virachola spp.

+

From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanica, Dichroplus spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.

+

From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.

+

From the order of the Symphyla, for example, Scutigerella spp.

+

From the order of the Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.

+

From the order of the Thysanura, for example, Lepisma saccharina.

+

The plant-parasitic nematodes include, for example, Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Trichodorus spp., Tylenchulus semipenetrans, Xiphinema spp.

+

If appropriate, the compounds according to the invention can, at certain concentrations or application rates, also be used as herbicides, safeners, growth regulators or agents to improve plant properties, or as microbicides, for example as fungicides, antimycotics, bactericides, viricides (including agents against viroids) or as agents against MLO (Mycoplasma-like organisms) and RLO (Rickettsia-like organisms). If appropriate, they can also be employed as intermediates or precursors for the synthesis of other active compounds.

+

The active compounds can be converted to the customary formulations, such as solutions, emulsions, wettable powders, water- and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, granules for broadcasting, suspension-emulsion concentrates, natural materials impregnated with active compound, synthetic materials impregnated with active compound, fertilizers and microencapsulations in polymeric substances.

+

These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants and/or foam-formers. The formulations are prepared either in suitable plants or else before or during the application.

+

Suitable for use as auxiliaries are substances which are suitable for imparting to the composition itself and/or to preparations derived therefrom (for example spray liquors, seed dressings) particular properties such as certain technical properties and/or also particular biological properties. Typical suitable auxiliaries are: extenders, solvents and carriers.

+

Suitable extenders are, for example, water, polar and nonpolar organic chemical liquids, for example from the classes of the aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), the alcohols and polyols (which, if appropriate, may also be substituted, etherified and/or esterified), the ketones (such as acetone, cyclohexanone), esters (including fats and oils) and (poly)ethers, the unsubstituted and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, the sulphones and sulphoxides (such as dimethyl sulphoxide).

+

If the extender used is water, it is also possible to employ, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents are: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and also their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethyl sulphoxide, and also water.

+

According to the invention, a carrier is a natural or synthetic organic or inorganic substance which may be solid or liquid and with which the active compounds are mixed or bonded for better applicability, in particular for application to plants or parts of plants. The solid or liquid carrier is generally inert and should be suitable for use in agriculture.

+

Suitable solid carriers are:

+

for example, ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates; suitable solid carriers for granules are: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as paper, sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-formers are: for example, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are nonionic and/or ionic substances, for example from the classes of the alcohol-POE and/or -POP ethers, acid and/or POP-POE esters, alkylaryl and/or POP-POE ethers, fat- and/or POP-POE adducts, POE- and/or POP-polyol derivatives, POE- and/or POP-sorbitan or -sugar adducts, alkyl or aryl sulphates, alkyl- or arylsulphonates and alkyl or aryl phosphates or the corresponding PO-ether adducts. Furthermore, suitable oligo- or polymers, for example those derived from vinylic monomers, from acrylic acid, from EO and/or PO alone or in combination with, for example, (poly)alcohols or (poly)amines. It is also possible to employ lignin and its sulphonic acid derivatives, unmodified and modified celluloses, aromatic and/or aliphatic sulphonic acids and their adducts with formaldehyde.

+

Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations.

+

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

+

Other possible additives are perfumes, mineral or vegetable, optionally modified oils, waxes and nutrients (including trace nutrients), such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

+

Stabilizers, such as low-temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents which improve chemical and/or physical stability may also be present.

+

The formulations generally comprise between 0.01 and 98% by weight of active compound, preferably between 0.5 and 90%.

+

The active compound according to the invention can be used in its commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, bactericides, acaricides, nematicides, fungicides, growth-regulating substances, herbicides, safeners, fertilizers or semiochemicals.

+

A mixture with other known active compounds, such as herbicides, fertilizers, growth regulators, safeners, semiochemicals, or else with agents for improving the plant properties, is also possible.

+

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergists. Synergists are compounds which increase the action of the active compounds, without it being necessary for the synergist added to be active itself.

+

When used as insecticides, the active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with inhibitors which reduce degradation of the active compound after use in the environment of the plant, on the surface of parts of plants or in plant tissues.

+

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight.

+

The compounds are employed in a customary manner appropriate for the use forms.

+

All plants and plant parts can be treated in accordance with the invention. Plants are to be understood as meaning in the present context all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and genetic engineering methods or by combinations of these methods, including the transgenic plants and including the plant cultivars protectable or not protectable by plant breeders' rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds, roots, tubers and rhizomes. The plant parts also include harvested material, and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

+

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.

+

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof, are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms “parts”, “parts of plants” and “plant parts” have been explained above.

+

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having novel properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.

+

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

+

The transgenic plants or plant cultivars (obtained by genetic engineering) which are preferably to be treated according to the invention include all plants which, by virtue of the genetic modification, received genetic material which imparted particularly advantageous, useful traits to these plants. Examples of such traits are better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products. Further and particularly emphasized examples of such traits are a better defence of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and/or viruses, and also increased tolerance of the plants to certain herbicidally active compounds. Examples of transgenic plants which may be mentioned are the important crop plants, such as cereals (wheat, rice), maize, soya beans, potatoes, sugar beet, tomatoes, peas and other vegetable varieties, cotton, tobacco, oilseed rape and also fruit plants (with the fruits apples, pears, citrus fruits and grapes), and particular emphasis is given to maize, soya beans, potatoes, cotton, tobacco and oilseed rape. Traits that are emphasized are in particular increased defence of the plants against insects, arachnids, nematodes and slugs and snails by virtue of toxins formed in the plants, in particular those formed in the plants by the genetic material from Bacillus thuringiensis (for example by the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof) (referred to hereinbelow as “Bt plants”). Traits that are also particularly emphasized are the increased defence of the plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits that are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulphonylureas, glyphosate or phosphinotricin (for example the “PAT” gene). The genes which impart the desired traits in question can also be present in combination with one another in the transgenic plants. Examples of “Bt plants” which may be mentioned are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize). Of course, these statements also apply to plant cultivars having these genetic traits or genetic traits still to be developed, which plant cultivars will be developed and/or marketed in the future.

+

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

+

The compounds of the formula (I) according to the invention (active compounds) have excellent herbicidal activity against a broad spectrum of economically important monocotylidonous and dicotylidonous annual harmful plants. The active compounds also act efficiently on perennial harmful plants which produce shoots from rhizomes, root stocks or other perennial organs and which are difficult to control.

+

The amount of active compound used may vary within a relatively wide range. It depends essentially on the nature of the desired effect. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil area, preferably between 5 g and 5 kg per ha.

+

The advantageous effect of the compatibility with crop plants of the active compound combinations according to the invention is particularly pronounced at certain concentration ratios. However, the weight ratios of the active compounds in the active compound combinations can be varied within relatively wide ranges. In general, from 0.001 to 1000 parts by weight, preferably from 0.01 to 100 parts by weight, particularly preferably from 0.05 to 20 parts by weight, of one of the crop plant compatibility-improving compounds (antidotes/safeners) mentioned above under (b′) are present per part by weight of active compound of the formula (I).

+

The active compound combinations according to the invention are generally applied in the form of finished formulations. However, the active compounds present in the active compound combinations can, as individual formulations, also be mixed during use, i.e. be applied in the form of tank mixtures.

+

For certain applications, in particular in the post-emergence method, it may furthermore be advantageous to include in the formulations, as further additives, mineral or vegetable oils which are tolerated by plants (for example the commercial preparation “Rako Binol”), or ammonium salts, such as, for example, ammonium sulphate or ammonium thiocyanate.

+

The novel active compound combinations can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is in the customary manner, for example by watering, spraying, atomizing, dusting or broadcasting.

+

The application rates of the active compound combinations according to the invention can be varied within a certain range; they depend, inter alia, on the weather and on soil factors. In general, the application rates are from 0.001 to 5 kg per ha, preferably from 0.005 to 2 kg per ha, particularly preferably from 0.01 to 0.5 kg per ha.

+

Depending on their properties, the safeners to be used according to the invention can be used for pretreating the seed of the crop plant (seed dressing) or can be introduced into the seed ferrules prior to the seed or be used separately prior to the herbicide or together with the herbicide, before or after emergence of the plants.

+

Examples of plants which may be mentioned are important crop plants, such as cereals (wheat, barley, rice), maize, soya beans, potatoes, cotton, oilseed rape, beet, sugar cane and also fruit plants (with the fruits apples, pears, citrus fruits and grapevines), greater emphasis being given to cereals, maize, soya beans, potatoes, cotton and oilseed rape.

+

All plants and plant parts can be treated with the active compounds according to the invention. Here, plants are to be understood as meaning all plants and plant populations such as wanted and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional plant breeding and optimization methods or by biotechnological and recombinant methods or by combinations of these methods, including the transgenic plants and inclusive of the plant cultivars protectable or not protectable by plant breeders rights. Plant parts are to be understood as meaning all parts and organs of plants above and below the ground, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stalks, stems, flowers, fruit bodies, fruits and seed and also roots, tubers and rhizomes. The plant parts also include harvested material, and also vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

+

Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on their surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, broadcasting, painting on or injection and, in the case of propagation material, in particular in the case of seed, also by applying one or more coats.

+

The present invention therefore also relates to a method of controlling unwanted plants or for regulating the growth of plants, preferably in crops of plants, where one or more compound(s) according to the invention is/are applied to the plants (for example harmful plants such as monocotyledonous or dicotyledonous weeds or unwanted crop plants), to the seed (for example grains, seeds or vegetative propagules such as tubers or shoot parts with buds) or to the area on which the plants grow (for example the area under cultivation). In this context, the compounds according to the invention can be applied for example pre-planting (if appropriate also by incorporation into the soil), pre-emergence or post-emergence. Examples of individual representatives of the monocotyledonous and dicotyledonous weed flora which can be controlled by the compounds according to the invention shall be mentioned, without the mention being intended as a limitation to certain species.

+

Monocotyledonous harmful plants of the genera: Aegilops, Agropyron, Agrostis, Alopecurus, Apera, Avena, Brachiaria, Bromus, Cenchrus, Commelina, Cynodon, Cyperus, Dactyloctenium, Digitaria, Echinochloa, Eleocharis, Eleusine, Eragrostis, Eriochloa, Festuca, Fimbristylis, Heteranthera, Imperata, Ischaemum, Leptochloa, Lolium, Monochoria, Panicum, Paspalum, Phalaris, Phleum, Poa, Rottboellia, Sagittaria, Scirpus, Setaria, Sorghum.

+

Dicotyledonous weeds of the genera: Abutilon, Amaranthus, Ambrosia, Anoda, Anthemis, Aphanes, Artemisia, Atriplex, Bellis, Bidens, Capsella, Carduus, Cassia, Centaurea, Chenopodium, Cirsium, Convolvulus, Datura, Desmodium, Emex, Erysimum, Euphorbia, Galeopsis, Galinsoga, Galium, Hibiscus, Ipomoea, Kochia, Lamium, Lepidium, Lindernia, Matricaria, Mentha, Mercurialis, Mullugo, Myosotis, Papaver, Pharbitis, Plantago, Polygonum, Portulaca, Ranunculus, Raphanus, Rorippa, Rotala, Rumex, Salsola, Senecio, Sesbania, Sida, Sinapis, Solanum, Sonchus, Sphenoclea, Stellaria, Taraxacum, Thlaspi, Trifolium, Urtica, Veronica, Viola, Xanthium.

+

The plants listed can be treated according to the invention in a particularly advantageous manner with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges stated above for the active compounds or mixtures also apply to the treatment of these plants. Particular emphasis is given to the treatment of plants with the compounds or mixtures specifically mentioned in the present text.

+

If the compounds according to the invention are applied to the soil surface before germination, either the emergence of the weed seedlings is prevented completely or the weeds grow until they have reached the cotyledon stage, but then stop their growth and, finally, die completely after three to four weeks have elapsed.

+

When the active compounds are applied post-emergence to the green plant parts, growth stops after the treatment, and the harmful plants remain in the growth stage of the time of application or die fully after a certain period of time, so that competition by weeds, which is harmful to the crop plants, is thus eliminated at an early point in time and in a sustained manner.

+

Although the compounds according to the invention display an outstanding herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops, for example dicotyledonous crops of the genera Arachis, Beta, Brassica, Cucumis, Cucurbita, Helianthus, Daucus, Glycine, Gossypium, Ipomoea, Lactuca, Linum, Lycopersicon, Miscanthus, Nicotiana, Phaseolus, Pisum, Solanum, Vicia, or monocotyledonous crops of the genera Allium, Ananas, Asparagus, Avena, Hordeum, Oryza, Panicum, Saccharum, Secale, Sorghum, Triticale, Triticum, Zea, are damaged only to an insignificant extent, or not at all, depending on the structure of the respective compound according to the invention and its application rate. This is why the present compounds are highly suitable for the selective control of unwanted vegetation in plant crops such as agriculturally useful plants or ornamentals.

+

Moreover, the compounds according to the invention (depending on their respective structure and the application rate applied) have outstanding growth-regulatory properties in crop plants. They engage in the plant metabolism in a regulatory fashion and can therefore be employed for the influencing, in a targeted manner, of plant constituents and for facilitating harvesting, such as, for example, by triggering desiccation and stunted growth. Moreover, they are also suitable for generally controlling and inhibiting unwanted vegetative growth without destroying the plants in the process. Inhibiting the vegetative growth plays an important role in many monocotyledonous and dicotyledonous crops since for example lodging can be reduced, or prevented completely, hereby.

+

As already mentioned above, it is possible to treat all plants and their parts according to the invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods, such as crossing or protoplast fusion, and parts thereof are treated. In a further preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The terms “parts”, “parts of plants” and “plant parts” have been explained above.

+

Particularly preferably, plants of the plant cultivars which are in each case commercially available or in use are treated according to the invention. Plant cultivars are to be understood as meaning plants having novel properties (“traits”) which have been obtained by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, bio- or genotypes.

+

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive (“synergistic”) effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the substances and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, higher, quality and/or a higher nutritional value of the harvested products, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.

+

Owing to their herbicidal and plant-growth-regulatory properties, the active compounds can also be employed for controlling harmful plants in crops of known genetically modified plants or genetically modified plants which are still to be developed. As a rule, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to certain pesticides, mainly certain herbicides, resistances to plant diseases or causative organisms of plant diseases, such as certain insects or microorganisms such as fungi, bacteria or viruses. Other special properties relate for example to the harvested material with regard to quantity, quality, storability, composition and specific constituents. Thus, transgenic plants with an increased starch content or a modified starch quality or those with a different fatty acid composition of the harvested material are known. Further particular properties may be tolerance or resistance to abiotec stresses, for example heat, cold, drought, salt and ultraviolet radiation.

+

It is preferred to use the compounds of the formula (I) according to the invention in economically important transgenic crops of useful plants and ornamentals, for example of cereals such as wheat, barley, rye, oats, sorghum and millet, rice, cassaya and maize or else crops of sugar beet, cotton, soya bean, oilseed rape, potato, tomato, peas and other vegetables.

+

It is preferred to employ the compounds of the formula (I) as herbicides in crops of useful plants which are resistant, or have been made resistant by recombinant means, to the phytotoxic effects of the herbicides.

+

Conventional ways of generating novel plants which, in comparison with existing plants, have modified properties are, for example, traditional breeding methods and the generation of mutants. Alternatively, novel plants with modified properties can be generated with the aid of recombinant methods (see, for example, EP-A-0221044, EP-A-0131624). For example, the following have been described in several cases: +

+

+

A large number of molecular-biological techniques by means of which novel transgenic plants with modified properties can be generated are known in principle; see, for example, I. Potrykus and G. Spangenberg (eds.) Gene Transfer to Plants, Springer Lab Manual (1995), Springer Verlag Berlin, Heidelberg. or Christou, “Trends in Plant Science” 1 (1996) 423-431.

+

To carry out such recombinant manipulations, it is possible to introduce nucleic acid molecules into plasmids, which permit a mutagenesis or sequence modification by recombination of DNA sequences. For example, base substitutions can be carried out, part-sequences can be removed, or natural or synthetic sequences may be added with the aid of standard methods. To link the DNA fragments with one another, it is possible to add adapters or linkers to the fragments; see, for example, Sambrook et al., 1989, Molecular Cloning, A Laboratory Manual, 2nd ed., Cold Spring Harbor Laboratory Press, Cold Spring Harbor, N.Y.; or Winnacker “Gene and Klone”, VCH Weinheim 2nd ed., 1996

+

The generation of plant cells with a reduced activity for a gene product can be achieved for example by the expression of at least one corresponding antisense RNA, a sense RNA for achieving a cosuppression effect or by the expression of at least one correspondingly constructed ribozyme, which specifically cleaves transcripts of the abovementioned gene product.

+

To this end, it is possible firstly to use DNA molecules which comprise all of the coding sequence of a gene product, including any flanking sequences which may be present, or else DNA molecules which only comprise parts of the coding sequence, it being necessary for these parts to be long enough to bring about an antisense effect in the cells. It is also possible to use DNA sequences which have a high degree of homology with the coding sequences of a gene product, but which are not entirely identical.

+

When expressing nucleic acid molecules in plants, the protein synthesized may be localized in any compartment of the plant cell. In order to achieve localization in a particular compartment, however, it is possible for example to link the coding region to DNA sequences which ensure the localization in a specific compartment. Such sequences are known to the skilled worker (see, for example, Braun et al., EMBO J. 11 (1992), 3219-3227; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850; Sonnewald et al., Plant J. 1 (1991), 95-106). The nucleic acid molecules can also be expressed in the organelles of the plant cells.

+

The transgenic plant cells can be regenerated by known techniques to give intact plants. In principle, the transgenic plants may be plants of any plant species, that is to say both monocotyledonous and dicotyledonous plants.

+

Thus, transgenic plants can be obtained which feature modified properties as the result of overexpression, suppression or inhibition of homologous (=natural) genes or gene sequences or expression of heterologous (=foreign) genes or gene sequences.

+

It is preferred to employ the compounds (I) according to the invention in transgenic crops which are resistant to growth regulators such as, for example, dicamba, or to herbicides which inhibit essential plant enzymes, for example acetolactate synthases (ALS), EPSP synthases, glutamine synthases (GS) or hydroxyphenylpyruvate dioxygenases (HPPD), or to herbicides from the group of the sulphonylureas, glyphosate, glufosinate or benzoylisoxazoles and analogous active compounds.

+

When the active compounds according to the invention are used in transgenic crops, effects are frequently observed—in addition to the effects on harmful plants which can be observed in other crops—which are specific for the application in the transgenic crop in question, for example a modified or specifically widened spectrum of weeds which can be controlled, modified application rates which may be employed for application, preferably good combinability with the herbicides to which the transgenic crop is resistant, and an effect on growth and yield of the transgenic crop plants.

+

The invention therefore also relates to the use of the compounds of the formula (I) according to the invention as herbicides for controlling harmful plants in transgenic crop plants.

+

The compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusting products or granules in the customary formulations. The invention therefore also provides herbicidal and plant growth-regulating compositions which comprise the compounds according to the invention.

+

The compounds according to the invention can be formulated in various ways according to which biological and/or physicochemical parameters are required. Possible formulations include, for example: wettable powders (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW) such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, capsule suspensions (CS), dusting products (DP), seed-dressing products, granules for scattering and soil application, granules (GR) in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes.

+

These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical technology], Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986, Wade van Valkenburg, “Pesticide Formulations”, Marcel Dekker, N.Y.; 1973; K. Martens, “Spray Drying” Handbook, 3rd Ed. 1979, G. Goodwin Ltd. London.

+

The necessary formulation assistants, such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J., H.v. Olphen, “Introduction to Clay Colloid Chemistry”; 2nd Ed., J. Wiley & Sons, N.Y.; C. Marsden, “Solvents Guide”; 2nd Ed., Interscience, N.Y. 1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Interface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Ed. 1986.

+

Based on these formulations, it is also possible to prepare combinations with other pesticidally active compounds, such as, for example, insecticides, acaracides, berbicides, fungicides, and also with safeners, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a tank mix.

+

Wettable powders are preparations which can be dispersed uniformly in water and, as well as the active compound, apart from a diluent or inert substance, also comprise surfactants of the ionic and/or nonionic type (wetting agents, dispersants), for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulphates, alkanesulphonates, alkylbenzenesulphonates, sodium lignosulphonate, sodium 2,2′-dinaphthylmethane-6,6′-disulphonate, sodium dibutylnaphthalenesulphonate or else sodium oleylmethyltauride. To prepare the wettable powders, the active herbicidal compounds are ground finely, for example in customary apparatus such as hammer mills, blower mills and air-jet mills and simultaneously or subsequently mixed with the formulation assistants.

+

Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else relatively high-boiling aromatics or hydrocarbons or mixtures of the organic solvents with addition of one or more surfactants of the ionic and/or nonionic type (emulsifiers). The emulsifiers used may, for example, be: calcium alkylarylsulphonates such as calcium dodecylbenzenesulphonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters, for example sorbitan fatty acid esters, or polyoxyethylene sorbitan esters, for example polyoxyethylene sorbitan fatty acid esters.

+

Dusting products are obtained by grinding the active compound with finely divided solid substances, for example talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.

+

Suspension concentrates may be water- or oil-based. They may be prepared, for example, by wet grinding by means of commercial bead mills and optional addition of surfactants as have, for example, already been listed above for the other formulation types.

+

Emulsions, for example oil-in-water emulsions (EW), can be prepared, for example, by means of stirrers, colloid mills and/or static mixers using aqueous organic solvents and optionally surfactants, as have, for example, already been listed above for the other formulation types.

+

Granules can be produced either by spraying the active compound onto adsorptive granulated inert material or by applying active compound concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or else mineral oils, onto the surface of carriers such as sand, kaolinites or of granulated inert material. It is also possible to granulate suitable active compounds in the manner customary for the production of fertilizer granules—if desired in a mixture with fertilizers.

+

Water-dispersible granules are prepared generally by the customary processes such as spray-drying, fluidized bed granulation, pan granulation, mixing with high-speed mixers and extrusion without solid inert material.

+

For the preparation of pan, fluidized bed, extruder and spray granules, see, for example, processes in “Spray-Drying Handbook” 3rd ed. 1979, G. Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical and Engineering 1967, pages 147 ff; “Perry's Chemical Engineer's Handbook”, 5th Ed., McGraw-Hill, New York 1973, pp. 8-57.

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For further details regarding the formulation of crop protection compositions, see, for example, G. C. Klingman, “Weed Control as a Science”, John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans, “Weed Control Handbook”, 5th Ed., Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

+

The agrochemical formulations contain generally from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of compounds according to the invention.

+

In wettable powders, the active compound concentration is, for example, from about 10 to 90% by weight; the remainder to 100% by weight consists of customary formulation constituents. In the case of emulsifiable concentrates, the active compound concentration may be from about 1 to 90% by weight, preferably from 5 to 80% by weight. Dust-type formulations contain from 1 to 30% by weight of active compound, preferably usually from 5 to 20% by weight of active compound; sprayable solutions contain from about 0.05 to 80% by weight, preferably from 2 to 50% by weight of active compound. In water-dispersible granules, the active compound content depends partly on whether the active compound is present in solid or liquid form and which granulation assistants, fillers, etc. are used. In the granules dispersible in water, the content of active compound is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.

+

In addition, the active compound formulations mentioned optionally comprise the respective customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, preservatives, antifreeze agents and solvents, fillers, carriers and dyes, defoamers, evaporation inhibitors and agents which influence the pH and the viscosity.

+

The term “active compounds” or “compounds” in each case also includes the active compound combinations mentioned herein.

+

According to the invention, the preparation of the compounds of the general structure (I) can be carried out by processes A to H.

+

Using, for example, according to process (A) methyl 2,2-dimethyl-8-[(2,6-diethyl-4-methyl)phenylacetyl]-1,3-dioxa-[4.4.0]-bicyclononane-7-carboxylate, the course of the process according to the invention can be represented by the reaction scheme below:

+

+embedded image + +

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Using, for example, according to process (B) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and pivaloyl chloride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (B) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and acetic anhydride as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

+

+embedded image + +

+

Using, for example, according to process (C) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and ethyl chloroformate as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

+

+embedded image + +

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Using, for example, according to process (D) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and methyl chloromonothioformate as starting materials, the course of the process according to the invention can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (E) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and methanesulphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (F) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and 2,2,2-trifluoroethyl methanethiophosphonyl chloride as starting materials, the course of the reaction can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (G) 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and NaOH as components, the course of the process according to the invention can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (H), variant α, 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1,3′,3a′,6α′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and ethyl isocyanate as starting materials, the course of the reaction can be represented by the reaction scheme below:

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+embedded image + +

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Using, for example, according to process (H), variant β, 5′-(2,6-diethyl-4-methylphenyl)-6′-hydroxy-2,2-dimethyl-1′,3′,3a′,6a′-tetrahydro-4′H-spiro[1,3-dioxolan-4,2′-pentalen]-4′-one and dimethylcarbamoyl chloride as starting materials, the course of the reaction may be represented by the scheme below:

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+embedded image + +

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The compounds, required as starting material in process (A) according to the invention, of the formula (II)

+

+embedded image + +

+

in which +
+A, B, X, Y, Z and R8 have the meaning given above +
+are novel. +

+

They can be prepared by methods known in principle.

+

The 5-aryl-4-ketocarboxylic esters of the formula (II) are obtained, for example, when 5-aryl-4-ketocarboxylic acids of the formula (XIII)

+

+embedded image + +

+

in which +
+X, Y, Z, A and B have the meaning given above +
+are esterified (cf., for example, Organikum, 15th Edition, Berlin, 1977, page 499) or alkylated (see Preparation Example). +

+

The arylketocarboxylic acids of the formula (XIII)

+

+embedded image + +

+

in which +
+A, B, X, Y and Z have the meaning given above +
+are novel; however, they can be prepared by methods known in principle (WO 07/080,066, WO 96/01 798, WO 97/14667, WO 98/39281, WO 01/74770). +

+

The arylketocarboxylic acids of the formula (XIII) are obtained, for example, when 2-phenyl-3-oxoadipic esters of the formula (XIV)

+

+embedded image + +

+

in which +
+A, B, X, Y and Z have the meaning given above and +
+R8 and R8′ represent alkyl (in particular C1-C8-alkyl) and, +
+when the compound of the formula (XVI) is used, R8 represents hydrogen +
+are decarboxylated, if appropriate in the presence of a diluent and if appropriate in the presence of a base or acid (cf., for example, Organikum, 15th Edition, Berlin, 1977, pages 519-521). +

+

The compound of the formula (XIV)

+

+embedded image + +

+

in which +
+A, B, X, Y, Z, R8, R8′ have the meaning given above and, +
+when the compound of the formula (XVI) is used, R8 represents hydrogen +
+are novel. +

+

The compounds of the formula (XIV) are obtained, for example,

+

when dicarboxylic semiester chlorides of the formula (XV)

+

+embedded image + +

+

in which +
+A, B and R8 have the meaning given above and +
+Hal represents chlorine or bromine +
+or carboxylic anhydrides of the formula (XVI) +

+

+embedded image + +

+

in which +
+A and B have the meaning given above +
+are acylated with a phenylacetic ester of the formula (XVII) +

+

+embedded image + +

+

in which +
+X, Y, Z and R8 have the meaning given above +
+in the presence of a diluent and in the presence of a base (cf., for example, M. S. Chambers, E. J. Thomas, D. J. Williams, J. Chem. Soc. Chem. Commun., (1987), 1228, cf. also the Preparation Examples). +

+

A further proven method for preparing the compounds, required as starting materials for process (A), of the formula (II) in which A, B, X, Y, Z and R8 have the meaning given above is also, for example, the coupling of benzyl zinc compounds of the general formula (XVIII)

+

+embedded image + +

+

in which X, Y and Z have the meaning given above and Hal represents a halogen atom, preferably chlorine or bromine, +
+if appropriate in the presence of a catalyst, with a dicarboxylic semiester chloride of the general formula (XV) or a carboxylic anhydride of the general formula (XVI). +

+

Both the preparation and the reaction of organic zinc compounds with carbonyl chlorides and carboxylic anhydrides are known in principle and can be carried out in close analogy to the processes described in the literature. More details are described, for example, in Chem. Commun. 2008, 5824, WO 2007/113294, Tetrahedron Letters 30, 5069-5072 (1989) or Chem. Rev. 1993, 93, 2117-2188.

+

The acid halides of the formula (III), carboxylic anhydrides of the formula (IV), chloroformic esters or chloroformic thioesters of the formula (V), chloromonothioformic esters or chlorodithioformic esters of the formula (VI), sulphonyl chlorides of the formula (VII), phosphorus compounds of the formula (VIII) and metal hydroxides, metal alkoxides or amines of the formulae (IX) and (X) and isocyanates of the formula (XI) and carbamoyl chlorides of the formula (XII) furthermore required as starting materials for carrying out the processes (B), (C), (D), (E), (F), (G) and (H) according to the invention are generally known compounds of organic of inorganic chemistry.

+

Some of the compounds of the formulae (XV), (XVI) and (XVII) are known compounds of organic chemistry or known from the patent applications cited at the outset and/or can be prepared in a simple manner by methods known in principle or can be prepared by the methods described in the patent applications cited at the outset.

+

To prepare benzyl zinc compounds of the formula (XVIII), benzyl compounds of the formula (XIX)

+

+embedded image + +

+

where X, Y and Z have the meaning given above and Hal represents a halogen atom, preferably chlorine or bromine, are used as starting material. Some benzyl compounds of the formula (XIX) are known, or they can be prepared by known processes (see, for example, Chem. Ber. 118, 1968 (1985), Monatshefte Chemie 135, 251 (2004), Acta Chem. Scand. 1963, 17 and Preparation Examples).

+

The process (A) is characterized in that compounds of the formula (II), in which A, B, X, Y, Z and R8 have the meaning given above are subjected to an intramolecular condensation in the presence of a base.

+

Suitable for use as diluents in the process (A) according to the invention are all organic solvents which are inert towards the reaction participants. Preference is given to using hydrocarbons, such as toluene and xylene, furthermore ethers, such as bibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, moreover polar solvents, such as dimethyl sulphoxide, sulpholane, dimethylformamide and N-methylpyrrolidone. It is furthermore possible to use alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol.

+

Suitable bases (deprotonating agents) for carrying out the process (A) according to the invention are all customary protonic ceptors. Preference is given to using alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, which may also be used in the presence of phase-transfer catalysts, such as, for example, triethylbenzylammonium chloride, tetrabutylammonium bromide, Adogen 464 (=methyltrialkyl(C8-C10)ammonium chloride) or TDA 1 (=tris(methoxyethoxyethyl)amine). It is furthermore possible to use alkali metals, such as sodium or potassium. Further, it is possible to employ alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and additionally also alkali metal alkoxides, such as sodium methoxide, sodium ethoxide and potassium tert-butoxide.

+

When carrying out the process (A) according to the invention, the reaction temperatures may be varied within a relatively wide range. In general, the process is carried out at temperatures between 0° C. and 250° C., preferably between 50° C. and 150° C.

+

The process (A) according to the invention is generally carried out under reduced pressure.

+

When carrying out the process (A) according to the invention, the reaction components of the formula (II) and the deprotonating bases are generally employed in about doubly equimolar amounts. However, it is also possible to use a relatively large excess (up to 3 mol) of one component or the other.

+

The process (B-α) is characterized in that compounds of the formula (I-a) are in each case reacted with carbonyl halides of the formula (III), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

Suitable for use as diluents in the process (B-α) according to the invention are all solvents which are inert towards the acid halides. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorbenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholan. If the acid halide is sufficiently stable to hydrolysis, the reaction can also be carried out in the presence of water.

+

Suitable acid binders for the reaction according to process (B-α) according to the invention are all customary acid acceptors. Preference is given to using tertiary amines, such as triethylamine, pyridine, diazabicyclooctane (DABCO), diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig-Base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.

+

The reaction temperatures in the process (B-α) according to the invention can be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.

+

When carrying out the process (B-α) according to the invention, the starting materials of the formula (I-a) and the carbonyl halide of the formula (III) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of the carbonyl halide. Work-up is carried out by customary methods.

+

The process (B-β) is characterized in that compounds of the formula (I-a) are reacted with carboxylic anhydrides of the formula (IV), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

Suitable diluents for use in the process (B-β) according to the invention are, preferably, the diluents which are also preferred when using acid halides. Besides this a carboxylic anhydride used in excess may simultaneously act as diluent.

+

Suitable acid binders, which are added, if appropriate, for process (B-β) are, preferably, the acid binders which are also preferred when using acid halides.

+

The reaction temperatures in the process (B-β) according to the invention may be varied within a relatively wide range. In general, the process is carried out at temperatures between −20° C. and +150° C., preferably between 0° C. and 100° C.

+

When carrying out the process (B-β) according to the invention, the starting materials of the formula (I-a) and the carboxylic anhydride of the formula (IV) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 5 mol) of carboxylic anhydride. Work-up is carried out by customary methods.

+

In general, diluent and excess carboxylic anhydride and the carboxylic acid formed are removed by distillation or by washing with an organic solvent or with water.

+

The process (C) is characterized in that compounds of the formula (I-a) are in each case reacted with chloroformic esters or chloroformic thio esters of the formula (V), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

Suitable acid binders for the reaction according to the process (C) according to the invention are all customary acid acceptors. Preference is given to use tertiary amines, such as triethylamine, pyrridine, DABCO, DBU, DBA, Hünig-Base and N,N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium oxide and calcium oxide, moreover alkali metal carbonates and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide.

+

Suitable diluents for use in the process (C) according to the invention are all solvents which are inert towards the chloroformic esters or chloroformic thio esters. Preference is given to using hydrocarbons, such as benzine, benzene, toluene, xylene and tetralin, furthermore halogenated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, moreover ketones, such as acetone and methyl isopropyl ketone, furthermore ethers, such as diethyl ether, tetrahydrofuran and dioxane, additionally carboxylic esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulphoxide and sulpholan.

+

When carrying out the process (C) according to the invention, the reaction temperatures can be varied within a relatively wide range. If the process is carried out in the presence of a diluent and an acid binder, the reaction temperatures, are generally between −20° C. and +100° C., preferably between 0° C. and 50° C.

+

The process (C) according to the invention is generally carried out under atmospheric pressure.

+

When carrying out the process (C) according to the invention, the starting materials of the formula (I-a) and the appropriate chloroformic ester or chloroformic thio ester of the formula (V) are generally each employed in approximately equivalent amounts. However, it is also possible to use a relatively large excess (up to 2 mol) of one component or the other. Work-up is carried out by customary methods. In general, precipitated salts are removed and the reaction mixture that remains is concentrated by removing the diluent under reduced pressure.

+

The process (D) according to the invention is characterized in that compounds of the formula (I-a) are in each case reacted with compounds of the formula (VI) in the presence of a diluent and, if appropriate, in the presence of an acid binder.

+

In preparation process (D), about one mol of chloromonothioformic ester or chlorodithioformic ester of the formula (VI) is employed per mole of the starting material of the formula (I-a) at from 0 to 120° C., preferably from 20 to 60° C.

+

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides, and also halogenated alkanes.

+

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

+

If, in a preferred embodiment, the enolate salt of the compounds (I-a) is prepared by addition of strong deprotonating agents, such as, for example, sodium hydride or potassium tert-butoxide, the further addition of acid binders may be dispensed with.

+

If acid binders are used, these are customary inorganic or organic bases; sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.

+

The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.

+

The process (E) according to the invention is characterized in that compounds of the formula (I-a) are in each case reacted with sulphonyl chlorides of the formula (VII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

In preparation process (E), about one mol of sulphonyl chloride of the formula (VII) is reacted per mole of the starting material of the formula (I-a) at from −20 to 150° C., preferably from 20 to 70° C.

+

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, nitrides, sulphones, sulphoxides or halogenated hydrocarbons, such as methylene chloride.

+

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.

+

If, in a preferred embodiment, the enolate salt of the compounds (I-a) is prepared by addition of strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.

+

If acid binders are used, these are customary inorganic or organic bases, for example sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine.

+

The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods.

+

The process (F) according to the invention is characterized in that compounds of the formula (I-a) are in each case reacted with phosphorus compounds of the formula (VIII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

In preparation process (F), to obtain compounds of the formula (I-e), from 1 to 2, preferably from 1 to 1.3, mol of the phosphorus compound of the formula (VIII) are reacted per mole of the compounds of the formula (I-a), at temperatures between −40° C. and 150° C., preferably between −10 and 110° C.

+

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, nitriles, alcohols, sulphides, sulphones, sulphoxides, etc.

+

Preference is given to using acetonitrile, dimethyl sulphoxide, tetrahydrofuran, dimethylformamide, methylene chloride.

+

Suitable acid binders which are added, if appropriate, are customary inorganic or organic bases, such as hydroxides, carbonates or amines. Sodium hydroxide, sodium carbonate, potassium carbonate, pyridine and triethylamine may be mentioned by way of example.

+

The reaction can be carried out at atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods of organic chemistry. The arising end products are preferably purified by crystallization, chromatographic purification or “incipient distillation” i.e. removal of the volatile components under reduced pressure.

+

The process (G) is characterized in that compounds of the formula (I-a) are reacted with metal hydroxides or metal alkoxides of the formula (IX) or amines of the formula (X), if appropriate in the presence of a diluent.

+

Suitable diluents for use in the process (G) according to the invention are, preferably, ethers, such as tetrahydrofuran, dioxane, diethyl ether, or else alcohols, such as methanol, ethanol, isopropanol, and also water.

+

The process (G) according to the invention is generally carried out under atmospheric pressure.

+

The reaction temperatures are generally between −20° C. and 100° C., preferably between 0° C. and 50° C.

+

The process (H) according to the invention is characterized in that compounds of the formula (I-a) are in each case reacted with (H-α) compounds of the formula (XI), if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, or (H-β) with compounds of the formula (XII), if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder.

+

In preparation process (H-α), about 1 mol of isocyanate of the formula (XI) is reacted per mole of starting material of the formula (I-a), at from 0 to 100° C., preferably from 20 to 50° C.

+

Suitable diluents which are added, if appropriate, are all inert organic solvents, such as ethers, amides, nitrides, sulphones, sulphoxides.

+

If appropriate, catalysts may be added to accelerate the reaction. Suitable for use as catalysts are, very advantageously, organotin compounds, such as, for example dibutyl tin dilaurate. The reaction is preferably carried out at atmospheric pressure.

+

In preparation process (H-β), about 1 mol of carbamoyl chloride of the formula (XII) is reacted per mole of starting material of the formula (I-a), at from −20 to 150° C., preferably at from 0 to 70° C.

+

Suitable diluents which are added, if appropriate, are all inert polar organic solvents, such as ethers, amides, sulphones, sulphoxides or halogenated hydrocarbons.

+

Preference is given to using dimethyl sulphoxide, tetrahydrofuran, dimethylformamide or methylene chloride.

+

If, in a preferred embodiment, the enolate salt of the compound of the formula (I-a) is prepared by addition of strong deprotonating agents (such as, for example, sodium hydride or potassium tert-butoxide), the further addition of acid binders may be dispensed with.

+

If acid binders are used, then customary inorganic or organic bases are suitable, for example sodium hydroxide, sodium carbonate, potassium carbonate, triethylamine or pyridine. The reaction can be carried at an atmospheric pressure or under elevated pressure and is preferably carried out at atmospheric pressure. Work-up is carried out by customary methods. The preparation and the use of the active compounds according to the invention is illustrated by the examples below.

+ + +PREPARATION EXAMPLES +Examples I-a-1 and I-a-2 +

+embedded image + +

+

In 50 ml of anhydrous N,N-dimethylformamide, 4.62 g (11.5 mmol) of methyl 8-[(2,6-diethyl-4-methylphenyl)acetyl]-2,2-dimethyl-1,3-dioxaspiro[4.4]nonane-7-carboxylate (according to Example (II-5)) and 2.57 g of potassium tert-butoxide are heated at 50° C. for 2 h. After cooling, the mixture is poured into ice-water, acidified to pH 3 using conc. hydrochloric acid and extracted three times with ethyl acetate. The organic phase is dried (magnesium sulphate), and the solvent is then distilled off and the residue is chromatographed on silica gel (ethyl acetate/hexane=50:50).

+Fraction A: +

anti-isomer (I-a-1); yield 1.70 g (40%); colourless crystals of m.p. 104-105° C.

+Fraction B: +

syn-isomer (I-a-2); yield 1.40 g (34%); colourless crystals of m.p. 88-89° C.

+Example I-a-3 +

+embedded image + +

+

In 40 ml of toluene, 0.79 g (2.64 mmol) of 2-(2,6-diethyl-4-methylphenyl)-3-hydroxy-3a,4,6,6a-tetrahydropentalene-1,5-dione (according to Example (I-a-4)), 0.58 g (6.6 mmol) of 2-methylidenepropane-1,3-diol and 20 mg of p-toluene sulphonic acid are heated on a water separator for 3 h, and the mixture is then concentrated using a rotary evaporator and taken up in ethyl acetate. The mixture is extracted with bicarbonate solution and water, dried (magnesium sulphate), the solvent is distilled off and the residue is chromatographed on silica gel (ethyl acetate/hexane v:v=35:65), which then affords the compound of the formula (I-a-3) in the form of colourless crystals.

+

Yield: 0.52 g (53%)

+

1H-NMR (400 MHz, CDCl3): δ=1.07 and 1.09 (in each case t, in each case 3H), 3.12 and 3.38 (in each case mc, in each case 1H), 4.10-4.37 (m, 4H), 4.39 (mc, 2H) ppm

+Example I-a-4 +

+embedded image + +

+

2 ml of a 2.5% strength solution of osmium tetroxide in t-butanol are added to 2.50 g (8.43 mmol) of 2-(2,6-diethyl-4-methylphenyl)-3-hydroxy-5-methylidene-4,5,6,6a-tetrahydropentalen-1(3 aH)-one (according to Example I-a-5) and 9.02 g (42.16 mmol) of sodium meta-periodate in 50 ml of a water/tert-butanol mixture (v/v=50:50), and the mixture is stirred at room temperature for 10 minutes. 50 ml of ethyl acetate are then added, and the mixture is stirred at room temperature for a further 2 h. The reaction mixture is then added to ice, taken up in ethyl acetate and extracted with water. After drying (magnesium sulphate) and distillative removal of the solvent, the residue is chromatographed on silica gel using ethyl acetate/hexane (v/v=30:70). This gives 1.86 g (74.1%) of the compound of the formula (I-a-4) as a viscose oil.

+

1H-NMR (400 MHz, CDCl3): δ=2.31 (s, 3H), 2.52 and 2.74 (in each case mc, broad, in each case 2H), 3.41 and 3.68 (in each case mc, broad, in each case 1H) ppm

+Example I-a-5 +

+embedded image + +

+

In 80 ml of N,N-dimethylformamide, 7.85 g (23.9 mmol) of methyl 2-[(2,6-diethyl-4-methyl-phenyl)acetyl]-4-methylidenecyclopentanecarboxylate (according to Example (II-1)) and 5.36 g (47.8 mmol) of potassium tert-butoxide are heated at 50° C. for 2 h. After cooling, the mixture is added to ice-water, acidified to pH 2 using conc. hydrochloric acid and extracted with ethyl acetate. The organic phase is washed twice with water, dried (magnesium sulphate) and concentrated using a rotary evaporator. Chromatographic purification on silica gel (mobile phase ethyl acetate/hexane v:v=40:60) gives 4.30 g (61%) of the compound of the formula (I-a-5) in the form of colourless crystals of melting point 127-128° C.

+

1H-NMR (400 MHz, CDCl3): δ=0.94 and 1.08 (in each case t, in each case 3H), 2.28 (s, 3H), 2.51 (mc, 4H), 4.89 (s, 2H) ppm

+Example I-a-18 +

+embedded image + +

+

0.164 g (1.62 mmol) of triethylamine is added to 0.161 g (0.54 mmol) of 2-(2,6-diethyl-4-methylphenyl)-3-hydroxy-3a,4,6,6a-tetrahydropentalen-1,5-dione (Example I-a-4) and 0.090 g (1.08 mmol) of N-methylhydroxylamine hydrochloride in 10 ml of acetonitrile, and the mixture is stirred at room temperature for 6 h. The mixture is then added to ice and taken up in ethyl acetate, and the organic phase is separated off and washed with water. Drying (magnesium sulphate), distillative removal of the solvent and chromatography on silica gel using ethyl acetate/hexane (v/v=25:75) finally affords 0.154 g (87%) of the desired compound of the formula (I-a-18) as a viscose yellowish oil.

+

1H-NMR (400 MHz, CDCl3): δ=2.62 (mc, 1H), 3.20 and 3.48 (in each case mc, in each case 1H), 3.82 (s, 3H) ppm

+

The following compounds of the formula (I-a) are obtained analogously to Examples (I-a-1) to (I-a-5) and (I-a-18) and in accordance with the general statements on the preparation:

+

+ + + + + + + + + +(I-a) + + + +embedded image + + + + + + + + + + + + + + + + + + +Ex. + + + + +M.p. [° C.] or 1H-NMR (400 MHz, + + + + + + + + + + + + + + + +No. +X +Y +Z +A +B +CDCl3, δ in ppm) +Isomerism + + + + + + + + + + + + + + + + +I-a-6 +C2H5 +CH3 +C2H5 +—O—CH(C2H5)—O—CH2— +181 +anti + + +I-a-7 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—O—CH2— +δ = 1.48 and 1.49 (2 s, in total 3 H), +anti + + + + + + + +3.74 (d, 1 H), 3.87 (d, 1H), 5.09 (s, br, 1 H) + + + +I-a-8 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +2.05-2.22 (m, 4H), 2.30 (s, 3H), 3.10 (mc, 1H), + + + + + + + + +3.38 (mc, 1 H), 3.88 (mc, 4H), 6.92 (s, 2H) + + + +I-a-9 +C2H5 +CH3 +C2H5 +—O—CH2—C(CH3)2—CH2—O— +96-97 + + + +I-a-10 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—O— +89-90 +syn/anti mixture + + +I-a-11 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +δ = 2.70-2.75 (m. 1H), 3.11 and 3.35 + + + + + + + + +(in each case mc, in each case 1H), + + + + + + + + +3.78 (mc, 1H), 3.88 (mc, 3H) + + + +I-a-12 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +117-118 +Mixture with respect + + + + + + + + +to the CH3-groups + + + + + + + + +at the acetal ring + + +I-a-13 +C2H5 +CH3 +C2H5 +—O—(CH2)4—O— +3.05 and 3.31 (in each case mc, in each + + + + + + + + +case 1H), 3.59 and 3.70 (in each case mc, + + + + + + + + +in each case 2H), 7.02 and + + + + + + + + +7.06 (in each case s, in each case 1H) + + + +I-a-14 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +3.10 and 3.39 (in each case mc, in each case 1H), + + + + + + + + +4.04-4.31 (m, 4H); 5.67 (s, 2H) + + + +I-a-15 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +79-80 +(R,R)-Configuration + + + + + + + + +of the CH3-groups + + + + + + + + +at the acetal ring + + +I-a-16 +C2H5 +CH3 +C2H5 +—S—(CH2)2—S— +δ = 2.61 (mc, 2H), 3.32 (mc, 1H), 6.98 (s, 1H) + + + +I-a-17 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +δ = 2.75-3.01 (m, 4H), 3.49 and 3.61 (in + + + + + + + + +each case mc, in each case 1H) + + + +I-a-18 +C2H5 +CH3 +C2H5 +═N—OCH3 +δ = 2.62 (mc, 1H), 3.20 and 3.48 (in each + + + + + + + + +case mc, in each case 1 H), 3.82 (s, 3 H) + + + +I-a-19 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—C(CH3)2—O— +δ = 1.09 and 1.12 (in each case t, + + + + + + + + +in each case 3 H), 1.14 and 1.15 + + + + + + + + +(in each case s, in each case 6H), + + + + + + + + +2.10-2.21 (m, 4 H), 3.08 and 3.34 + + + + + + + + +(in each case mc, in each case 1 H) + + + +I-a-20 +C2H5 +CH3 +C2H5 +—S—(CH2)3—O— +93-94 +syn/anti mixture + + +I-a-21 +C2H5 +C2H5 +C2H5 +CH2═ +173-174 + + + +I-a-22 +C2H5 +C2H5 +C2H5 +O═ +243-244 + + + +I-a-23 +C2H5 +C2H5 +C2H5 +—O—(CH2)2—O— +193-194 + + + +I-a-24 +C2H5 +C2H5 +C2H5 +—O—(CH2)3—O— +196-197 + + + +I-a-25 +C2H5 +CH3 +C2H5 +—OCH2CH(CH3)CH2O— +89-90 + + + +I-a-26 +C2H5 +CH3 +C2H5 +—OCH2CH(OCH3)CH2O— +171-172 + + + +I-a-27 +C2H5 +CH3 +C2H5 +—OCH2CH(OCH2C6H5)CH2O— +75-76 + + + +I-a-28 +C2H5 +CH3 +C2H5 +—OCH2CH(OC2H5)CH2O— +75-76 + + + +I-a-29 +C2H5 +CH3 +C2H5 +═NOi-C3H7 +143 + + + +I-a-30 +C2H5 +CH3 +C2H5 +═NO-cyclopropyl +79-80 + + + +I-a-31 +C2H5 +CH3 +C2H5 +═NOCH2-cyclopropyl +70-71 + + + +I-a-32 +C2H5 +CH3 +C2H5 +═NOCH(CH3)—C≡CH + 70 + + + +I-a-33 +C2H5 +CH3 +C2H5 +═NOCH2—C≡CH +61-62 + + + +I-a-34 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH2—O— +89-90 +syn/anti mixture + + +I-a-35 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +246 +syn/anti mixture + + +I-a-36 +CH3 +CH3 +CH3 +═CH2 +202-203 + + + +I-a-37 +CH3 +CH3 +CH3 +—O—(CH2)3—O— +225-226 + + + +I-a-38 +CH3 +CH3 +CH3 +—OCH2CH(CH3)CH2O— +225 + + + +I-a-39 +CH3 +CH3 +CH3 +—O—(CH2)2—O— +236 + + + +I-a-40 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +216-217 + + + +I-a-41 +CH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +203-204 + + + +I-a-42 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +186-187 + + + +I-a-43 +CH3 +CH3 +CH3 +═NOCH2—C≡CH +70-71 + + + +I-a-44 +CH3 +CH3 +CH3 +═NOCH3 +105-106 + + + +I-a-45 +OCH3 +CH3 +CH3 +CH2═ +201-202 + + + +I-a-46 +OCH3 +CH3 +CH3 +O═ +230 + + + +I-a-47 +OCH3 +CH3 +CH3 +—O—(CH2)3—O— +2.12 and 2.30 (in each case s, in each + + + + + + + + +case 3H), 3.09 and 3.34 (in each case mc, + + + + + + + + +in each case 1H), 3.27 (s, 3H) + + + +I-a-48 +OCH3 +CH3 +CH3 +—O—(CH2)2—O— +144-145 + + + +I-a-49 +OCH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +184-185 + + + +I-a-50 +OCH3 +CH3 +CH3 +—O—(CH2)4—O— +202-203 + + + +I-a-51 +OCH3 +CH3 +C2H5 +CH2═ +206 + + + +I-a-52 +OCH3 +CH3 +C2H5 +O═ +244 + + + +I-a-53 +OCH3 +CH3 +C2H5 +—O—(CH2)2—O— +263 + + + +I-a-54 +OCH3 +CH3 +C2H5 +—O—(CH2)3—O— +78-79 + + + +I-a-55 +C2H5 +CH3 +CH3 +CH2═ +164-165 + + + +I-a-56 +C2H5 +CH3 +CH3 +O═ +175 + + + +I-a-57 +C2H5 +CH3 +CH3 +—O—(CH2)2—O— +195 + + + +I-a-58 +C2H5 +CH3 +CH3 +—O—(CH2)3—O— +135-136 + + + +I-a-59 +C2H5 +CH3 +CH3 +—O—CH2—C(CH3)2—CH2—O— + + + + +I-a-60 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +198-199 + + + +I-a-61 +C2H5 +CH3 +CH3 +—O—(CH2)4—O— +208-209 + + + +I-a-62 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +81-82 +anti + + +I-a-63 +C2H5 +CH3 +H +—O—C(CH3)2—O—CH2— + + + + +I-a-64 +C2H5 +CH3 +H +—O—(CH2)4—O— +1.12 (t, 3H), 2.32 (s, 3H), 2.49 (1, 2H), + + + + + + + + +3.55 and 3.70 (in each case mc, + + + + + + + + +in each case 2H), 6.91 (d, 1H), + + + + + + + + +7.02 (d, 2H), 7.11 (s, 1H) + + + +I-a-65 +C2H5 +CH3 +H +—O—CH2—CH═CH—CH2—O— + + + + +I-a-66 +C2H5 +CH3 +H +—O—(CH2)3—O— +1.12 (t, 3H), 2.31 (s, 3H), 2.72 (mc, 1H), + + + + + + + + +3.08 (mc, 1H), 3.30 (mc, 1H), + + + +I-a-67 +C2H5 +CH3 +H +—O—(CH2)2—O— +79-80 + + + +I-a-68 +C2H5 +CH3 +C2H5 +═NOt-C4H9 +1.00 and 1.09 (in each case t, in each + + + + + + + + +case 3H), 1.22 (s, 9H), 2.30 (s, 3H) + + + +I-a-69 +C2H5 +CH3 +C2H5 +═NOi-C4H9 +0.90 (mc, 6H), 1.92 (hept, 1H), 3.20 and + + + + + + + + +3.39 (in each case mc, in each case 1H), + + + + + + + + +3.79 (mc, 2H), 6.91 and 6.93 + + + + + + + + +(in each case s, in each case 1H) + + + +I-a-70 +C2H5 +CH3 +C2H5 +═NOCH2CF3 +2.60-2.86 (m, 3H), 3.22 and 3.51 (in each + + + + + + + + +case mc, in each case 1H), 4.48 (mc, 2H) + + + +I-a-71 +C2H5 +CH3 +H +CH2═ +172 + + + +I-a-72 +C2H5 +CH3 +C2H5 +═NOH +119-120 + + + +I-a-73 +C2H5 +CH3 +H +O═ +68-69 + + + +I-a-74 +C2H5 +CH3 +C2H5 +—O—CH(C2H5)—CH2—O + +syn/anti mixture + + +I-a-75 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH(CH3)—O— + +Mixture with respect + + + + + + + + +to the CH3-groups at + + + + + + + + +the acetal ring + + + + + + +
+ +

+Example I-b-1 +

+embedded image + +

+

At room temperature, 0.100 g (0.27 mmol) of the compound I-a-1 according to the invention (anti-isomer), 23.3 mg (0.297 mmol) of acetyl chloride and 82 mg (0.297 mmol) of triethylamine are stirred in 5 ml of dichloromethane for 2 h. The reaction mixture is poured onto ice, taken up in dichloromethane, washed with water, dried (magnesium sulphate) and concentrated using a rotary evaporator. Chromatography on silica gel (mobile phase ethyl acetate/hexane v:v=30:70) gives the compound of the formula (I-b-1) according to the invention as a colourless oil. Yield 76.6 mg (68%).

+

1H-NMR (400 MHz, CDCl3): δ 1.39 (s, 6H), 2.10 (s, 3H), 2.21 (s, 3H), 3.85 (dd, 2H) ppm

+

The following compounds of the formula (I-b) are obtained analogously to Example (I-b-1) and in accordance with the general statements on the preparation:

+

+ + + + + + + + + +(I-b) + + + +embedded image + + + + + + + + + + + + + + + + + + + + +Ex. + + + + + + +M.p. [° C.] or 1H-NMR (400 MHz, + + + +No. +X +Y +Z +A +B +R1 +CDCl3, δ in ppm) +Isomerism + + + + + + + + + + + + + + + + + +I-b-2 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +C2H5 + 83 +anti + + +I-b-3 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +i-C3H7 +108-109 +anti + + +I-b-4 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +H3C—O—CH2— +3.29 (s, 3H), 3.39 (mc, 1 H), 3.88 (dd, +anti + + + + + + + + +2H), 4.02 (s, 2 H) + + + +I-b-5 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +t-C4H9 +114-115 +anti + + +I-b-6 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +C2H5 +1.12 (t, 3 H), 2.49 (q, 2 H), 3.90 (dd, 2 H) +syn + + +I-b-7 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +i-C3H7 +δ = 1.32 (d, 6H), 2.60 (hept, 1H), 3.19 +syn + + + + + + + + +(mc, 1H), 4.01 (mc, 1H) + + + +I-b-8 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +t-C4H9 + 73 +syn + + +I-b-9 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +C2H5 +δ = 1.01 (3 × t, 9 H), 2.70-2.98 (m, 5 H) + + + +I-b-10 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +H3C—O—CH2— +δ = 2.62 (mc, 1 H), 2.70-2.97 (m, 5 H), + + + + + + + + + +3.32 (s, 3 H), 4.02 (dd, 2H) + + + +I-b-11 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +i-C3H7 +δ = 1.09 (d, 6 H), 2.58 (hept, 1 H), 3.48 + + + + + + + + + +and 4.20 (in each case mc, in each case + + + + + + + + + +1H) + + + +I-b-12 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +i-C3H7 +116-117 + + + + + + +I-b-13 +C2H5 +CH3 +C2H5 + +embedded image + + +i-C3H7 +108-109 + + + + + + +I-b-14 +C2H5 +CH3 +C2H5 +—OCH2CH(CH3)CH2O— +i-C3H7 +116 + + + +I-b-15 +C2H5 +CH3 +C2H5 +—O—CHCH3—CH2—CHCH3—O— +i-C3H7 +1.00-1.26 (m, 18H), 2.58, hept, 1H), 3.20 +(R,R)-Configuration + + + + + + + + +(mc, 1H), 3.90-4.00 (m, 2 + 1H) +of the CH3-groups + + + + + + + + + +at the acetal ring + + +I-b-16 +C2H5 +CH3 +C2H5 +—OCH2CH(OC2H5)CH2O— +i-C3H7 +2.59 (hept, 1H), 3.19 (mc, 1H), 3.40 mc, + + + + + + + + + +1H), 3.50 (mc, 3H), 3.98 (mc, 2H), 4.22 + + + + + + + + + +(mc, 1H) + + + +I-b-17 +C2H5 +CH3 +C2H5 +—OCH2CH(OCH2C6H5)CH2O— +i-C3H7 +1.09 m, 3H), 3.18 (mc, 1H), 3.40 (mc, + + + + + + + + + +1H), 3.69-4.00 (m, 5H), 4.60 (s, 2H) + + + +I-b-18 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +CH3 +132 + + + +I-b-19 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +t-C4H9 +129-130 +syn/anti mixture + + +I-b-20 +C2H5 +CH3 +C2H5 +—S—(CH2)3—O— +t-C4H9 +1.07 (s, 9H), 2.98-3.03 (m, 2H), 3.76 (mc, +syn/anti mixture + + + + + + + + +2H), 4.00 (mc, 1H) + + + +I-b-21 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +i-C3H7 +1.04 (mc, 6H), 2.60 (hept, 1H), 3.01 (mc, +syn/anti mixture + + + + + + + + +1H), 3.95-4.12 (m, 3H) + + + +I-b-22 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +t-C4H9 +1.05 (s, 9H), 2.77 (mc, 1H), 3.18 (mc, + + + + + + + + + +1H), 3.75-3.94 (m, 5H) + + + +I-b-23 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +CH3 +2.11 and 2.32 (jes, in each case 3H), 3.18 + + + + + + + + + +(mc, 1H), 3.72-3.90 (m, 4H), 3.95 (mc, + + + + + + + + + +1H) + + + +I-b-24 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +C2H5 + 99-100 + + + +I-b-25 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +C(CH3)2CH2Cl +1.10 and 1.15 (in each case s, in each case + + + + + + + + + +3H), 1.58 (mc, 2H), 1.82 (mc, 1H), 2.03- + + + + + + + + + +2.10 (m. 2H), 3.40 and 3.48 (in each case + + + + + + + + + +d, in each case 1H) + + + +I-b-26 +C2H5 +CH3 +C2H5 +CH2═ +t-C4H9 +1.05 (s, 9H), 2.22-2.40 (m, 5H), 2.54-2.74 + + + + + + + + + +(m, 5H), 4.91 (mc, 2H) + + + +I-b-27 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +t-C4H9 +77-78 + + + +I-b-28 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +H3C—O—CH2— +94-95 + + + +I-b-29 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +i-C3H7 +95-96 + + + +I-b-30 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +—C(CH3)2C2H5 +93-94 + + + +I-b-31 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +i-C3H7 +1.05 and 1.10 (in each case mc, in each + + + + + + + + + +case 6H), 2.59 (hept, 1H), 3.20 (mc, 1H), + + + + + + + + + +3.90 (mc, 4H), 4.00 (mc, 1H) + + + +I-b-32 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +t-C4H9 +108-109 + + + +I-b-33 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +C6H5 +2.28 (s, 3H), 3.90 (mc, 4H), 6.88 and 6.91 + + + + + + + + + +(in each case s, in each case 1H), 7.41 (t, + + + + + + + + + +2H), 7.60 (t, 2H), 7.90 (d, 2H) + + + +I-b-34 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +p-Cl—C6H5 +2.30 (s, 3H), 3.88 (mc, 4H), 7.40 (d, 2H), + + + + + + + + + +7.82 (d, 2H) + + + +I-b-35 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +p-CH3—C6H5 +2.30 and 2.38 (in each case s, in each case + + + + + + + + + +3H), 3.88 (mc, 4H), 4.21 (mc, 1H), 7.20 + + + + + + + + + +(d, 2H), 7.79 (d, 2H) + + + +I-b-36 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +p-OCH3—C6H5 +120-121 + + + +I-b-37 +CH3 +CH3 +CH3 +CH2═ +t-C4H9 + 87 + + + +I-b-38 +CH3 +CH3 +CH3 +CH2═ +i-C3H7 +1.03 and 1.11 (2 × d, Σ 6H), 2.00, 2.05 + + + + + + + + + +and 2.21 (in each case s, in each case 3H), + + + + + + + + + +2.57 (hept, 1H), 4.90 (mc, 2H) + + + +I-b-39 +CH3 +CH3 +CH3 +—O—(CH2)2—O— +i-C3H7 +1.02 and 1.08 (2 × d, Σ 6H), 2.03, 2.11 + + + + + + + + + +and 2.23 (in each case s, in each case 3H), + + + + + + + + + +2.58 (hept, 1H), 3.88 (mc, 4H) + + + +I-b-40 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +t-C4H9 +134-135 + + + +I-b-41 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +i-C3H7 +106-107 + + + +I-b-42 +CH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +i-C3H7 +1.02 and 1.09 (2 × d, Σ 6H), 2.57 (hept, + + + + + + + + + +1H), 3.88 (mc, 4H), 4.00-4.31 (m, 4H), + + + + + + + + + +5.65 (mc, 2H) + + + +I-b-43 +CH3 +CH3 +CH3 +—OCH2CH(CH3)CH2O— +i-C3H7 +0.71 and 0.88 (in each case d, Σ 3H), 1.02 + + + + + + + + + +and 1.10 (in each case mc, in each case + + + + + + + + + +3H), 2.58 (mc, 1H), 3.30-3.45 (rn, 2H), + + + + + + + + + +3.40-3.88 (m, 3H) + + + +I-b-44 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +i-C4H9 +0.88 (mc, 6H), 1.48 (s, 6H), 3.31 (mc, +syn/anti mixture + + + + + + + + +1H), 3.83 and 3.89 (in each case d, in each + + + + + + + + + +case IH), 6.82 (s, 2H) + + + +I-b-45 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +—C(CH3)2C2H5 + 88 +syn/anti mixture + + +I-b-46 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +i-C3H7 +1.01 (mc, 6H), 1.38 (s, 6H), 2.58 (hept, +syn/anti mixture + + + + + + + + +1H), 3.32 (mc, 1H), 3.85 and 3.90 (in each + + + + + + + + + +case d, in each case 2H), 3.88 (mc, 1H) + + + +I-b-47 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +H3C—O—CH2— +1.38 (s, 6H), 3.28 (s. 3H), 3.85 and 3.89 +syn/anti mixture + + + + + + + + +(in each case d, in each case 1H), 3.98 and + + + + + + + + + +4.04 (in each case d, in each case 1H), + + + + + + + + + +6.84 (s, 2H) + + + +I-b-48 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +t-C4H9 +97-98 +syn/anti mixture + + +I-b-49 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +CH3 +1.40 (s, 6H), 2.05 (s, 3H), 2.10 (s, 6H), +syn/anti mixture + + + + + + + + +2.26 (s, 3H), 3.84 and 3.88 (in each case + + + + + + + + + +d, in each case 1H) + + + +I-b-50 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +C2H5 +1.05 (t, 3H), 1.39 (s, 6H), 2.38 (q, 2H), +syn/anti mixture + + + + + + + + +3.34 (mc, 1H), 3.85 and 3.90 (in each case + + + + + + + + + +d, in each case 1H), 3.92 (mc, 1H) + + + +I-b-51 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +C(CH3)2CH2Cl +90-91 +syn/anti mixture + + +I-b-52 +CH3 +CH3 +CH3 +O═ +C(CH3)2CH2Cl +1.12 and 1.17 (in each case s, in each case + + + + + + + + + +3H), 3.43 and 3.46 (in each case d, in each + + + + + + + + + +case 3H), 6.83 (s, 2H) + + + +I-b-53 +CH3 +CH3 +CH3 +O═ +H3C—O—CH2— +1.99, 2.09 and 2.25 (in each case s, in + + + + + + + + + +each case 3H), 3.30 (s, 3H), 3.51 (mc, + + + + + + + + + +1H), 4.03 (s, 2H) + + + +I-b-54 +CH3 +CH3 +CH3 +O═ +i-C3H7 +1.04 and 1.07 (in each case d, in each case + + + + + + + + + +3H), 2.56 (hept, 1H), 3.50 and 4.12 (in + + + + + + + + + +each case mc, in each case 1H) + + + +I-b-55 +CH3 +CH3 +CH3 +O═ +—C(CH3)2C2H5 +0.61 (t, 3H), 1.42 (q, 2H), 2.39-2.85 (m, + + + + + + + + + +4H), 6.83 (s, 2H) + + + +I-b-56 +CH3 +CH3 +CH3 +O═ +i-C4H9 +0.80 (mc, 6H), 1.95 (hept, I H), 2.40-2.85 + + + + + + + + + +(m, 4H) + + + +I-b-57 +CH3 +CH3 +CH3 +O═ +C2H5 +1.05 (t, 3H), 2.40 (q, 2H), 3.49 and 4.16 + + + + + + + + + +(in each case mc, in each case 1H) + + + +I-b-58 +CH3 +CH3 +CH3 +═NOCH2—C≡CH +i-C3H7 +1.02 and 1.11 (in each case d, in each case + + + + + + + + + +3H), 2.41 (mc, 1H), 2.55-2.94 (m, 5H), + + + + + + + + + +4.51 (mc, 2H) + + + +I-b-59 +CH3 +CH3 +CH3 +═NOCH2—C≡CH +t-C4H9 +1.09 (s, 9H), 2.42 (mc, 1H), 2.63-3.08 (m, + + + + + + + + + +4H), 4.52 (mc, 1H) + + + +I-b-60 +CH3 +CH3 +CH3 +═O +t-C4H9 +1.08 (s, 9H), 1.99, 2.06 and 2.22 (in each + + + + + + + + + +case s, in each case 3H), 3.50 and 4.11 (in + + + + + + + + + +each case mc, in each case 1H) + + + +I-b-61 +OCH3 +CH3 +CH3 +═O +i-C3H7 +1.10 (mc, 6h), 2.30 (s, 3H), 3.48 (mc, + + + + + + + + + +1H), 3.68 (s, 3H), 4.12-4.28 (m, 1H) + + + +I-b-62 +OCH3 +CH3 +CH3 +═CH2 +i-C3H7 +1.10 (mc, 6H), 2.00 and 2.29 (in each case + + + + + + + + + +s, in each case 3H), 3.65 (s, 3H), 4.90 + + + + + + + + + +(mc, 2H) + + + +I-b-63 +OCH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +i-C3H7 +1.05-1.14 (m, 5H), 2.60 (hept, 1H), 3.68 + + + + + + + + + +and 3.70 (in each case s, Σ 3H), 5.63 (mc, + + + + + + + + + +2H) + + + +I-b-64 +OCH3 +CH3 +CH3 +—O—(CH2)3—O— +i-C3H7 +1.08-1.15 (m, 6H), 2.61 (hept, 1H), 3.66 + + + + + + + + + +(s, 3H), 6.50 and 6.63 (in each case s, in + + + + + + + + + +each case 1H) + + + +I-b-65 +OCH3 +CH3 +CH3 +—O—(CH2)2—O— +i-C3H7 +1.10 (mc, 6H), 2.62 (hept, 1H), 3.68 s, + + + + + + + + + +3H), 3.88 (mc, 4H) + + + +I-b-66 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +CH3 +1.07 and 1.10 (in each case t, Σ6H), 1.40 +anti + + + + + + + + +(s, 6H), 2.05 and 2.06 (in each case s, in + + + + + + + + + +each case 3H), 3.84 and 3.88 (in each case + + + + + + + + + +d, in each case 1H) + + + +I-b-67 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +C2H5 +1.05 (mc, 3H), 1.10 (t, 3H), 2.05 and 2.28 +anti + + + + + + + + +(in each case s, in each case 3H), 2.34 + + + + + + + + + +(mc, 2H) + + + +I-b-68 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +i-C4H9 +0.79 (mc, 6H), 1.38 (s, 6H), 3.32 (mc, +anti + + + + + + + + +1H), 3.85 (mc, 2H), 3.94 (mc, 1H) + + + +I-b-69 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +i-C3H7 +1.05 (mc, 6H), 1.39 (s, 6H), 2.55 (hept, +anti + + + + + + + + +1H), 3.33 (mc, 1H), 3.89 (mc, 2H), 3.97 + + + + + + + + + +(mc, 1H) + + + +I-b-70 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +t-C4H9 +79-80 +anti + + +I-b-71 +C2H5 +CH3 +CH3 +O═ +t-C4H9 +1.06 (s, 9H), 2.27 (s, 3H), 3.50 and 4.15 + + + + + + + + + +(in each case mc, in each case 1H) + + + +I-b-72 +C2H5 +CH3 +CH3 +CH2═ +i-C3H7 +0.95-1.10 (m, 9H), 2.26 (s, 3H), 2.52-2.70 + + + + + + + + + +(m, 4H), 4.90 (mc, 2H) + + + +I-b-73 +C2H5 +CH3 +CH3 +CH2═ +t-C4H9 +0.98 and 1.03 (in each case t, Σ 3H), 1.06 + + + + + + + + + +(s, 9H), 3.18 and 3.88 (in each case mc, in + + + + + + + + + +each case 1H), 4.91 (mc, 2H) + + + +I-b-74 +C2H5 +CH3 +CH3 +—O—(CH2)3—O— +t-C4H9 +1.08 (s, 9H), 2.25-2.33 (m, 1H), 3.15 (mc, + + + + + + + + + +1H), 3.70-3.90 (m, 5H) + + + +I-b-75 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +t-C4H9 +103-104 + + + +I-b-76 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +i-C3H7 +84-85 + + + +I-b-77 +C2H5 +CH3 +CH3 +—O—(CH2)4—O— +i-C3H7 +101 + + + +I-b-78 +C2H5 +CH3 +CH3 +—O—(CH2)4—O— +t-C4H9 +119-120 + + + +I-b-79 +C2H5 +CH3 +CH3 +—O—(CH2)2—O— +i-C3H7 +1.06 (mc, 6H), 2.47 (hept, 1H), 3.19 (mc, + + + + + + + + + +1H), 3.85-3.95 (m, 5H) + + + + + + +
+ +

+Example I-e-1 +

+embedded image + +

+

At room temperature, 82 mg (0.81 mmol) of triethylamine are added to 0.100 g (0.27 mmol) of the compound (I-a-1) according to the invention and 28 mg (0.30 mmol) of methyl chloroformate in 5 ml of dichloromethane, and the mixture is stirred for another 1 h. The reaction mixture is poured into ice-water, taken up in dichloromethane, washed with water, dried (magnesium sulphate), and the solvent is distilled off.

+

Chromatographic purification on silica gel (ethyl acetate/hexane v/v=20:80) gives 104 mg (90%) of the desired compound of the formula (I-c-1) in the form of colourless crystals of melting point 111-112° C.

+Example I-c-17 +

+embedded image + +

+

0.98 ml of 2.5% strength solution of osmium tetroxide in n-butanol is added to 1.50 g (4.05 mmol) of 2-(2,6-diethyl-4-methylphenyl)-5-methylidene-3-oxo-3,3a,4,5,6,6a-hexahydropentalen-1-yl ethyl carbonate (Example I-c-5) and 4.33 g (20.24 mmol) of sodium meta-periodate in 150 ml of a water/tert-butanol mixture (v/v=50:50), and the mixture is stirred at room temperature for 10 minutes. 50 ml of ethyl acetate are then added, and the mixture is stirred at room temperature for another 2 h.

+

The reaction mixture is poured onto ice, taken up in ethyl acetate and extracted with water. After drying (magnesium sulphate) and distillative removal of the solvent, the residue is chromatographed on silica gel using ethyl acetate/hexane (v/v=30:70). This gives 1.00 g (66%) of the desired compound of the formula (I-c-17) as a viscose oil.

+

1H-NMR (400 MHz, CDCl3): δ=1.26 (t, 3H), 3.51 and 4.31 (in each case mc, in each case 1H), 4.20 (mc, 2H) ppm

+

The following compounds of the formula (I-c) are obtained analogously to Examples (I-c-1) and (I-c-17) and in accordance with the general statements on the preparation:

+

+ + + + + + + + + +(I-c) + + + +embedded image + + + + + + + + + + + + + + + + + + + + +Ex. + + + + + + +M.p. [° C.] or 1H-NMR (400 MHz, + + + +No. +X +Y +Z +A B +M +R2 +CDCL3, δ in ppm) +Isomerism + + + + + + + + + + + + + + + + + + +I-c-2 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +O +i-C3H7 +δ = 1.21 (d, 6 H), 1.88 and 1.98 (in +anti + + + + + + + + + +each case mc, in each case 1 H), 3.89 + + + + + + + + + + +(dd. 2 H), 4.81 (quint, 1H) + + + +I-c-3 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +O +i-C3H7 +δ =1.32 (d, 6 H), 1.92-2.13 (m, 3 H), +syn + + + + + + + + + +3.92 (dd, 2H), 4.83 (quint, 1 H) + + + +I-c-4 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +O +CH3 +132-133 +syn + + +I-c-5 +C2H5 +CH3 +C2H5 +═CH2 +O +C2H5 +δ = 1.26 (t, 3H), 3.20 (mc, 1 H), 4.02 + + + + + + + + + + +(mc, 1H), 4.82 (mc, 2 H). + + + +I-c-6 +C2H5 +CH3 +C2H5 +—O—CH2—C(CH3)2—CH2—O— +O +C2H5 +125-126 + + + +I-c-7 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +O +C2H5 +δ = 1.08, 1.09 and 1.22 (in each case t, + + + + + + + + + + +in each case 3H), 3.20 (mc, 1 H), 3.89 + + + + + + + + + + +(mc, 4 H), 4.04 (mc, 1H), 4.19 (mc, + + + + + + + + + + +2H) + + + +I-c-8 +C2H5 +CH3 +C2H5 +—O—CHCH3—CH2—O— +O +C2H5 +79 +syn/anti mixture + + +I-c-9 +C2H5 +CH3 +C2H5 +—O—(CH2)4—O— +O +C2H5 +113 + + + +I-c-10 +C2H5 +CH3 +C2H5 +—O—CHCH3—CH2—CHCH3—O— +O +C2H5 +δ = 1.02-1.28 (m, 15 H), 3.20 (mc, +Isomer mixture with + + + + + + + + + +1H), 3.80-4.01 (m, 3 H), 4.18 (mc, +CH3-groups at the acetal + + + + + + + + + +2H) +ring + + +I-c-11 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +O +C2H5 +δ = 1.08. 1.12 and 1.24 (in each case t, + + + + + + + + + + +in each case 3 H), 4.01-4.32 (m, 7 H), + + + + + + + + + + +5.65 (s, 2 H) + + + + + + +I-c-12 +C2H5 +CH3 +C2H5 + +embedded image + + +O +C2H5 +119 + + + + + + +I-c-13 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)O— +O +C2H5 +δ = 1.05-1.25 (m, 15H), 3.20 and 3.92 +(R,R)-Configuration of + + + + + + + + + +(in each case mc, in each case 1 H), +the CH3-groups at the + + + + + + + + + +4.00 (mc, 2H), 4.18 (mc, 2 H) +acetal ring + + +I-c-14 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +O +C2H5 +110 + + + +I-c-15 +C2H5 +CH3 +C2H5 +—S—(CH2)2—S— +O +C2H5 +δ = 1.25 (t, 3H), 2.61 (mc, 2H), 3.35 + + + + + + + + + + +(mc, 5H), 4.19 (mc, 3H), 6.90 (s, 2H) + + + +I-c-16 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +O +C2H5 +δ = 1.26 (t, 3H), 2.83 (mc, 3H), 2.93 + + + + + + + + + + +(mc, 3H), 4.20 (mc, 2H), 4.22 (mc, + + + + + + + + + + +1H) + + + +I-c-17 +C2H5 +CH3 +C2H5 +═O +O +C2H5 +1.26 (t, 3 H), 3.51 and 4.31 (in each + + + + + + + + + + +case mc, in each case 1 H), 4.20 (mc, + + + + + + + + + + +2H) + + + +I-c-18 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—C(CH3)2—O— +O +C2H5 +116-117 + + + +I-c-19 +C2H5 +CH3 +C2H5 +—S—(CH2)3—O— +O +C2H5 +1.24 (t, 3H), 3.00 (mc, 2H), 3.72 (mc, +syn/anti mixture + + + + + + + + + +2H), 4.18 (mc, 1H) + + + +I-c-20 +C2H5 +CH3 +C2H5 +—S—(CH2)3—S— +O +CH3 +2.62 (mc, 1H), 2.80-2.98 (m, 5H), 3.49 + + + + + + + + + + +(mc, 1H), 3.78 (s, 1H), 4.23 (mc, 1H) + + + +I-c-21 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +O +CH3 +1.08 and 1.12 (in each case t, in each + + + + + + + + + + +case 3H), 3.75 (s, 3H), 4.02 (mc, 2H), + + + + + + + + + + +4.16-4.32 (m, 3H), 5.67 (s, 2H) + + + +I-c-22 +C2H5 +CH3 +C2H5 +—O—CH2—C(CH3)2—CH2—O— +O +C2H5 +98-99 + + + +I-c-23 +C2H5 +CH3 +C2H5 +—O—CH2—C(CH3)2—CH2—O— +O +CH3 +126-127 + + + +I-c-24 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)O— +O +CH3 +1.03-1.22 (m, 12H), 3.20 (mc, 1H), +(R,R)-Configuration of + + + + + + + + + +3.75 (doubled singlet, Σ 3H), 3.90- +the CH3-groups at the + + + + + + + + + +4.02 (m, 3H) +acetal ring + + +I-c-25 +C2H5 +CH3 +C2H5 +—O—CH2—C(OCH3)—CH2—O— +O +C2H5 +1.23 (t, 3H), 2.70-2.79 (m, 1H), 4.19 + + + + + + + + + + +(mc, 2H), 3.10 (mc, 1H), 3.38 (s, 3H), + + + +I-c-26 +C2H5 +CH3 +C2H5 +—O—CH2CH(OC2H5)CH2—O— +O +C2H5 +1.03-1.28 (m, 12H); 3.20 and 3.39 (in + + + + + + + + + + +each case mc, in each case 1H), 3.95- + + + + + + + + + + +4.05 (m, 2H), 4.11-4.25 (m, 3H) + + + +I-c-27 +C2H5 +CH3 +C2H5 +—OCH2—CH(OC2H5)CH2—O— +O +CH3 +1.00-1.21 (m, 12H), 3.76 (s, 3H), 3.92- + + + + + + + + + + +4.05 (m, 2H), 4.21 (mc, 1H) + + + +I-c-28 +C2H5 +CH3 +C2H5 +—OCH2—CH(OCH2C6H5)CH2—O— +O +C2H5 +1.22 (t, 3H), 2.95 (mc, 2H), 4.15 (mc, + + + + + + + + + + +2H), 4.55 (s, 2H), 6.88 and 6.91 (in + + + + + + + + + + +each case s, in each case 1H), 7.27- + + + + + + + + + + +7.85 (m, 5H) + + + +I-c-29 +C2H5 +CH3 +C2H5 +—OCH2—CH(OCH2C6H5)CH2—O— +O +CH3 +2.05-2.12 (m, 2H), 3.41 (mc, 1H), 3.74 + + + + + + + + + + +(s, 3H), 4.60 (s, 2H), + + + +I-c-30 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +O +C2H5 +94-95 +syn/anti mixture + + +I-c-31 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +O +CH3 +3.00 (mc, 2H), 3.77 (s, 3H), 3.96 (mc, +syn/anti mixture + + + + + + + + + +1H), 4.02-4.10 (m, 2H) + + + +I-c-32 +C2H5 +CH3 +C2H5 +—S—(CH2)3—O— +O +CH3 +2.95-3.05 (m, 2H), 3.25 (mc, 1H), 3.72 +syn/anti mixture + + + + + + + + + +(mc, 2H), 3.75 (s, 3H), 4.08 (mc, 1H) + + + +I-c-33 +C2H5 +CH3 +C2H5 +—S—(CH2)2—O— +O +i-C3H7 +1.23 (6H), 3.01 (mc, 2H), 4.08 (mc, +syn/anti mixture + + + + + + + + + +2H), 4.81 (mc, 1H) + + + +I-c-34 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +O +i-C3H7 +1.22 (mc, 6H), 3.18 (mc, 1H), 3.79 + + + + + + + + + + +(mc, 2H), 3.88 (mc, 2H), 3.99, (mc, + + + + + + + + + + +1H), 4.81 (hept, 1H) + + + +I-c-35 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +O +CH3 +2.00-2.12 (m, 2H), 3.19 (mc, 1H), 3.73 + + + + + + + + + + +(s, 3H), 3.88 (mc, 1H), 3.99 (mc, 1H) + + + +I-c-36 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +O +i-C3H7 +110-111 + + + +I-c-37 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +O +CH3 +116 + + + +I-c-38 +C2H5 +CH3 +C2H5 +═NOtC4H9 +O +C2H5 +1.24 (s, 9H), 1.28 (mc, 3H), 2.62-2.90 + + + + + + + + + + +(m, 4H), 4.15 (mc, 1H), 4.20 (mc, 2H) + + + +I-c-39 +C2H5 +CH3 +C2H5 +═NOi-C3H7 +O +C2H5 +1.03 (mc, 6H), 1.15-1.30 (m, 9H), 2.35 + + + + + + + + + + +(hept, 2H), 3.32 (mc, 1H), 4.20 (mc, + + + + + + + + + + +2H), 4.25 (mc, 1H) + + + +I-c-39 +C2H5 +CH3 +C2H5 +═NOCyclopentyl +O +C2H5 +1.52-1.80 (m, 8H), 3.30 (mc, 1H), + + + + + + + + + + +4.12-4.22 (m, 3H), 4.62 (mc, 1H) + + + +I-c-40 +C2H5 +CH3 +C2H5 +═NOCH2-cyclopropyl +O +C2H5 +0.23 and 0.51 (in each case mc, in + + + + + + + + + + +each case 2H), 3.19-3.49 (m, 1H), 3.82 + + + + + + + + + + +(mc, 2H), 4.12-4.24 (m, 3H) + + + +I-c-41 +C2H5 +CH3 +C2H5 +═NOCH2C≡CH +O +C2H5 +1.25 (mc, 3H), 2.47 (mc, 1H), 4.15- + + + + + + + + + + +4.25 (m, 3H), 4.61 (d, 2H) + + + +I-c-42 +C2H5 +CH3 +C2H5 +O═ +O +CH3 +2.60-2.85 (m, 3H), 3.51 (mc, 1H), 3.79 + + + + + + + + + + +(s, 3H), 4.30 (mc, 1H) + + + +I-c-43 +C2H5 +CH3 +C2H5 +═NOCH(CH3)—C≡CH +O +C2H5 +1.28 (t, 3H), 1.48 (mc, 3H), 2.43 (mc, + + + + + + + + + + +1H), 3.34 (mc, 1H), 4.80 (mc, 1H) + + + +I-c-44 +CH3 +CH3 +CH3 +—O—(CH2)2—O— +O +C2H5 +1.21 (t, 3H), 2.05, 2.12 and 2.22 (in + + + + + + + + + + +each case s, in each case 3H), 3.19 + + + + + + + + + + +(mc, 1H), 3.89 (mc, 4H), 3.91 (mc, + + + + + + + + + + +1H), 4.12 (mc, 2H) + + + +I-c-45 +CH3 +CH3 +CH3 +CH2═ +O +C2H5 +1.21 (t, 3H), 1.98, 2.06 and 2.24 (in + + + + + + + + + + +each case s, in each case 3H), 4.15 + + + + + + + + + + +(mc, 2H), 4.90 (mc, 2H) + + + +I-c-46 +CH3 +CH3 +CH3 +CH2═ +O +CH3 +1.99, 2.05 and 2.22 (in each case s, in + + + + + + + + + + +each case 3H), 2.40-2.72 (m, 4H), 3.72 + + + + + + + + + + +(s, 3H), 4.90 (mc, 2H) + + + +I-c-47 +CH3 +CH3 +CH3 +—O—(CH2)3—O— +O +C2H5 +1.20 (t, 3H), 2.80 (mc, 1H), 3.16 (mc, + + + + + + + + + + +1H), 3.70-3.90 (m, 5H), 4.12 (mc, 2H) + + + +I-c-48 +CH3 +CH3 +CH3 +—O—CH2—CH(CH3)—CH2—O +O +C2H5 +0.71 and 0.82 (in each case d, Σ 3H), + + + + + + + + + + +2.45-2.50 (m, 1H), 3.28-3.45 (m, 2H), + + + + + + + + + + +4.12 (mc, 2H) + + + +I-c-49 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +O +CH3 +122 + + + +I-c-50 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +O +C2H5 +131 + + + +I-c-51 +CH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +C2H5 +1.21 (t, 3H), 4.00-4.31 (m, 6H), 5.65 + + + + + + + + + + +(mc, 2H), 6.85 (mc, 2H) + + + +I-c-52 +CH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +CH3 +3.70 (s, 3H), 3.94 (mc, 1H), 3.96-4.30 + + + + + + + + + + +(m, 4H), 5.64 (mc, 2H) + + + +I-c-53 +CH3 +CH3 +CH3 +—O—CH2—CH(CH3)—CH2—O— +O +CH3 +0.70 and 0.82 (in each case t, Σ 3H), + + + + + + + + + + +2.48 (mc, 1H), 3.15 (mc, 1H), 3.29- + + + + + + + + + + +3.45 (m, 2H), 3.71 (s, 3H) + + + +I-c-54 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +C2H5 +1.20 (t, 3H), 1.48 (s, 6H), 3.34 (mc, +syn/anti mixture + + + + + + + + + +1H), 3.85 and 3.89 (in each case d, in + + + + + + + + + + +each case 1H), 4.12 (q, 2H) + + + +I-c-55 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +i-C3H7 +1.15 and 1.19 (in each case d, Σ 6H), +syn/anti mixture + + + + + + + + + +1.38 (s, 6H), 3.85 and 3.90 (in each + + + + + + + + + + +case d, in each case 1H), 4.72 (hept, + + + + + + + + + + +1H) + + + +I-c-56 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +CH3 +1.38 (s, 6H), 3.36 (mc, 1H), 3.71 (s, +syn/anti mixture + + + + + + + + + +3H), 4.00 (mc, 1H) + + + +I-c-57 +CH3 +CH3 +CH3 +═O +O +CH3 +1.98, 2.10 and 2.26 (in each case s, in + + + + + + + + + + +each case 3H), 3.50 (mc, 1H), 3.75 (s, + + + + + + + + + + +3H), 4.19 (mc, 1H) + + + +I-c-58 +CH3 +CH3 +CH3 +═O +O +C2H5 +1.22 (t, 3H), 2.00, 2.11 and 2.26 (in + + + + + + + + + + +each case s, in each case 3H), 2.42- + + + + + + + + + + +2.85 (m, 4H), 4.10-4.22 (3H), + + + +I-c-59 +CH3 +CH3 +CH3 +═NOCH2C≡CH +O +CH3 +2.45 (mc, 1H), 2.70-3.08 (m, 4H), 3.75 + + + + + + + + + + +(s, 3H), 4.61 (mc, 2H), + + + +I-c-60 +CH3 +CH3 +CH3 +═NOCH2C≡CH +O +C2H5 +1.23 (mc, 3H), 2.44 (mc, 1H), 2.70- + + + + + + + + + + +3.08 (m, 4H), 4.18 (mc, 2H), 4.61 (mc, + + + + + + + + + + +2H) + + + +I-c-61 +OCH3 +CH3 +CH3 +CH2═ +O +C2H5 +2.30 (s, 3H), 2.39-2.70 (m, 4H), 3.70 + + + + + + + + + + +(s, 3H), 4.18 (mc, 2H) + + + +I-c-62 +OCH3 +CH3 +CH3 +CH2═ +O +CH3 +2.38-2.70 (m, 4H), 3.70 and 3.75 (in + + + + + + + + + + +each case s, in each case 1H), 4.89 + + + + + + + + + + +(mc, 2H) + + + +I-c-62 +OCH3 +CH3 +CH3 +O═ +O +C2H5 +1.25 (mc, 3H), 2.30(s, 3H), 2.40-2.85 + + + + + + + + + + +(m, 4H), 3.50 (mc, 1H), 4.10 (mc, 2H) + + + +I-c-63 +OCH3 +CH3 +CH3 +—O—(CH2)3—O— +O +C2H5 +1.22 (t, 3H), 2.09 and 2.29 (in each + + + + + + + + + + +case s, in each case 3H), 2.76-2.80 (m, + + + + + + + + + + +1H), 3.18 (mc, 1H), 3.70 (s, 3H) + + + +I-c-64 +OCH3 +CH3 +CH3 +—O—(CH2)2—O— +O +C2H5 +21.12 and 2.30 (in each case s, in each + + + + + + + + + + +case 3H), 3.70 (s, 3H), 3.85 (mc, 4H), + + + + + + + + + + +4.18 (q, 2H) + + + +I-c-65 +OCH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +C2H5 +1.25 (t, 3H), 3.70 (s, 3H), 3.86-430 + + + + + + + + + + +(m, 7H), 5.64 (mc, 2H) + + + +I-c-66 +OCH3 +CH3 +CH3 +—O—(CH2)4—O— +O +C2H5 +1.22 (t, 3H), 2.22 and 2.30 (in each + + + + + + + + + + +case s, in each case 3H), 3.12 (mc, + + + + + + + + + + +1H), 3.70 (s, 3H), 4.16 (q, 2H) + + + +I-c-67 +OCH3 +CH3 +C2H5 +CH2═ +O +C2H5 +0.99 and 1.08 (in each case t, Σ 3H), + + + + + + + + + + +1.26 (mc, 3H), 3.61 and 3.68 (in each + + + + + + + + + + +case s, Σ 3H), 4.89 (mc, 2H) . + + + +I-c-68 +OCH3 +CH3 +C2H5 +O═ +O +C2H5 +1.05 and 1.11 (in each case t, Σ 3H), + + + + + + + + + + +1.26 (mc, 3H), 2.25-2.83 (m, 4H), 2.30 + + + + + + + + + + +(s, 3H), 4.20 (mc, 2H) + + + +I-c-69 +OCH3 +CH3 +C2H5 +—O—(CH2)2—O— +O +C2H5 +1.09 (t, 3H), 1.24 (t, 3H), 2.31 (s, 3H), + + + + + + + + + + +3.70 (s, 3H), 3.88 (mc, 4H), 4.19 (q, + + + + + + + + + + +2H) + + + +I-c-70 +OCH3 +CH3 +C2H5 +—O—(CH2)3—O— +O +C2H5 +1.10 and 1.15 (in each case t, in each + + + + + + + + + + +case 3H), 3.70 (s, 3H), 3.70-4.00 (m, + + + + + + + + + + +4H), 4.18 (q, 2H) + + + +I-c-71 +C2H5 +CH3 +CH3 +—O—(CH2)2—O— +O +C2H5 +1.08 and 1.22 (in each case t, in each + + + + + + + + + + +case 3H), 3.88 (mc, 4H), 3.96 (mc, + + + + + + + + + + +1H), 4.15 (mc, 2H) + + + +I-c-72 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +C2H5 +124-125 + + + +I-c-73 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +CH3 +1.08 (t, 3H), 3.18 (mc, 1H), 3.71 (s, + + + + + + + + + + +3H), 3.95-4.31 (m, 5H), 5.65 (mc, 2H) + + + +I-c-74 +C2H5 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +O +i-C3H7 +1.20 (mc, 6H), 3.91-4.32 (m, 5H), 4.79 + + + + + + + + + + +(hept, 1H), 5.64 (mc, 2H) + + + +I-c-75 +C2H5 +CH3 +CH3 +—O—(CH2)4—O— +O +C2H5 +102 + + + +I-c-76 +C2H5 +CH3 +CH3 +CH2═ +O +C2H5 +0.96 and 1.08 (in each case t, Σ 3H), + + + + + + + + + + +1.22 (t, 3H), 2.26 (s, 3H), 4.15 (mc, + + + + + + + + + + +2H), 4.91 (mc, 1H) + + + +I-c-77 +C2H5 +CH3 +CH3 +CH2═ +O +CH3 +0.97 and 1.05 (in each case t, Σ 3H), + + + + + + + + + + +3.75 (s, 3H), 4.92 (mc, 2H) + + + +I-c-78 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +i-C3H7 +116-117 +syn/anti mixture + + +I-c-79 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +CH3 +1.02-1.11 (m, 3H), 1.38 (s, 6H), 3.74 +syn/anti mixture + + + + + + + + + +(s, 3H), 3.85 and 3.88 (in each case d, + + + + + + + + + + +in each case 1H) + + + +I-c-80 +C2H5 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +O +C2H5 +1.20 (t, 3H), 1.38 (s, 6H), 2.30 (s, 3H), +syn/anti mixture + + + + + + + + + +3.86 and 4.00 (in each case d, in each + + + + + + + + + + +case 1H), 4.15 (mc, 2H) + + + +I-c-81 +C2H5 +C2H5 +C2H5 +CH2═ +O +C2H5 +0.98 and 1.07 (in each case t, in each + + + + + + + + + + +case 3H), 1.22-1.29 (m, 6H), 4.20 (mc, + + + + + + + + + + +2H), 4.92 (mc, 2H) + + + +I-c-82 +C2H5 +C2H5 +C2H5 +O═ +O +C2H5 +103 + + + +I-c-83 +C2H5 +C2H5 +C2H5 +—O—(CH2)3—O— +O +C2H5 +122 + + + +I-c-84 +C2H5 +C2H5 +C2H5 +—O—(CH2)2—O— +O +C2H5 +98 + + + +I-c-85 +C2H5 +CH3 +H +—O—(CH2)3—O— +O +C2H5 + + + + +I-c-86 +C2H5 +CH3 +H +—O—(CH2)3—O— +O +CH3 + + + + +1-c-87 +C2H5 +CH3 +H +—O—(CH2)4—O— +O +C2H5 + + + + +I-c-88 +C2H5 +CH3 +H +—O—(CH2)2—O— +O +C2H5 + + + + +I-c-89 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH2—O— +O +C2H5 +1.05-1.28 (m, 12H), 2.32 (s, 3H), 3.70- +syn/anti mixture + + + + + + + + + +4.05 (m, 4H), 4.18 (mc, 2H) + + + + + + + +
+ +

+Example I-d-1 +

+embedded image + +

+

At room temperature, 57 mg (0.29 mmol) of p-toluenesulphonyl chloride and 0.1 ml of triethylamine are added to 100 mg (0.27 mmol) of the compound (I-a-1) in 5 ml of dichlormethane. After 1 h of stirring, the mixture is diluted with water and the organic phase is separated off and washed twice with 1 N hydrochloric acid. Drying with magnesium sulphate and distillative removal of the solvent affords 120 mg (87%) of the desired substance as a colourless oil.

+

1H-NMR (400 MHz, CDCl3): δ=0.98 and 1.03 (in each case t, in each case 3H), 2.30 and 2.39 (in each case s, in each case 1H), 3.15 and 3.90 (in each case mc, in each case 1H), 3.98-4.35 (m, 4H), 5.65 (s, 2H) ppm.

+

The following compounds of the formula (I-d) are obtained analogously to Example (I-d-1) and in accordance with the general statements on the preparation:

+

+ + + + + + + + + +(I-d) + + + + + + +embedded image + + + + + + + + + + + + + + + + + + + +Ex. + + + + + +M.p. [° C.] or 1H-NMR (400 MHz, d6- + + + +No. +X +Y +Z +A B +R3 +DMSO, δ in ppm) +Isomerism + + + + + +I-d-2 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +C6H5 +1.40 (s, 6H), 3.85 and 3.88 (in each case d, +anti + + + + + + + + +in each case 1H), 7.39 (mc, 2H), 7.61 (mc, + + + + + + + + + +3H) + + + +I-d-3 +C2H5 +CH3 +C2H5 +—O—C(CH3)2—O—CH2— +CH3 +1.12 (t, 3H), 1.40 (s, 6H), 2.78 (s, 3H), 3.41 +anti + + + + + + + + +(mc, 1H), 3.88 and 3.91 (in each case d, in + + + + + + + + + +each case 1H), 3.93 (mc, 1H) + + + +I-d-4 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +CH3 +54-55 +syn/anti mixture + + +I-d-5 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +C6H5 +140 +syn/anti mixture + + +I-d-6 +CH3 +CH3 +CH3 +—O—C(CH3)2—O—CH2— +pCH3C6H5 +144-145 +syn/anti mixture + + +I-d-7 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +CH3 +133-134 + + + +I-d-8 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +C6H5 +129-130 + + + +I-d-9 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +pCH3C6H5 +121-122 + + + +I-d-10 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +CH3 +146-147 + + + +I-d-11 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +C6H5 +145-146 + + + +I-d-12 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +pCH3C6H5 +80 + + + +I-d-13 +C2H5 +CH3 +C2H5 +═NOCH2C≡CH +CH3 +143-144 + + + +I-d-14 +C2H5 +CH3 +C2H5 +═NOCH2C≡CH +C6H5 + + + + +I-d-15 +C2H5 +CH3 +C2H5 +═NOCH2C≡CH +pCH3C6H5 +2.30 and 2.42 (in each case s, in each case + + + + + + + + + +3H), 2.45 (t, 1H), 3.99-4.08 (m, 1H), 4.60 + + + + + + + + + +(mc, 2H), 7.21 (d, 2H), 7.54 (d, 2H) + + + + + + +
+ +

+Example I-f-1 +

+embedded image + +

+

0.040 g (0.242 mmol) of sodium methoxide are added to 0.094 g (0.242 mmol) of the compound (I-a-17) in 3 nil of absolute methanol, and the mixture is stirred at room temperature for another 30 min.

+

Distillative removal of the solvent gives 0.096 g (96%) of the compound of the formula (I-f-1) according to the invention in the form of colourless crystals of melting point >300° C.

+

1H-NMR (400 MHz, d6-DMSO): δ=0.92 and 0.95 (in each case t, in each case 3H), 2.22 (s, 3H), 6.68 (mc, 2H) ppm

+

The following compounds of the formula (I-f) are obtained analogously to Example (I-f-1) and in accordance with the general statements on the preparation:

+

+ + + + + + + + + +(I-f) + + + +embedded image + + + + + + + + + + + + + + + + + + + +Ex. + + + + + +M.p. [° C.] or 1H-NMR (400 MHz, + + + +No. +X +Y +Z +A B +E +d6-DMSO, δ in ppm) +Isomerism + + + + + +I-f-2 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +Na+ +δ = 1.12 (d, 6H), 3.91 (mc, 2H), 6.68 (s, +(R,R)-Configuration of + + + + + + + + +2H) +the CH3-groups at the + + + + + + + + + +acetal ring + + +I-f-3 +CH3 +CH3 +CH3 +—O—CH(CH3)—CH2—CH(CH3)—O— +Na+ +1.22 (s, 6H), 1.95, 2.00 and 2.12 (in each +(R,R)-Configuration of + + + + + + + + +case s, in each case 3H) +the CH3-groups at the + + + + + + + + + +acetal ring + + +I-f-4 +OCH3 +CH3 +CH3 +—O—(CH2)3—O— +Na+ +6.42 and 4.46 (in each case s, in each case + + + + + + + + + +1H) + + + +I-f-5 +OCH3 +CH3 +CH3 +—O—(CH2)4—O— +Na+ +6.42 (s, 1H), 6.48 (s, 1H) + + + +I-f-6 +OCH3 +CH3 +CH3 +—O—(CH2)2—O— +Na+ +3.52 (s, 1H), 6.42 (s, 1H), 6.45 (s, 1H) + + + +I-f-7 +OCH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +Na+ +6.43 and 6.47 (in each case s, in each case + + + + + + + + + +1H) + + + +I-f-8 +CH3 +CH3 +CH3 +—O—CH2—CH═CH—CH2—O— +Na+ +5.61 (s, 2H), 6.62 (s, 2H) + + + +I-f-9 +CH3 +CH3 +CH3 +—O—CH2—CH(CH3)—CH2—O— +Na+ +0.70 (d, 3H), 3.61 and 3.72 (in each case + + + + + + + + + +mc, in each case 2H, 6.62 (s, 2H) + + + +I-f-10 +CH3 +CH3 +CH3 +—O—(CH2)4—O— +Na+ +3.48 and 3.55 (in each case mc, in each + + + + + + + + + +case 2H), 6.62 (s, 2H) + + + +I-f-11 +CH3 +CH3 +CH3 +—O—(CH2)2—O— +Na+ +2.00 (s, 6H), 2.15 (s, 3H), 3.75 (mc, 4H), + + + + + + + + + +6.62 (s, 2H) + + + +I-f-12 +C2H5 +CH3 +C2H5 +—O—CH2—CH═CH—CH2—O— +Na+ +0.93 (t, 6H), 2.33 (q, 4H), 5.62 (s, 2H), + + + + + + + + + +6.68 (s, 2H) + + + +I-f-13 +C2H5 +CH3 +C2H5 +—O—CH2—CH(OCH3)—CH2—O— +Na+ +0.91 (t, 6H), 3.25 (s, 3H), 3.55 and 3.62 + + + + + + + + + +(in each case mc, in each case 1H), 6.66 + + + + + + + + + +(s, 2H) + + + +I-f-14 +C2H5 +CH3 +C2H5 +—O—CH2—CH(OC2H5)—CH2—O— +Na+ +168-169 + + + +I-f-15 +C2H5 +CH3 +C2H5 +—O—(CH2)2—O— +Na+ +0.95 (mc, 6H), 1.70 and 1.88 (in each case + + + + + + + + + +mc, in each case 2H), 3.78 (mc, 4H), 6.68 + + + + + + + + + +(mc, 2H) + + + +I-f-16 +C2H5 +CH3 +C2H5 +—O—CH2—CH(OCH2C6H5)—CH2—O— +Na+ +4.52 (s, 2H), 6.55 (s, 2H, 7.25-7.37 (m, + + + + + + + + + +5H) + + + +I-f-17 +C2H5 +CH3 +C2H5 +—O—(CH2)4—O— +Na+ +288-289 + + + +I-f-18 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +Na+ +1.12 (mc, 6H), 1.50 (mc, 2H), 1.61 (mc, +(R,R)-Configuration of + + + + + + + + +1H), 3.91 (mc, 2H), 6.68 (s, 2H) +the CH3-groups at the + + + + + + + + + +acetal ring + + +I-f-19 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +Na+ +1.03 and 1.12 (in each case d, Σ 6H), +Isomer mixture with + + + + + + + + +1.50-1.71 (m, 3H), 3.79 and 3.91 (in each +respect to the CH3-groups + + + + + + + + +case mc, Σ 2H) +at the acetal ring + + + + + +I-f-20 +C2H5 +CH3 +C2H5 + +embedded image + + +Na+ +0.93 (t, 6H), 2.32 (q, 4H), 4.15, 4.22, 4.82 and 6.68 (in each case s, in each case 2H) + + + + + + +I-f-21 +C2H5 +CH3 +C2H5 +CH2═ +Na+ +117-118 + + + +I-f-22 +OCH3 +CH3 +CH3 +CH2═ +Na+ +4.64 (s, 3H), 6.41 and 6.47 (in each case + + + + + + + + + +d, in each case 2H) + + + +I-f-23 +CH3 +CH3 +CH3 +CH2═ +Na+ +1.90, 2.01 and 2.15 (in each case s, in + + + + + + + + + +each case 3H), 4.65 (s, 2H), 6.61 (mc, 2H) + + + +I-f-24 +OCH3 +CH3 +CH3 +O═ +Na+ +6.45 (mc, 2H) + + + +I-f-25 +C2H5 +CH3 +C2H5 +—O—(CH2)3—O— +Na+ +6.62 (s, 2H) + + + + + + +
+ +

+Preparation of Starting Materials +2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-methylidenecyclohexanecarboxylic acid +Example (XIII-1) +

+embedded image + +

+

At −30° C., 14.48 g (65.7 mmol) of methyl 2-ethyl-4,6-dimethylphenyl acetate (XVII-1) are slowly added dropwise to a solution of lithium diisopropylamide in 250 ml of THF, prepared from 16.3 g (164 mmol) of diisopropylamine and the equimolar amount of a solution of n-butyllithium in hexane, and the mixture is stirred at room temperature for 45 min. At −20° C., 10.00 g (65.7 mmol) of 4-methylenecyclopentane-1,2-dicarboxylic anhydride (XVI-1), dissolved in 20 ml of THF, are then added, and the mixture is stirred at room temperature for around 12 h. For work-up, 100 ml of sat. ammonium chloride solution are added, a layer of ethyl acetate is added on top and the mixture is washed with water, dried (magnesium sulphate) and concentrated using a rotary evaporator. This gives 22.3 g of the compound (XIV-1) as a reddish oil which can be reacted without further purification.

+

1H-NMR (400 MHz, CDCl3): δ=1.11 and 1.12, in each case t, in each case 3H), 2.25-2.50 (m, 4H), 2.35 (s, 3H), 2.69 (mc, 2H), 2.72-2.90 (m, 4H), 3.66 (s, 3H), 4.85 (s, 2H) ppm

+

10 g of potassium hydroxide in 100 ml of water are added to 22.3 g of intermediate (XIV-1), and the mixture is heated at reflux for 24 h. The mixture is then allowed to cool to room temperature, acidified to pH 2 with 2N hydrochloric acid and stirred at room temperature for 1 h, and the precipitated solid is filtered off with suction. This gives 10.3 g (45%) of 2-[(2,6-diethyl-4-methyl-phenyl)acetyl]-4-methylidenecyclohexanecarboxylic acid (XIII-1) as a yellowish solid which can be used without further purification for the next reaction step.

+

1H-NMR (400 MHz, CDCl3): δ=1.12 (t, 6H), 2.45 (q, 4H), 3.90 (s, 2H), 4.91 (mc, 2H), 6.89 (s, 2H) ppm

+

The following intermediates of the general formula (XIII) were prepared analogously:

+

+ + + + + + + + + +(XIII) + + + +embedded image + + + + + + + + + + + + + + + + + +Ex. + + + + +M.p. [° C.] or 1H-NMR (400 MHz, CDCl3, δ in + + +No. +X +Y +Z +A B +ppm) + + + + + +XIII-2 +OCH3 +CH3 +C2H5 +CH2═ +3.28-3.40 (m, 2H), 3.78 (mc, 2H), 3.72 and 3.80 + + + + + + + +(s, in total 3H), 4.88 (mc, 2H) + + +XIII-3 +CH3 +CH3 +CH3 +CH2═ +2.15 (s, 6H), 2.25 (s, 3H), 3.83 (mc, 2H), 4.90 + + + + + + + +(mc, 2H) + + +XIII-4 +C2H5 +CH3 +CH3 +CH2═ +1.20 (t, 3H), 2.12 (s, 3H), 2.22 (s, 6H), 3.70 (s, + + + + + + + +2H), 4.90 (mc, 2H) + + +XIII-5 +OCH3 +CH3 +C2H5 +CH2═ +1.17 (mc, 3H), 3.28-3.40 (m, 2H), 3.72 and 3.79 + + + + + + + +(in each case s, he 3H), 4.89 (mc, 2H) + + +XIII-6 +C2H5 +CH3 +H +CH2═ +96-100 + + + + + + +
+ +

+

The following intermediates of the general formula (XIV) were prepared analogously:

+

+ + + + + + + + + + + +(XIV) + + + +embedded image + + + + + + + + + + + + + + + + + + +Ex. + + + + + +M.p.[° C.] or 1H-NMR (400 MHz, CDCl3, δ in + + +No. +X +Y +Z +A B +R8 +ppm) + + + + + +XIV-2 +CH3 +CH3 +CH3 +CH2═ +C2H5 +118-119 + + +XIV-3 +C2H5 +CH3 +CH3 +CH2═ +CH3 +167-168 + + +XIV-4 +OCH3 +CH3 +CH3 +CH2═ +CH3 +2.20 and 2.31 (in each case s, in each case 3H), + + + + + + + + +3.13 and 3.58 (in each case s, in each case 3H), + + + + + + + + +4.85 (mc, 2H) + + +XIV-5 +OCH3 +CH3 +C2H5 +CH2═ +CH3 +1.08-1.18 (m, 3H), 2.69-3.00 (m, 4H), 4.88 + + + + + + + + +(mc, 2H), 13.20 (s, br, 1H) + + +XIV-6 +C2H5 +CH3 +H +CH2═ +CH3 +106-107 + + + + + + +
+ +

+Methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-methylidenecyclopentanecarboxylate +Example (II-1) +

+embedded image + +

+

5.45 g (17.33 mmol) of 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-methylidenecyclohexane-carboxylic acid (XIII-1), together with 2.38 g of potassium carbonate and 2.62 g (20.8 mmol) of dimethylsulphate, are boiled at reflux in 50 ml of acetone for 5 h, and after cooling, the reaction mixture is taken up in ethyl acetate, extracted with water and dried (magnesium sulphate), and the solvent is distilled off. Chromatography on silica gel using ethyl acetate/hexane (v/v=30:70) gives 3.93 g (69%) of methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-methylidenecyclohexane-carboxylate of the formula (II-1).

+

1H-NMR (400 MHz, CDCl3): δ=3.58 (s, 3H), 3.89 (s, 2H), 4.88 (s, 2H), 6.89 (s, 2H) ppm

+Ethyl 2-[(2-ethyl-4,6-dimethylphenyl)acetyl]-4-oxocyclopentanecarboxylic +Example (II-2) +

+embedded image + +

+

5.62 g (25.7 mmol) of 2-ethyl-4,6-dimethylbenzyl chloride in 30 ml of THF are slowly added dropwise to a suspension of 3.85 g (28.3 mmol) of dry zinc chloride, 1.56 g (64.2 mmol) of magnesium turnings and 1.36 g (42.4 mmol) of lithium chloride such that the internal temperature does not exceed 35° C. After the addition has ended, the mixture is stirred at room temperature for another 2 h. At room temperature, the solution formed is slowly added dropwise to a mixture of 5.62 g (25.7 mmol) of ethyl 2-(chlorocarbonyl)-4-oxocyclopentanecarboxylate and 85 mg of bis(triphenylphosphine)palladium(II) chloride in 40 ml of THF, and the mixture is then stirred at room temperature for another 3 h.

+

The mixture is added to water, extracted twice with in each case 50 ml of methyl tert-butyl ether and dried (magnesium sulphate), and the solvent is distilled off. Chromatography on silica gel using ethyl acetate/hexane (v/v=30:70) gives 4.89 g (57%) of the desired intermediate in the form of colourless crystals of M.p. 75° C.

+

1H-NMR (400 MHz, CDCl3): δ=1.14 and 1.27 (in each case t, in each case 3H), 3.42-3.58 (m, 2H), 3.90 (s, 2H), 4.19 (q, 2H) ppm

+Ethyl 2-[(2,4,6-trimethylphenyl)acetyl]-4-oxocyclopentanecarboxylate +Example (II-3) +

+embedded image + +

+

Over a period of 2 h, 4.08 g (17.4 mmol) of 2,4,6-trimethylbenzylchloride in 40 ml of THF are added dropwise to 1.70 g (26.1 mmol) of zinc dust, activated with hydrochloric acid and dried under reduced pressure, and 0.50 g of trimethylsilyl chloride in 30 ml of THF, and the mixture is stirred at room temperature for another 2 h.

+

Under reduced pressure, 1.56 g (17.4 mmol) of copper(I) cyanide and 1.65 g (38.8 mmol) of lithium chloride are heated at 150° C. for 8 h and, after cooling, vented with argon and taken up in 25 ml of THF. At −25° C., the solution of 2,4,6-trimethylbenzylzinc chloride prepared above is added dropwise over a period of 20 min, and the mixture is stirred at this temperature for a further 20 min.

+

The mixture is cooled to −40° C., and a solution of 3.77 g (17.3 mmol) of ethyl 2-(chlorocarbonyl)-4-oxocyclopentanecarboxylate in 20 ml of THF is added over a period of 30 min, and the mixture is allowed to warm to room temperature and stirred for another 3 h.

+

For work-up, 100 ml of water are added, the mixture is extracted with ethyl acetate and the extract is dried (magnesium sulphate) and concentrated using a rotary evaporator. Chromatography on silica gel (ethyl acetate/hexane v/v=30:70) gives 1.98 g (27%) of the desired product.

+

1H-NMR (400 MHz, CDCl3): δ=2.18 (s, 6H), 2.23 (s, 3H), 3.48 (mc, 2H), 3.82 and 3.88 (in each case d, in each case 1H), 4.18 (q, 2H) ppm

+Methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-hydroxy-4-(hydroxymethyl)cyclopentanecarboxylate +Example (II-4) +

+embedded image + +

+

2.39 g (7.27 mmol) of methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-methylidenecyclohexane-carboxylate according to Example (II-2) are added to 1.37 ml of osmium tetroxide solution (2.5% strength solution in n-butanol) and 1.02 g (8.7 mmol) of N-methylmorpholine N-oxide in 25 ml of acetone/water (v/v=5:1), and the mixture is stirred at room temperature for 14 h. 0.745 g (3.64 mmol) of sodium dithionite is then added, the mixture is stirred at room temperature for 10 min and the solvent is then removed under reduced pressure. The residue is taken up in ethyl acetate, and the mixture is extracted with water, dried (magnesium sulphate) and then concentrated using a rotary evaporator. This gives 2.45 g (92%) of a yellowish viscose oil which can be reacted further without further purification.

+

1H-NMR (400 MHz, CDCl3): δ=1.70-2.25 (m, 4H), 3.34 (mc, 1H), 3.89 (dd, 2H) ppm

+Methyl 8-[(2,6-diethyl-4-methylphenyl)acetyl]-2,2-dimethyl-1,3-dioxaspiro[4.4]nonane-7-carboxylate +(Example II-5) +

+embedded image + +

+

1.16 g (3.19 mmol) of methyl 2-[(2,6-diethyl-4-methylphenyl)acetyl]-4-hydroxy-4-(hydroxymethyl)cyclopentanecarboxylate, 10 ml of 2,2-dimethoxypropane and 30 mg of p-toluene sulphonic acid are heated at reflux for 1 h. After cooling, the mixture is added to ice-water and extracted with ethyl acetate, the extract is washed successively with 1 N sodium bicarbonate solution and water and dried (magnesium sulphate) and the solvent is distilled off under reduced pressure. Chromatography on silica gel (mobile phase ethyl acetate/hexane v/v=35:65) gives 0.92 g (71%) of a colourless oil. According to 1H-NMR, an endo/exo isomer mixture of the compound of the formula (II-5) is present.

+

1H-NMR (400 MHz, CDCl3): δ=1.33-1.37 (Singlets split, in total 6H), 2.26 (s, 3H), 3.22 (mc, 1H), 3.80-3.90 (m, 4H), 6.89 (s, 2H) ppm

+Ethyl 8-[(2-ethyl-4,6-dimethylphenyl)acetyl]-1,4-dioxaspiro[4.4]nonane-7-carboxylate +(Example II-16) +

+embedded image + +

+

1.20 g (3.63 mmol) of ethyl 2-[(2-ethyl-4,6-dimethylphenyl)acetyl]-4-oxocyclopentane-carboxylate according to Example (II-2), 338 mg (5.4 mmol) of ethanediol, 578 mg (5.4 mmol) of trimethyl orthoformate and 20 mg of p-toluene sulphonic acid in 30 ml of toluene are stirred at room temperature for 24 h. The solvent is then distilled off and the residue is chromatographed on silica gel (mobile phase ethyl acetate/hexane v/v=15:85). This gives 819 mg (60%) of the desired compound in the form of colourless crystals of m.p. 72-73° C.

+

The following intermediates of the general formula (II) were prepared analogously

+

+ + + + + + + + + +(II) + + + +embedded image + + + + + + + + + + + + + + + + + + + +Ex. + + + + + + + + + +No. +X +Y +Z +A B +R8 +1H-NMR (400 MHz, CDCl3, δ in ppm) +Isomerism + + + + + +II-6 +OCH3 +CH3 +C2H5 +CH2═ +CH3 +3.38 and 3.59 (in each case q, in each case +trans + + + + + + + + +1H), 3.67 (s, 3H), 3.71 (mc, 2H), 3.75 (s, 3H), + + + + + + + + + +4.86 (mc, 2H) + + + +II-7 +CH3 +CH3 +CH3 +CH2═ +CH3 +2.15 (s, 6H), 2.27 (s, 3H), 3.40 (mc, 2H), 3.74 +trans + + + + + + + + +(mc, 2H), 4.90 (mc, 2H) + + + +II-8 +CH3 +CH3 +C2H5 +CH2═ +CH3 +1.15 (t, 3H), 3.28-3.40 (m, 2H), 3.67 (s, 2H), +trans + + + + + + + + +3.85 (s, 3H), 4.88 (mc, 2H) + + + +II-9 +CH3 +CH3 +CH3 +CH2═ +CH3 +3.10 and 3.40 (in each case mc, in each case +cis + + + + + + + + +1H), 3.62 (s, 3H), 3.78 and 3.90 (in each case + + + + + + + + + +q, in each case 1H) + + + +II-10 +C2H5 +CH3 +C2H5 +CH2═ +t-C4H9 +1.42 (s, 9H), 3.16 and 3.38 (in each case q, in +cis + + + + + + + + +each case 1H), 3.88 (s, 2H), 4.86 (mc, 1H) + + + +II-11 +C2H5 +CH3 +C2H5 +—OCH2CH═CHCH2O— +C2H5 +2.29 (s, 3H), 2.45 (q, 4H), 3.88 (s, 2H), 4.14- +trans + + + + + + + + +4.25 (m, 6H), 5.68 (mc, 2H) + + + +II-12 +C2H5 +CH3 +C2H5 +—O(CH2)2O— +C2H5 +1.12 (mc, 6H), 1.24 (t, 3H), 3.39 and 3.49 (in +trans + + + + + + + + +each case mc, in each case 1H), 3.90 (mc, + + + + + + + + + +4H), 4.14 (q, 2H) + + + +II-13 +C2H5 +CH3 +CH3 +—O(CH2)4O— +C2H5 +1.12 and 1.23 (in each case t, in each case +trans + + + + + + + + +3H), 2.49 (q, 2H), 3.61 (mc, 4H), 3.82 (s, + + + + + + + + + +2H), 4.12 (q, 2H) + + + +II-14 +C2H5 +CH3 +CH3 +—OCH2CH═CHCH2O— +C2H5 +3.35-3.50 (m, 2H), 3.85 (s, 2H), 4.10-4.25 (m, +trans + + + + + + + + +6H), 5.68 (s, 2H) + + + +II-15 +C2H5 +CH3 +CH3 +—O(CH2)3O— +C2H5 +2.24 and 2.28 (in each case s, in each case +trans + + + + + + + + +3H), 3.35-3.48 (m, 2H), 3.80-3.95 (m, 6H) + + + +II-16 +C2H5 +CH3 +CH3 +—O(CH2)2O— +C2H5 +72-73 +trans + + +II-17 +C2H5 +CH3 +C2H5 +—O(CH2)3O— +C2H5 +1.24 (t, 3H), 3.31-3.40 (m, 2H), 3.80-3.95 (m, +trans + + + + + + + + +6H), 4.15 (q, 2H) + + + +II-18 +C2H5 +CH3 +C2H5 +O═ +C2H5 +2.28 (s, 3H), 3.33-3.46 (m, 3H), 3.87 and 3.95 +cis + + + + + + + + +(in each case d, in each case 1H), 6.90 (s, 2H) + + + +II-19 +C2H5 +CH3 +C2H5 +CH2═ +C2H5 +3.35-3.51 (m, 2H), 3.89 (s, 2H), 4.20-4.48 (m, +trans + + + + + + + + +4H), 4.90 (s, 2H) + + + +II-20 +C2H5 +CH3 +C2H5 +—O—CH(CH3)—CH2—CH(CH3)—O— +C2H5 +1.10-1.28 (m, 15H), 3.35-3.58 (m, 2H), 3.70- +trans + + + + + + +mixture with respect to the + +4.00 (m, 4H), 4.12 (mc, 2H) + + + + + + + +CH3-groups at the acetal + + + + + +II-21 +C2H5 +CH3 +C2H5 +—S(CH2)3O— +C2H5 +3.40-3.63 (m, 2H), 3.82 (mc, 2H), 3.88 (mc, +trans + + + + + + + + +2H), 4.14 (mc, 2H)6.89 (s, 2H) + + + +II-22 +C2H5 +CH3 +C2H5 +—OCH2CH(CH3)CH2O— +C2H5 +0.76 and 0.82 (in each case d, in total 3 H), +trans + + + + + + + + +2.00 (mc, 1H), 3.28-3.50 (m, 3H), 3.75-3.90 + + + + + + + + + +(m, 2H) + + + +II-23 +C2H5 +CH3 +C2H5 +—S(CH2)O— +C2H5 +3.05 (mc, 2H), 3.87 and 3.91 (in each case d, +trans + + + + + + + + +in each case 2H), 4.05 (mc, 2H), 4.12 (q, 2H) + + + + + + +II-24 +C2H5 +CH3 +C2H5 + +embedded image + + +C2H5 +3.38-3.50 (m, 2H), 3.89 (s, 2H), 4.20-4.39 (m, 4H), 4.90 (s, 2H) +trans + + + + + +II-25 +OCH3 +CH3 +C2H5 +CH2═ +CH3 +1.14 (t, 3H), 2.31 (s, 3H), 3.68 (s, 3H), 3.72 +trans + + + + + + + + +(s, 3H, 4.85 (mc, 2H), 6.52 and 6.65 (in each + + + + + + + + + +case s, in each case 1H) + + + +11-26 +C2H5 +CH3 +H +CH2═ +CH3 +1.14 (t, 3H), 2.31 (s, 3H), 3.68 (s, 3H), 3.72 +trans + + + + + + + + +(s, 3H, 4.85 (mc, 2H), 6.52 and 6.65 (in each + + + + + + + + + +case s, in each case 1H) + + + + + + +
+ +

+2,6-Diethyl-4-methylbenzyl chloride +Example (XIX-1) +

+embedded image + +

+

With ice-cooling, 48.0 g (3 equivalent) of N,N-dimethylformamide, dissolved in 50 ml of THF, are slowly added dropwise to a solution of 2,6-diethyl-4-methylphenylmagnesium bromide, prepared from 6.00 g of magnesium turnings and 50 g of 1-bromo-2,6-diethyl-4-methylbenzene in 220 ml of THF, and the mixture is stirred at room temperature for another 3 h. The mixture is poured onto a sat. ammonium chloride solution and extracted with ethyl acetate, and the extract is dried (magnesium sulphate) giving, after distillative removal of the solvent, 38.70 g (99%) of 2,6-diethyl-4-methylbenzaldehyde as a colourless oil, 1H-NMR (400 MHz, CDCl3): δ=1.22 (t, 6H), 2.32 (s, 3H), 2.93 (q, 4H), 6.91 (s, 2H), 10.52 (s, 1H)

+

The following compounds were prepared analogously:

+

2-ethyl-4,6-dimethylbenzaldehyde:

+

1H-NMR (400 MHz, CDCl3): 1.22 (t, 3H), 2.32 (s, 3H), 2.57 (s, 3H), 2.95 (q, 2H), 6.92 (mc, 2H), 10.55 (s, 1H) ppm +

+

+

A solution of 35.5 g (201.4 mmol) of 2,6-diethyl-4-methylbenzaldehyde, dissolved in 80 ml of diethyl ether is added dropwise to a suspension of 2.10 g (55.4 mmol) of lithium aluminium hydride in 200 ml of diethyl ether. The mixture is then heated at reflux for another 1 h. After cooling, the mixture is hydrolyzed with water and 10% strength sulphuric acid, the phases are separated and the aqueous phase is extracted two more times with diethyl ether. Drying (magnesium sulphate), distillative removal of the solvent and chromatography of the resulting crude product on silica gel (ethyl acetate/hexane=30:70) gives 33.10 g (92%) of 2,6-diethyl-4-methylbenzyl alcohol in the form of colourless crystals of m.p. 71-72° C. 1H-NMR (400 MHz, CDCl3): δ=1.22 (t, 6H), 2.30 (s, 3H), 2.74 (q, 4H), 4.71 (s, 2H), 6.90 (s, 2H).

+Direct preparation of 2,6-diethyl-4-methylbenzyl alcohol from 1-bromo-2,6-diethyl-4-methylbenzene +

+embedded image + +

+

Over a period of 30 min, gaseous formaldehyde (generated from 5.56 g of paraformaldehyde) is introduced with stirring into a solution of 2,6-diethyl-4-methylphenylmagnesium bromide, prepared from 12.40 g (54.6 mmol) of 1-bromo-2,6-diethyl-4-methylbenzene and 1.47 g (60.65 mmol) of magnesium turnings in 50 ml of THF, and the mixture is then stirred at room temperature for another 2 h. Distillative removal of the solvent and chromatography on silica gel (see above) gives 6.88 g (71%) of 2,6-diethyl-4-methylbenzyl alcohol.

+

The following compounds are prepared analogously: +

+

+

11.20 g (94.16 mmol) of thionyl chloride are slowly added dropwise to 15.26 g (85.6 mmol) of 2,6-diethyl-4-methylbenzyl alcohol in 200 ml of dichloromethane, and the mixture is then heated at reflux for 2 h. After cooling, the mixture is stirred with 50 ml of water for 10 min, and the organic phase is separated off, dried (magnesium sulphate), concentrated using a rotary evaporator and chromatographed in silica gel (ethyl acetate/hexane=15:85). This gives 16.18 g (96%) 2,6-diethyl-4-methylbenzyl chloride as a colourless oil. 1H-NMR (400 MHz, CDCl3): δ=1.26 (t, 6H), 2.30 (s, 3H), 2.76 (q, 4H), 4.70 (s, 2H), 6.88 (s, 2H).

+2,6-Diethyl-4-methylbenzyl bromide +Example (XIX-2) +

+embedded image + +

+

14.7 g (82.5 mmol) of 2,6-diethyl-4-methylbenzyl alcohol in 150 ml of hydrobromic acid are stirred at 100° C. for 4 h. After cooling, the mixture is extracted with dichloromethane and the extract is washed with water, dried (magnesium sulphate) and concentrated using a rotary evaporator. Distillation (110° C. bath temperature, 0.3 mbar) gives 17.82 g (89%) of 2,6-diethyl-4-methylbenzyl bromide as a colourless oil. 1H-NMR (400 MHz, CDCl3): δ=1.28 (t, 6H), 2.30 (s, 3H), 2.73 (q, 4H), 4.61 (s, 2H), 6.90 (s,

+

The following precursors and intermediates of the formula (XIX) were obtained in an analogous manner:

+

+ + + + + + + + + +(XIX) + + + +embedded image + + + + + + + + + + + + + + + + + + + + + + +M.p. °C. or 1H-NMR (400 MHz, + + +Ex. No. +Hal +X +Y +Z +CDC13, δ in ppm) + + + + + +XIX-3 +Cl +C2H5 +CH3 +CH3 +1.26 (t, 3H), 2.28 (s, 3H), 2.41 (s, 3H), + + + + + + + +2.72 (q, 2H), 4.69 (s, 2H) + + +XIX-4 +Br +C2H5 +CH3 +CH3 +2.28 (s, 3H), 2.39 (s, 3H), 2.73 (q, 2H), + + + + + + + +4.60 (s, 2H), 6.85 and 6.88 (in each case + + + + + + + +s, in each case 1H) + + +XIX-5 +Cl +OCH3 +CH3 +CH3 +2.21 and 2.38 (in each case s, in each + + + + + + + +case 3H), 3.75 (s, 3H), 4.72 (s, 2H), 6.59 + + + + + + + +and 6.62 (in each case s, in each case + + + + + + + +1H) + + +XIX-6 +Cl +cyclopropyl +CH3 +C2H5 + + + +XIX-7 +Br +cyclopropyl +CH3 +C2H5 + + + + + + +
+ +

+Example No. 1 +1. Herbicidal Pre-Emergence Action +

Seeds of monocotylidonous and dicotylidonous weed and crop plants are placed in sandy loam in wood fibre pots and covered with soil. The test compounds, formulated in the form of wettable powders (WP), are then, as an aqueous suspension with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, applied to the surface of the covering soil in different amounts.

+

After the treatment, the pots are placed in a greenhouse and kept under good growth conditions for the test plants. The visual assessment of the emergence damage on the test plants is carried out after a trial period of three weeks by comparison with the untreated controls (herbicidal effect in percent: 100% effect=the plants have died, 0% effect=like control plants).

+

In addition to the compounds mentioned above, the following compounds, applied by the pre-emergence method at 320 g/ha a.i., show an effect of ≧80% against Alopecurus myosuroides, Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: I-a-3, I-a-6, I-a-7, I-a-8, I-a-9, I-a-10, I-a-11, I-a-12, I-a-13, I-a-14, I-b-4, I-b-5, I-b-6, I-b-7, I-b-8, I-c-3, I-c-4, I-c-5, I-c-7, I-c-9, I-c-10, I-c-11, I-c-12, I-c-14

+2. Herbicidal Post-Emergence Action +

Seeds of monocotylidonous and dicotylidonous weed and crop plants are placed in sandy loam in wood fibre pots, covered with soil and cultivated in a greenhouse under good growth conditions. Two to three weeks after sowing, the test plants are treated at the one-leaf stage. The test compounds, formulated as wettable powders (WP), are then with a water application rate of 600 l/ha (converted), with 0.2% of wetting agent added, sprayed onto the green parts of the plants in different amounts. After the test plants have been kept in the greenhouse under optimum growth conditions for about three weeks, the effect of the preparations is assessed visually in comparison to untreated controls (herbicidal effect in percent: 100% effect=the plants have died, 0% effect=like control plants).

+

In addition to the compounds mentioned above, the following compounds, applied by the pre-emergence method at 80 g/ha, show an effect of ≧80% against Alopecurus myosuroides, Echinocloa crus-galli, Lolium multiflorum and Setaria viridis: I-a-2, I-a-3, I-a-6, I-a-7, I-a-8, I-a-10, I-a-11, I-a-12, I-a-13, I-a-14, I-b-2, I-b-6, I-b-7, I-c-3, I-c-7, I-c-8, I-c-9, I-c-10, I-c-11, I-c-12, I-c-14, I-c-15, I-f-1

+Use of Safeners: +

If it is to be additionally tested as to whether safeners can improve the plant compatibility of test substances in the case of crop plants, the following options are used for applying the safeners: +

+

+Container Trials with Cereals in the Greenhouse +

+

+ + + + + + + + + +Mefenpyr 1 day prior to herbicide application + + + + + + + + + + + + + + + + + + +28 days after application + + + + + + + + + + + + + +Application rate +Summer wheat + + + + +g of a.i./ha +observed (%) + + + + + + + +I-a-2 +50 +60 + + + + +25 +50 + + + + +  12.5 +40 + + + +I-a-2 + +50 + 50 +5 + + + +mefenpyr +25 + 50 +5 + + + + +12.5 + 50   +0 + + + + + + + + + + + + + + +10 days after application + + + + + + + + + + + + + +Application rate +Summer wheat + + + + +g of a.i./ha +observed (%) + + + + + + + +I-a-10 +50 +60 + + + + +25 +50 + + + + +  12.5 +30 + + + +I-a-10 + +50 + 50 +5 + + + +mefenpyr +25 + 50 +3 + + + + +12.5 + 50   +2 + + + +I-c-7 +50 +60 + + + + +25 +50 + + + + +  12.5 +40 + + + +I-c-7 + +50 + 50 +5 + + + +mefenpyr +25 + 50 +5 + + + + +12.5 + 50   +3 + + + +I-a-11 +50 +70 + + + + +25 +50 + + + + +  12.5 +30 + + + +I-a-11 + +50 + 50 +10 + + + +mefenpyr +25 + 50 +10 + + + + +12.5 + 50   +8 + + + +I-a-14 +50 +60 + + + + +25 +60 + + + + +  12.5 +50 + + + +I-a-14 + +50 + 50 +10 + + + +mefenpyr +25 + 50 +10 + + + + +12.5 + 50   +5 + + + +I-a-13 +50 +60 + + + + +25 +50 + + + + +  12.5 +40 + + + +I-a-13 + +50 + 50 +5 + + + +mefenpyr +25 + 50 +2 + + + + +12.5 + 50   +2 + + + + + + + + + + + + + + +28 days after application + + + + + + + + + + + + + +Application rate +Summer wheat + + + + +g of a.i./ha +observed (%) + + + + + + + +I-c-9 +100  +50 + + + + +50 +40 + + + + +25 +30 + + + +I-c-9 + +100 + 50  +10 + + + +mefenpyr +50 + 50 +5 + + + + +25 + 50 +0 + + + + + + + + + + + + + + + + + +Summer wheat + + + + +Application rate +observed (%) + + + + +g of a.i./ha +10 days after application + + + + + + + +I-a-8 +100  +60 + + + + +50 +50 + + + + +25 +40 + + + + +  12.5 +20 + + + +I-a-8 + +100 + 50  +5 + + + +mefenpyr +50 + 50 +5 + + + + +25 + 50 +2 + + + + +12.5 + 50   +0 + + + + + + + + + + + + + + + + + +Summer wheat + + + + +Summer barley +observed (%) + + + +Application rate +observed (%) +10 days after + + + +g of a.i./ha +10 days after application +application + + + + + +I-a-8 +100  +20 +30 + + + +50 +20 +30 + + + +25 +10 +20 + + +I-a-8 + +100 + 50  +10 +5 + + +mefenpyr +50 + 50 +8 +5 + + + +25 + 50 +5 +3 + + + + + + + + +Summer wheat + + + + +Summer barley +observed (%) + + + +Application rate +observed (%) +28 days after + + + +g of a.i./ha +28 days after application +application + + + + + +I-c-14 +100  +20 +70 + + + +50 +10 +60 + + + +25 + +50 + + + +  12.5 + +40 + + +I-c-14 + +100 + 50  +5 +5 + + +mefenpyr +50 + 50 +0 +5 + + + +25 + 50 + +5 + + + +12.5 + 50   + +0 + + + + + + + + + + + + + + + + +Summer wheat + + + + +Application rate +observed (%) + + + + +g of a.i./ha +28 days after application + + + + + + + +I-c-7 +100  +30 + + + + +50 +30 + + + + +25 +30 + + + + +  12.5 +10 + + + +I-c-7 + +100 + 50  +2 + + + +mefenpyr +50 + 50 +2 + + + + +25 + 50 +0 + + + + +12.5 + 50   +0 + + + + + + + + + + + + + + + + + +Summer wheat + + + + +Summer barley +observed (%) + + + +Application rate +observed (%) +28 days after + + + +g of a.i./ha +28 days after application +application + + + + + +I-a-11 +100  +10 +70 + + + +50 +8 +60 + + + +25 + +50 + + + +  12.5 + +10 + + +I-a-11 + +100 + 50  +0 +2 + + +mefenpyr +50 + 50 +0 +0 + + + +25 + 50 + +0 + + + +12.5 + 50   + +0 + + +I-c-3 +100  +95 +99 + + + +50 +30 +60 + + + +25 +15 +20 + + + +  12.5 + +10 + + +I-c-3 + +100 + 50  +20 +15 + + +mefenpyr +50 + 50 +15 +10 + + + +25 + 50 +10 +5 + + + +12.5 + 50   + +5 + + +I-a-3 +100  +70 +85 + + + +50 +60 +70 + + + +25 +20 +60 + + + +  12.5 + +10 + + +I-a-3 + +100 + 50  +20 +20 + + +mefenpyr +50 + 50 +10 +10 + + + +25 + 50 +10 +8 + + + +12.5 + 50   + +5 + + +I-a-14 +100  +20 +70 + + + +50 +10 +30 + + + +25 +8 +30 + + + +  12.5 +5 +10 + + +I-a-14 + +100 + 50  +8 +8 + + +mefenpyr +50 + 50 +5 +5 + + + +25 + 50 +0 +5 + + + +12.5 + 50   +0 +0 + + +I-c-10 +100  +95 + + + +50 +50 +95 + + + +25 + +50 + + + +  12.5 + +15 + + +I-c-10 + +100 + 50  +30 + + +mefenpyr +50 + 50 +20 +40 + + + +25 + 50 + +20 + + + +12.5 + 50   + +10 + + +I-a-25 +100  +85 +85 + + + +50 +60 +70 + + + +25 + +30 + + + +  12.5 + +10 + + +I-a-25 + +100 + 50  +20 +10 + + +mefenpyr +50 + 50 +10 +8 + + + +25 + 50 + +5 + + + +12.5 + 50   + +0 + + +I-b-13 +100  +50 +85 + + + +50 +20 +80 + + + +25 + +40 + + + +  12.5 + +20 + + +I-b-13 + +100 + 50  +10 +10 + + +mefenpyr +50 + 50 +5 +10 + + + +25 + 50 + +5 + + + +12.5 + 50   + +0 + + +I-f-19 +100  +50 +99 + + + +50 +20 +97 + + + +25 +10 +90 + + + +  12.5 +10 +20 + + +I-f-19 + +100 + 50  +10 +20 + + +mefenpyr +50 + 50 +5 +10 + + + +25 + 50 +0 +10 + + + +12.5 + 50   +0 +10 + + +I-a-58 +100  +15 +60 + + + +50 +10 +20 + + + +25 +5 +15 + + + +  12.5 + +10 + + +I-a-58 + +100 + 50  +5 +5 + + +mefenpyr +50 + 50 +0 +0 + + + +25 + 50 +0 +0 + + + +12.5 + 50   + +0 + + + + + + +
+ +

+Pre-Emergence Method +

+

+ + + + + + + + + +80 g/ha + + + + + + + + + + + + +Example +ALOMY +AVEFA +ECHCG +LOLMU +SETVI + + + + + + + + + + + + + + + +I-a-1 +90 +80 +50 +100 +60 + + +I-a-2 +90 +50 +90 +100 +50 + + +I-a-3 +100 +80 +100 +100 +100 + + +I-a-5 +60 +60 +80 +90 +70 + + +I-a-6 +100 +60 +60 +100 +60 + + +I-a-7 +100 +80 +70 +90 +70 + + +I-a-8 +100 +60 +90 +100 +90 + + +I-a-9 +90 +70 +100 +100 +90 + + +I-a-10 +70 +50 +80 +100 +60 + + +I-a-11 +90 +50 +100 +100 +70 + + +I-a-12 +100 +80 +100 +100 +90 + + +I-a-13 +90 +80 +100 +100 +90 + + +I-a-14 +100 +80 +100 +100 +90 + + +I-a-15 +80 +40 +70 +100 +70 + + +I-a-19 +90 +20 +0 +100 +20 + + +I-a-25 +100 +70 +90 +100 +90 + + +I-a-26 +100 +70 +100 +100 +100 + + +I-a-27 +90 +80 +100 +100 +90 + + +I-a-28 +100 +80 +100 +100 +90 + + +I-a-29 +90 + +70 +80 +20 + + +I-a-30 +80 +0 + +70 +70 + + +I-a-31 +80 +40 +100 +100 +90 + + +I-a-32 +90 +60 +40 +100 +20 + + +I-a-35 +80 +80 +70 +100 +70 + + +I-a-36 +60 +70 +80 +90 +80 + + +I-a-38 +100 +40 +40 +100 +90 + + +I-a-39 +80 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+ +

+Post-Emergence Method +

+

+ + + + + + + + + +80 g/ha + + + + + + + + + + + + +Example +ALOMY +AVEFA +ECHCG +LOLMU +SETVI + + + + + + + + + + + + + + + +I-a-1 +100 +90 +100 +100 + + + +I-a-2 +100 +70 +100 +100 +90 + + +I-a-3 +90 +90 +100 +100 +100 + + +I-a-4 +60 +30 +100 +20 +100 + + +I-a-5 +60 +50 +100 +90 +100 + + +I-a-6 +90 +70 +100 +100 +90 + + +I-a-7 +90 +60 +100 +100 +90 + + +I-a-8 +100 +100 +100 +100 +100 + + +I-a-9 +60 +60 +100 +90 +90 + + +I-a-10 +90 +80 +100 +100 +90 + + +I-a-11 +90 +90 +100 +100 +100 + + +I-a-12 +100 +100 +100 +100 +100 + + +I-a-13 +90 +90 +100 +100 +90 + + +I-a-14 +90 +90 +100 +100 +100 + + +I-a-15 +90 +90 +100 +100 +90 + + +I-a-16 +30 +30 +90 +80 +80 + + +I-a-17 +30 +40 +90 +90 +80 + + +I-a-18 +90 +60 +100 +100 +90 + + +I-a-19 +80 +0 +90 +100 +50 + + +I-a-20 +90 +80 +100 +100 +90 + + +I-a-25 +100 +100 +100 +100 +100 + + +I-a-26 +100 +100 +100 +100 +100 + + +I-a-27 +100 +100 +100 +100 +90 + + +I-a-28 +100 +100 +100 +100 +100 + + +I-a-29 +100 +60 +100 +100 +80 + + +I-a-30 +90 +0 +100 +90 +50 + + +I-a-31 +100 +80 +100 +100 +100 + + +I-a-32 +80 +0 +100 +100 +20 + + +I-a-33 +100 +0 +100 +100 +90 + + +I-a-35 +100 +80 +100 +100 +90 + + +I-a-36 +50 +0 +90 +90 +90 + + +I-a-37 +60 +90 +100 +100 +60 + + +I-a-38 +100 +90 +80 +100 +90 + + +I-a-39 +100 +20 +90 +100 +90 + + +I-a-40 +80 +60 +90 +90 +80 + + +I-a-41 +100 +40 +90 +100 +100 + + +I-a-43 +20 +0 +90 +40 +40 + + +I-a-44 +20 +0 +100 +20 +80 + + +I-a-45 +0 +0 +80 +0 +80 + + +I-a-46 +0 +0 +100 +0 +40 + + +I-a-47 +20 +80 +100 +100 +100 + + +I-a-48 +80 +90 +100 +100 +100 + + +I-a-49 +100 +100 +100 +100 +100 + + +I-a-50 +100 +100 +100 +100 +100 + + +I-a-55 +20 +0 +100 +40 +100 + + +I-a-56 +0 +0 +100 +0 +100 + + +I-a-57 +100 +100 +100 +100 +100 + + +I-a-58 +100 + +100 +100 +100 + + +I-a-60 +100 +90 +100 +100 +100 + + +I-a-61 +90 +90 +100 +100 +90 + + +I-a-62 +100 +80 +100 +100 +90 + + +I-a-68 +90 +0 +100 +100 +40 + + +I-a-69 +90 +30 +100 +100 +80 + + +I-a-70 +90 +0 +100 +100 +60 + + +I-b-1 +100 +60 +100 +100 +40 + + +I-b-2 +100 +60 +90 +100 +80 + + +I-b-3 +100 +40 +100 +100 +20 + + +I-b-4 +100 +90 +100 +100 +60 + + +I-b-5 +90 +20 +80 +100 +0 + + +I-b-6 +90 +100 +100 +100 +90 + + +I-b-7 +90 +100 +100 +100 +90 + + +I-b-8 +90 +70 +80 +100 +60 + + +I-b-9 +90 +0 +90 +40 +40 + + +I-b-10 +90 +20 +90 +70 +70 + + +I-b-12 +90 +100 +100 +100 +100 + + +I-b-13 +100 +100 +100 +100 +100 + + +I-b-14 +100 +100 +100 +100 +100 + + +I-b-15 +100 +90 +100 +100 +100 + + +I-b-16 +100 +90 +100 +100 +100 + + +I-b-17 +90 +90 +100 +100 +90 + + +I-b-18 +100 +100 +100 +100 +100 + + +I-b-19 +20 +30 +100 +40 +80 + + +I-b-20 +0 +30 +100 +60 +0 + + +I-b-21 +90 +90 +100 +100 +90 + + +I-b-22 +100 +100 +100 +100 +100 + + +I-b-23 +100 +100 +100 +100 +100 + + +I-b-24 +100 +100 +100 +100 +100 + + +I-b-25 +100 +100 +100 +100 +100 + + +I-b-27 +100 +100 +100 +100 +100 + + +I-b-28 +100 +100 +100 +100 +100 + + +I-b-29 +100 +90 +100 +100 +100 + + +I-b-30 +20 +100 +100 +100 +90 + + +I-b-37 +0 +0 +90 +70 +90 + + +I-b-38 +40 +0 +90 +70 +90 + + +I-b-39 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+100 +100 +100 +100 + + +I-c-24 +100 +80 +100 +100 +100 + + +I-c-25 +100 +100 +100 +100 +100 + + +I-c-26 +100 +100 +100 +100 +100 + + +I-c-27 +100 +100 +100 +100 +100 + + +I-c-28 +100 +100 +100 +100 +100 + + +I-c-30 +80 +40 +100 +100 +70 + + +I-c-31 +70 +90 +100 +100 +90 + + +I-c-32 +80 +90 +90 +90 +80 + + +I-c-33 +80 +90 +100 +90 +80 + + +I-c-34 +100 +100 +100 +100 +90 + + +I-c-35 +100 +100 +100 +100 +100 + + +I-c-38 +70 +0 +80 +90 +30 + + +I-c-39 +90 +0 +100 +100 +70 + + +I-c-39 +20 +0 +100 +100 +20 + + +I-c-40 +100 +0 +100 +100 +100 + + +I-c-41 +100 +80 +100 +100 +20 + + +I-c-42 +0 +0 +100 +0 +100 + + +I-c-43 +100 +0 +100 +100 +0 + + +I-c-44 +40 +80 +100 +100 +90 + + +I-c-45 +40 +0 +90 +100 +90 + + +I-c-46 +40 +0 +80 +90 +90 + + +I-c-47 +100 +90 +100 +100 +60 + + +I-c-48 +20 +20 +90 +100 +80 + + +I-c-49 +100 +80 +90 +100 +80 + + +I-c-50 +60 +0 +80 +100 +80 + + +I-c-51 +100 +40 +100 +100 +100 + + +I-c-52 +100 +80 +90 +100 +100 + + +I-c-53 +100 +80 +90 +100 +90 + + +I-c-54 +90 +0 +90 +80 +40 + + +I-c-55 +80 +20 +100 +100 +30 + + +I-c-56 +90 +20 +80 +80 +40 + + +I-c-57 +90 +0 +100 +0 +90 + + +I-c-58 +0 +0 +100 +0 +100 + + +I-c-59 +0 +0 +100 +60 +20 + + +I-c-60 +20 +0 +100 +80 +0 + + +I-c-61 +40 +0 +90 +70 +90 + + +I-c-62 +0 +50 +100 +90 +100 + + +I-c-63 +100 +100 +100 +100 +100 + + +I-c-64 +80 +80 +100 +100 +100 + + +I-c-65 +100 +100 +100 +100 +100 + + +I-c-66 +100 +100 +100 +100 +100 + + +I-c-71 +80 +90 + +100 +100 + + +I-c-72 +100 +70 +100 +100 +100 + + +I-c-73 +100 +0 +100 +100 +100 + + +I-c-74 +60 +70 +100 +100 +100 + + +I-c-75 +60 +50 +100 +100 +100 + + +I-c-76 +10 +0 +100 +90 +100 + + +I-c-77 +0 +0 +100 +90 +90 + + +I-c-78 +100 +0 +90 +100 +80 + + +I-c-79 +100 +70 +100 +100 +90 + + +I-c-80 +90 +70 +100 +100 +90 + + +I-f-1 +80 +40 +90 +90 +80 + + +I-f-2 +80 +90 +100 +100 +90 + + +I-f-3 +90 +0 +90 +90 +80 + + +I-f-4 +100 +90 +100 +100 +100 + + +I-f-5 +100 +100 +100 +100 +100 + + +I-f-6 +100 +80 +100 +100 +100 + + +I-f-7 +100 +100 +100 +100 +100 + + +I-f-8 +100 +90 +100 +100 +100 + + +I-f-9 +80 +90 +80 +100 +100 + + +I-f-10 +100 +80 +90 +100 +90 + + +I-f-11 +60 +40 +90 +100 +80 + + +I-f-12 +100 +100 +100 +100 +100 + + +I-f-13 +100 +100 +100 +100 +100 + + +I-f-14 +100 +100 +100 +100 +100 + + +I-f-15 +80 +90 +100 +100 +100 + + +I-f-16 +100 +100 +100 +100 +100 + + +I-f-17 +100 +100 +100 +100 +100 + + +I-f-19 +100 +100 +100 +100 +100 + + +I-f-20 +100 +100 +100 +100 +100 + + +I-f-21 +80 +80 +100 +100 +100 + + +I-f-22 +30 +40 +100 +80 +100 + + +I-f-23 +0 +0 +90 +60 +80 + + + + + +ALOMY: Alopecurus myosuroide + + +AVEFA: Avena fatua + + +ECHCG: Echinochloa crus-galli + + +LOLMU: Lolium multiflorum + + +SETVI: Setaria viridis + + + +
+ +

+Example No. 3 +Method Crop Compatibility Small Plot Trial Outdoors +

+

+

+

Treatment was carried out using a plot sprayer. The safener was applied together with the test substance as a tank mix using 300 l of water/ha (amounts of herbicide and safener are stated in g of ai/ha). Post-emergence application was carried out at the five-leaf stage of maize. Crop compatibility was assessed visually 14 and 27 days after the treatment (in percent compared to an untreated control), 100% damage=the plants have died, 0% damage=like control plants). +

+

+

+ + + + + + + + + + + + + + + + + +Magixx + + + + + + +Cultivar +Duo +Oldham +Magixx Duo +Oldham + + + + + + + + + +days after application/% damage + + + + + + + + + + + + + +g ai/ha +14 days +14 days +27 days +27 days + + + + + + + + + + + + + + + + +Ex. I-a-8 +60 +0% +94% +0% +93% + + +SL 450 + + +Ex. I-a-8 + +60 + 60 +0% +23% +0% +13% + + +cyprosulphamide + + +WP 50 + + + + + + +
+ +

+Example No. 4 +Myzus test (MYZUPE spray treatment) +

+

+

+

To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.

+

Discs of Chinese cabbage leaves (Brassica pekinensis) which are infested by all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration.

+

After six days, the effect in percent is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.

+

In this test, for example, the following compounds of the Preparation Examples show an effect of ≧80% at an application rate of 500 g/ha:

+Ex.: I-a-10, I-c-10, I-c-14 +Example No. 5 +Heliothis virescens Test—Treatment of Transgenic Plants +

+

+

+

To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration.

+

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trademark of Monsanto Comp. USA) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with the tobacco budworm Heliothis virescens while the leaves are still moist.

+

After the desired period of time, the kill of the insects is determined.

+Example No. 6 +Critical Concentration Test/Soil Insects—Treatment of Transgenic Plants +

+

+

+

To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

+

The preparation of active compound is poured onto the soil. Here, the concentration of active compound in the preparation is virtually immaterial; only the amount by weight of active compound per volume unit of soil, which is stated in ppm (mg/l) matters. The soil is filled into 0.25 l pots, and these are allowed to stand at 20° C.

+

Immediately after the preparation, five pregerminated maize corns of the cultivar YIELD GUARD (trademark of Monsanto Comp., USA) are placed into each pot. After two days, the appropriate test insects are placed into the treated soil. After a further seven days, the efficacy of the active compound is determined by counting the maize plants that have emerged (1 plant=20% activity).

+Example No. 7 +

Increase of penetration into the plant by ammonium or phosphonium salts and synergistic increase of penetration into the plant by ammonium/phosphonium salts in combination with penetrants.

+

In this test, the penetration of active compounds through enzymatically isolated cuticles of apple tree leaves was measured.

+

Use was made of leaves which, fully developed, were cut from apple trees of the cultivar Golden Delicious. The cuticles were isolated by +

+

+

Only the cuticles, free from hairs and stoma, of the upper sides of the leaves were then used. They were washed repeatedly alternating with water and a buffer solution of pH 7. The clean cuticles obtained were then mounted on Teflon plates and smoothed and dried with a gentle stream of air.

+

In the next step, the cuticle membranes obtained in this manner were placed into stainless steel diffusion cells (=transport chambers) for membrane transport studies. To this end, the cuticles were placed with a pincet into the centre of the edges, coated with silicone fat, of the diffusion cells and closed with a ring, which had also been treated with fat. The arrangement was chosen such that the morphological outside of the cuticles was facing outwards, i.e. exposed to air, whereas the original inside was facing the interior of the diffusion cells.

+

The diffusion cells were filled with a 30% strength ethylene glycol/water solution. To determine the penetration, in each case 10 μl of the spray liquor of the composition below were applied to the outside of the cuticles. The spray liquor was prepared using local tap water of medium hardness.

+

After the spray liquors had been applied, the water was allowed to evaporate and the chambers were inverted and placed into thermostatic taps in which temperature and atmospheric humidity over the cuticles could be adjusted using a gentle stream of air onto the cuticles with the spray coating (20° C., 60% rh). At regular intervals, an autosampler took aliquots and the active compound content was determined by HPLC.

+

The test results are shown in the table below. The stated numbers are average values of eight to ten measurements.

+

+ + + + + + + + + + + + +Penetration after 24 h/% + + + + + + + + + + + + + + +a.i. + +a.i. + + + + + +a.i. + +Edenor Me SU 500 +Edenor ME SU 500 + + +Active compound +a.i. +AS +EW +EW + AS + + + + + + + + + + + + + + +Example I-a-1 +2.5 +4 +11.5 +13 + + +Example I-a-14 +0 +3 +5 +16 + + +Example I-a-42 +0 +2 +23 +39 + + + + + +a.i. (0.2 g/l) + + +AS = ammonium sulphate (0.7 g/l) + + +Edenor Me SU 500 EW (2 g/l) + + + +
+ +

+ + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + + +1. A compound of the formula (I) + +embedded image + +in which +X represents alkyl, cycloalkyl or alkoxy, +Y represents hydrogen, alkyl or alkoxy, +Z represents hydrogen, alkyl or cycloalkyl, +where +A and B together with the carbon atom to which they are attached represent a saturated or unsaturated unsubstituted or substituted cycle which optionally contains at least one heteroatom, +or +A and B together with the carbon atom to which they are attached represent a carbonyl group, a C1-C4-alkylene group or a ═N—OR9 group, +G represents hydrogen (a) or represents one of the groups + + +embedded image + + +in which +E represents a metal ion equivalent or an ammonium ion, + +L represents oxygen or sulphur, +M represents oxygen or sulphur, +R1 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, alkylthioalkyl, polyalkoxyalkyl or optionally halogen-, alkyl- or alkoxy-substituted cycloalkyl which may be interrupted at least one heteroatom, in each case optionally substituted phenyl, phenylalkyl, hetaryl, phenoxyalkyl or hetaryloxyalkyl, +R2 represents in each case optionally halogen-substituted alkyl, alkenyl, alkoxyalkyl, polyalkoxyalkyl or represents in each case optionally substituted cycloalkyl, phenyl or benzyl, +R3, R4 and R5 independently of one another represent in each case optionally halogen-substituted alkyl, alkoxy, alkylamino, dialkylamino, alkylthio, alkenylthio, cycloalkylthio or represent in each case optionally substituted phenyl, benzyl, phenoxy or phenylthio, +R6 and R7 independently of one another represent hydrogen, in each case optionally halogen-substituted alkyl, cycloalkyl, alkenyl, alkoxy, alkoxyalkyl, represent optionally substituted phenyl, represent optionally substituted benzyl, or together with the nitrogen atom to which they are attached represent a cycle which is optionally interrupted by oxygen or sulphur, +R9 represents hydrogen, represents in each case optionally substituted alkyl, cycloalkyl, CH2-cycloalkyl, alkenyl, alkinyl, arylalkyl or hetarylalkyl. + + + +2. The compound of the formula (I) according to claim 1 in which +X represents C1-C4-alkyl, C3-C6-cycloalkyl or C1-C4-alkoxy, +Y represents hydrogen, C1-C4-alkyl or C1-C4-alkoxy, +Z represents hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, +A, B and the carbon atom to which they are attached represent C3-C8-cycloalkyl or C5-C8-cycloalkenyl, in which optionally one or two ring members are replaced by oxygen and/or sulphur and which are optionally mono- to tetrasubstituted by C1-C8-alkyl, C1-C8-alkenyl, C1-C4-alkylene, C1-C8-halogenalkyl, C1-C6-alkoxy-C1-C4-alkyl, C1-C6-alkoxy, C1-C6-halogenalkoxy, hydroxyl, hydroxy-C1-C4-alkyl or benzyloxy, or a further fused-on C3-C8-cycloalkyl ring in which optionally one or two ring members are replaced by oxygen or sulphur, or which is optionally mono- or disubstituted by C1-C8-alkyl, or +A, B and the carbon atom to which they are attached represent a carbonyl group, represent a C1-C4-alkylene group or represent a ═N—OR9 group, +G represents hydrogen (a) or represents one of the groups + + +embedded image + +in which +E represents a metal ion equivalent or an ammonium ion, +L represents oxygen or sulphur, and +M represents oxygen or sulphur, +R1 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C1-C8-alkyl, C1-C8 alkyl, poly-C1-C8-alkoxy-C1-C8-alkyl or optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl in which optionally one or more not directly adjacent ring members are replaced by oxygen and/or sulphur, +represents optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenalkyl-, C1-C6-halogenalkoxy-, C1-C6-alkylthio- or C1-C6-alkylsulphonyl-substituted phenyl, +represents optionally halogen-, nitro-, cyano-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenalkyl- or C1-C6-halogenalkoxy-substituted phenyl-C1-C6-alkyl, +represents optionally halogen- or C1-C6-alkyl-substituted 5- or 6-membered heteroaryl, +represents optionally halogen- or C1-C6-alkyl-substituted phenoxy-C1-C6-alkyl or +represents optionally halogen-, amino- or C1-C6-alkyl-substituted 5- or 6-membered heteroaryloxy-C1-C6-alkyl, + +R2 represents in each case optionally halogen-substituted C1-C20-alkyl, C2-C20-alkenyl, C1-C8-alkoxy-C2-C8-alkyl, poly-C1-C8-alkoxy-C2-C8-alkyl, +represents optionally halogen-, C1-C6-alkyl- or C1-C6-alkoxy-substituted C3-C8-cycloalkyl or +represents in each case optionally halogen-, cyano-, nitro-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C6-halogenalkyl- or C1-C6-halogenalkoxy-substituted phenyl or benzyl, + +R3 represents optionally halogen-substituted C1-C8-alkyl or represents in each case optionally halogen-, C1-C6-alkyl-, C1-C6-alkoxy-, C1-C4-halogenalkyl-, C1-C4-halogenalkoxy-, cyano- or nitro-substituted phenyl or benzyl, +R4 and R5 independently of one another represent in each case optionally halogen-substituted C1-C8-alkyl, C1-C8-alkoxy, C1-C8-alkylamino, Di-(C1-C8-alkyl)amino, C1-C8-alkylthio, C2-C8-alkenylthio, C3-C7-Cycloalkylthio or represent in each case optionally halogen-, nitro-, cyano-, alkoxy-, C1-C4-halogenalkoxy-, C1-C4-alkylthio-, C1-C4-halogenalkylthio, C1-C4-alkyl- or C1-C4-halogenalkyl-substituted phenyl, phenoxy or phenylthio, +R6 and R7 independently of one another represent hydrogen, represent in each case optionally halogen-substituted C1-C8-alkyl, C3-C8-cycloalkyl, C1-C8-alkoxy, C3-C8-alkenyl, C1-C8-alkoxy-C1-C8-alkyl, represent optionally halogen-, C1-C8-halogenalkyl-, C1-C8-alkyl- or C1-C8-alkoxy-substituted phenyl, optionally halogen-, C1-C8-alkyl-, C1-C8-halogenalkyl- or C1-C8-alkoxy-substituted benzyl or together represent an optionally C1-C4-alkyl-substituted C3-C6-alkylene radical in which optionally one carbon atom is replaced by oxygen or sulphur, +R9 represents hydrogen, represents C1-C6-alkyl, C3-C6-cycloalkyl, CH2C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, each of which is optionally mono- to pentasubstituted by halogen, or represents phenyl-C1-C2-alkyl or heteroaryl-C1-C2-alkyl, each of which is optionally mono- to trisubstituted by alkyl, halogen, alkoxy, halogenalkyl or halogenalkoxy. + + + + +3. The compound of the formula (I) according to claim 1 in which +X represents methyl, ethyl, cyclopropyl, methoxy or ethoxy, +Y represents hydrogen, methyl or ethyl, +Z represents hydrogen, methyl, ethyl or cyclopropyl, +A, B and the carbon atom to which they are attached represent C3-C8-cycloalkyl or C5-C8-cycloalkenyl in which optionally one or two ring members are replaced by oxygen and/or sulphur and which is optionally mono- to tetrasubstituted by C1-C4-alkyl, C1-C4-alkenyl, a ═CH2 group, trifluoromethyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C2-alkyl or by one of the groups + + +embedded image + + +or + +A, B and the carbon atom to which they are attached represent a carbonyl group, represent a C1-C4-alkylene group or represent a ═N—OR9 group, +G represents hydrogen (a) or represents one of the groups + + +embedded image + +in which +E represents a metal ion equivalent or an ammonium ion, +L represents oxygen or sulphur and +M represents oxygen or sulphur, +R1 represents C1-C8-alkyl, C2-C8-alkenyl, C1-C4-alkoxy-C1-C2-alkyl, C1-C4-alkylthio-C1-C2-alkyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents C3-C6-cycloalkyl which is optionally mono- or disubstituted by fluorine, chlorine, C1-C2-alkyl or C1-C2-alkoxy and in which optionally one or two not directly adjacent ring members are replaced by oxygen, +represents phenyl which is optionally mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C4-alkoxy, C1-C2-haloalkyl or C1-C2-haloalkoxy, + +R2 represents C1-C8-alkyl, C2-C8-alkenyl or C1-C4-alkoxy-C2-C4-alkyl, each of which is optionally mono- to trisubstituted by fluorine, +represents C3-C6-cycloalkyl which is optionally monosubstituted by C1-C2-alkyl or C1-C2-alkoxy or +represents phenyl or benzyl, each of which is optionally mono- or disubstituted by fluorine, chlorine, bromine, cyano, nitro, C1-C4-alkyl, C1-C3-alkoxy, trifluoromethyl or trifluoromethoxy, + +R3 represents C1-C6-alkyl which is optionally mono- to trisubstituted by fluorine or represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, C1-C4-alkoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro, +R4 represents C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino, Di-(C1-C6-alkyl)amino, C1-C6-alkylthio, C3-C4-alkenylthio, C3-C6-cycloalkylthio, each of which is optionally mono- to trisubstituted by fluorine or chlorine, or represents phenyl, phenoxy or phenylthio, each of which is optionally monosubstituted by fluorine, chlorine, bromine, nitro, cyano, C1-C3-alkoxy, C1-C3-haloalkoxy, C1-C3-alkylthio, C1-C3-haloalkylthio, C1-C3-alkyl or trifluoromethyl, +R5 represents C1-C6-alkylthio or C1-C6-alkoxy which is optionally monosubstituted by chlorine, +R6 represents hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-alkoxy, C3-C6-alkenyl, C1-C6-alkoxy-C1-C4-alkyl, represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, trifluoromethyl, C1-C4-alkyl or C1-C4-alkoxy, represents benzyl which is optionally monosubstituted by fluorine, chlorine, bromine, C1-C4-alkyl, trifluoromethyl or C1-C4-alkoxy, +R7 represents C1-C6-alkyl, C3-C6-alkenyl or C1-C6-alkoxy-C1-C4-alkyl, +R6 and R7 together represent an optionally methyl- or ethyl-substituted C4-C5-alkylene radical in which optionally one methylene group is replaced by oxygen or sulphur, +R9 represents hydrogen, represents C1-C4-alkyl, C3-C6-cycloalkyl, CH2—C3-C6-cycloalkyl, C3-C4-alkenyl, C3-C4-alkynyl, each of which is optionally mono- to trisubstituted by fluorine or chlorine, represents benzyl or pyridinylmethyl, each of which is optionally mono- or disubstituted by C1-C2-alkyl, C1-C2-alkoxy, fluorine, chlorine, bromine, trifluoromethyl or trifluoromethoxy. + + + + +4. The compound of the formula (I) according to claim 1 in which +X represents methyl, ethyl, cyclopropyl, methoxy or ethoxy, +Y represents hydrogen, methyl or ethyl, +Z represents hydrogen, methyl, ethyl or cyclopropyl, +A, B and the carbon atom to which they are attached represent C3-C7-cycloalkyl or C5-C7-cycloalkenyl in which optionally one or two ring members are replaced by oxygen and/or sulphur and which is optionally mono-, di-, tri- or tetrasubstituted by methyl, in each case monosubstituted by ethyl, a ═CH2 group, methoxy or ethoxy, +A, B and the carbon atom to which they are attached represent a carbonyl group, represent a ═CH2 group, represent a ═CH2—CH3 group, represent a ═CH2—C2H5 group or represent a ═N—OR9 group, +G represents hydrogen (a) or represents one of the groups + + +embedded image + +in which +E represents a metal ion equivalent, +L represents oxygen or sulphur and +M represents oxygen or sulphur, + +R1 represents C1-C6-alkyl, C2-C6-alkenyl, C1-C2-alkoxy-C1-alkyl, C1-C2-alkylthio-C1-alkyl or C3-C6-cyclopropyl which is optionally monosubstituted by fluorine, chlorine, methyl or methoxy or represents C1-C4-alkyl which is monosubstituted by chlorine, +represents phenyl which is optionally monosubstituted by fluorine, chlorine, bromine, cyano, nitro, methyl, methoxy, trifluoromethyl or trifluoromethoxy, + +R2 represents C1-C8-alkyl, C2-C6-alkenyl or C1-C4-alkoxy-C2-C3-alkyl, each of which is optionally mono- to trisubstituted by fluorine, represents phenyl or benzyl, +R3 represents C1-C6-alkyl or represents phenyl which is optionally monosubstituted by chlorine or C1-C4-alkyl, +R9 represents hydrogen, represents in each case optionally fluorine-substituted methyl, ethyl, propyl, n-butyl, isobutyl, s-butyl or tert-butyl, represents allyl, chloroallyl, propynyl, butynyl, chlorobenzyl, chloropyridylmethyl, CH(CH3)—C≡CH, cyclopropyl, cyclobutyl, cyclopentyl, CH2-cyclopropyl, CH2-cyclobutyl or CH2-cyclopentyl. + + + +5. The compound of the formula (I) according to claim 1 in which +X represents methyl, ethyl or methoxy, +Y represents methyl or ethyl, +Z represents hydrogen, methyl or ethyl, +A, B and the carbon atom to which they are attached represent C5-C7-cycloalkyl or C7-cycloalkenyl which optionally two ring members are replaced by oxygen and/or sulphur and which is optionally mono-, di- or tetrasubstituted by methyl, in each case monosubstituted by ethyl, a ═CH2 group, methoxy, ethoxy or benzyloxy, +A, B and the carbon atom to which they are attached represent a carbonyl group, represent a ═CH2 group or represent a ═N—OR9 group, +G represents hydrogen (a) or represents one of the groups + + +embedded image + +in which +E represents a metal ion equivalent, +L represents oxygen and +M represents oxygen, +R1 represents C1-C6-alkyl or C1-C2-alkoxy-C1-alkyl or C1-C4-alkyl which is monosubstituted by chlorine, +represents phenyl which is optionally monosubstituted by chlorine, methyl or methoxy, + +R2 represents C1-C8-alkyl, +R3 represents methyl, phenyl or p-methylphenyl, +R9 represents hydrogen, methyl, isopropyl, isobutyl, tert-butyl, CH2CF3, CH2—C≡CH, CH(CH3)—C≡CH, cyclopropyl, cyclopentyl, CH2-cyclopropyl, CH2-cyclopentyl. + + + + +6. A process for preparing a compound of formula (I) according to claim 1 comprising: +(A) Cyclising intramolecularly, optionally in the presence of a diluent and optionally in the presence of a base, a +ketocarboxylic ester of the formula (II) + + +embedded image + +in which +A, B, X, Y and Z have the meaning given in claim 1, and +R8 represents alkyl, to obtain a compound of the formula (I-a) + + +embedded image + + in which A, B, X, Y and Z have the meaning given in claim 1; or +(B) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent and optionally in the presence of an acid binder +(α) with an acid halides of the formula (III) + + +embedded image + +in which +R1 has the meaning given in claim 1 and +Hal represents halogen +or +(β) with a carboxylic anhydride of the formula (IV) + +
+R1—CO—O—CO—R1  (IV) + + + +in which +R1 has the meaning given in claim 1, to obtain a compound of the formula (I-b) + + +embedded image + + in which A, B, R1, X, Y and Z have the meanings given in claim 1; +or +(C) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent and optionally in the presence of an acid binder +with a chloroformic ester or a chloroformic thio ester of the formula (V) + +
+R2-M-CO—Cl  (V) + + +in which +R2 and M have the meanings given in claim 1, to obtain a compound of the formula (I-c) + + +embedded image + + in which A, B, R2, M, X, Y and Z have the meanings given in claim 1 and L represents oxygen; +or +(D) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent and optionally in the presence of an acid binder +with a chloromonothioformic ester or a chlorodithioformic ester of the formula (VI) + + +embedded image + +in which +M and R2 have the meanings given in claim 1, to obtain a compound of the formula (I-c) + + +embedded image + + in which A, B, R2, M, X, Y and Z have the meanings given in claim 1 and L represents sulphur; +or +(E) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent and optionally in the presence of an acid binder, +with a sulphonyl chloride of the formula (VII) + +
+R3—SO2—Cl  (VII) + + +in which +R3 has the meaning given in claim 1, to obtain a compound of the formula (I-d) + + +embedded image + + in which A, B, R3, X, Y and Z have the meanings given in claim 1; or +(F) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent and optionally in the presence of an acid binder +with a phosphorus compound of the formula (VIII) + + +embedded image + +in which +L, R4 and R5 have the meanings given in claim 1 and +Hal represents halogen, to obtain a compound of the formula (I-e) + + +embedded image + + in which A, B, L, R4, R5, X, Y and Z have the meanings given in claim 1; or +(G) Reacting a compound the formula (I-a) in which A, B, X, Y and Z have the meanings given in claim 1, optionally in the presence of a diluent +with a metal compound or an amine of the formulae (IX) and (X) respectively, + + +embedded image + +in which +Me represents a mono- or divalent metal, +t represents the number 1 or 2 and +R10, R11, R12 independently of one another represent hydrogen or alkyl, to obtain a compound of the formula (I-f) + + +embedded image + + in which A, B, E, X, Y and Z have the meanings given in claim 1; or +(H) Reacting a compound of the formula (I-a) shown above in which A, B, X, Y and Z have the meanings given in claim 1, +(α) with an isocyanate or an isothiocyanate of the formula (XI) + +
+R6—N═C=L  (XI) + + +in which +R6 and L have the meanings given in claim 1, +optionally in the presence of a diluent and optionally in the presence of a catalyst, or +(β) with a carbamoyl chloride or a thiocarbamoyl chloride of the formula (XII) + + +embedded image + +in which +L, R6 and R7 have the meanings given in claim 1, +optionally in the presence of a diluent and optionally in the presence of an acid binder, to obtain a compound of the formula (I-g) + + +embedded image + + in which A, B, L, R6, R7, X, Y and Z have the meanings given in claim 1. + + + +7. A composition for controlling pests and/or unwanted vegetation comprising at least one compound of the formula (I) according to claim 1. + + +8. A method for controlling animal pests and/or unwanted vegetation comprising administering a compound of the formula (I) according to claim 1 on the pests, unwanted vegetation and/or their habitat. + + +9. (canceled) + + +10. A process for preparing a composition for controlling pests and/or unwanted vegetation comprising mixing a compound of the formula (I) according to claim 1 with an extender and/or an surfactant. + + +11. (canceled) + + +12. A composition comprising an effective amount of an active compound combination comprising, as components, +(a′) at least one compound of the formula (I) in which A, B, G, X, Y and Z have the meaning given in claim 1 +and +(b′) at least one crop plant compatibility-improving compound selected from the group consisting of +S1, a compound having the formula of + + +embedded image + +wherein +nA is a natural number from 0 to 5; +RA1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; +WA is an unsubstituted or substituted divalent heterocyclic radical selected from the group consisting of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms, wherein the hetero ring atom is selected from the group consisting of N and O, and wherein at least one nitrogen atom and at most one oxygen atom is present in the ring; + +S2, a compound having the formula of + + +embedded image + +wherein +RB1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; +nB is a natural number from 0 to 5, preferably from 0 to 3; +RB2 is ORB3, SRB3 or NRB3RB4 or a saturated +or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, which is attached via the nitrogen atom to the carbonyl group in (S2) and which is unsubstituted or substituted by a radical selected from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy and optionally substituted phenyl; + +RB3 is hydrogen, an unsubstituted or a substituted aliphatic hydrocarbon radical having a total of 1 to 18 carbon atoms; +RB4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl; +TB is a (C1- or C2)-alkanediyl chain which is unsubstituted or substituted by one or two (C1-C4)-alkyl radicals or by [(C1-C3)-alkoxy]carbonyl; +S3, a compound having the formula of + + +embedded image + +wherein +RC1 is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, or (C3-C7)-cycloalkyl; +RC2, RC3 are identical or different and are hydrogen, (C1-C4)-alkyl, (C2-C4) alkenyl, (C2-C4)-alkenyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkylcarbamoyl-(C1-C4)-alkyl, (C2-C4)-alkenylcarbamoyl-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, dioxolanyl-(C1-C4)-alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or RC2 and RC3 together form a substituted or unsubstituted heterocyclic ring; +S4, a compound having the formula of + + +embedded image + +wherein +XD is CH or N; +RD1 is CO—NRD5RD6 or NHCO—RD7; +RD2 is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; +RD3 is hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl or (C2-C4)-alkynyl; +RD4 is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulphinyl, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; +RD5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl which contains a vD heteroatom selected from the group consisting of nitrogen, oxygen and sulphur, wherein the (C2-C6)-alkenyl, (C2-C6)-alkynyl, or the phenyl or 3- to 6-membered heterocyclyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulphinyl, (C1-C2)-alkylsulphonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, (C1-C4)-alkylcarbonyl and phenyl, and wherein the (C3-C6)-cycloalkyl, (C5-C6)-cycloalkenyl, or the phenyl or 3- to 6-membered heterocyclyl is substituted by a vD heteroatom selected from the group consisting of nitrogen, oxygen, sulphur, (C1-C4)-alkyl and (C1-C4)-haloalkyl; +RD6 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, wherein the (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl is substituted by a vD radical selected from the group consisting of halogen, hydroxy, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio, or +RD5 and RD6 together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical; +RD7 is hydrogen, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl; wherein the (C1-C6)-alkyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy and (C1-C4)-alkylthio; and wherein the (C3-C6)-cycloalkyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkyl, and (C1-C4)-haloalkyl; +nD is 0, 1 or 2; +mD is 1 or 2; +vD is 0, 1, 2 or 3; +S5, an active compound selected from the class of the hydroxyaromatics or aromatic-aliphatic carboxylic acid derivatives; +S6, an active compound selected from the class of the 1,2-dihydroquinoxalin-2-ones; +S7, a compound having the formula of + + +embedded image + +wherein +RE1, RE2 independently of one another are halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, or nitro; +AE is COORE3 or COSRE4 +RE3, RE4 independently of one another are hydrogen, (C1-C4)-alkyl, (C2-C6)-alkenyl, (C2-C4)-alkynyl, cyanoalkyl, (C1-C4)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or alkylammonium, +nE1 is 0 or 1; +nE2, nE3 independently of one another are 0, 1 or 2; +S8, a compound having the formula of + + +embedded image + +wherein +XF is CH or N, +nF is, if XF═N, an integer from 0 to 4 and +is, if XF═CH, an integer from 0 to 5, + +RF1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkylthio, (C1-C4)-alkylsulphonyl, or (C1-C4)-alkoxycarbonyl, or optionally substituted phenyl, or optionally substituted phenoxy, +RF2 is hydrogen or (C1-C4)-alkyl, +RF3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, identical or different radicals selected from the group consisting of halogen and alkoxy and salts thereof; +S9, an active compound selected from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones; +S10, a compound having the formula of (S10a) or (S10b): + + +embedded image + +wherein +RG1 is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3 +YG, ZG independently of one another are O or S, +nG is an integer from 0 to 4, +RG2 is (C1-C16)-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; +benzyl, or halobenzyl, + +RG3 is hydrogen or (C1-C6)-alkyl; + +S11, an oxyimino compound; +S12, an isothiochromanone compound; +S13, at least one compound selected from the group consisting of naphthalic anhydride, fenclorim, flurazole, CL-304415 (CAS Reg. No.: 31541-57-8), MG-191 (CAS Reg. No.: 96420-72-3), MG-838 (CAS Reg. No.: 133993-74-5), disulfoton, dietholate and mephenate; and +S14, at least one compound selected from the group consisting of S-1-methyl-1-phenylethyl piperidine-1-carbothioate, 1-(1-methyl-1-phenylethyl)-3-p-tolylurea, 3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, 3,3′-dimethyl-4-methoxybenzophenone and 1-bromo-4-(chloromethylsulphonyl)benzene. + + + +13. A composition according to claim 12 in which the crop plant compatibility-improving compound is cloquintocet-mexyl. + + +14. A composition according to claim 12 in which the crop plant compatibility-improving compound is mefenpyr-diethyl. + + +15. A composition according to claim 12 in which the crop plant compatibility-improving compound is cyprosulfamide. + + +16. A method for controlling unwanted vegetation in plants or their surroundings, comprising administering a composition according to claim 12 to the plants or their surroundings. + + +17. (canceled) + + +18. A method for controlling unwanted vegetation in plants or their surroundings, comprising administering a compound of the formula (I) according to claim 1 and at least one crop plant compatibility-improving compound selected from the group consisting of +S1, a compound having the formula of + + +embedded image + +wherein +nA is a natural number from 0 to 5; +RA1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; +WA is an unsubstituted or substituted divalent heterocyclic radical selected from the group consisting of partially unsaturated or aromatic five-membered heterocycles having 1 to 3 hetero ring atoms, wherein the hetero ring atom is selected from the group consisting of N and O, and wherein at least one nitrogen atom and at most one oxygen atom is present in the ring; + +S2, a compound having the formula of + + +embedded image + +wherein +RB1 is halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, nitro or (C1-C4)-haloalkyl; +nB is a natural number from 0 to 5, preferably from 0 to 3; +RB2 is ORB3, SRB3 or NRB3RB4 or a saturated +or unsaturated 3- to 7-membered heterocycle having at least one nitrogen atom and up to 3 heteroatoms, which is attached via the nitrogen atom to the carbonyl group in (S2) and which is unsubstituted or substituted by a radical selected from the group consisting of (C1-C4)-alkyl, (C1-C4)-alkoxy and optionally substituted phenyl; +RB3 is hydrogen, an unsubstituted or a substituted aliphatic hydrocarbon radical having a total of 1 to 18 carbon atoms; +RB4 is hydrogen, (C1-C6)-alkyl, (C1-C6)-alkoxy or substituted or unsubstituted phenyl; + +TB is a (C1- or C2)-alkanediyl chain which is unsubstituted or substituted by one or two (C1-C4)-alkyl radicals or by [(C1-C3)-alkoxy]carbonyl; +S3, a compound having the formula of + + +embedded image + +wherein +RC1 is (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C2-C4)-alkenyl, (C2-C4)-haloalkenyl, or (C3-C7)-cycloalkyl; +RC2, RC3 are identical or different and are hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl, (C1-C4)-haloalkyl, (C2-C4)-haloalkenyl, (C1-C4)-alkylcarbamoyl-(C1-C4)-alkyl, (C2-C4)-alkenylcarbamoyl-(C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, dioxolanyl-(C1-C4)-alkyl, thiazolyl, furyl, furylalkyl, thienyl, piperidyl, substituted or unsubstituted phenyl, or RC2 and RC3 together form a substituted or unsubstituted heterocyclic ring; +S4, a compound having the formula of + + +embedded image + +wherein +XD is CH or N; +RD1 is CO—NRD5RD6 or NHCO—RD7; +RD2 is halogen, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; +RD3 is hydrogen, (C1-C4)-alkyl, (C2-C4)-alkenyl or (C2-C4)-alkynyl; +RD4 is halogen, nitro, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-haloalkoxy, (C3-C6)-cycloalkyl, phenyl, (C1-C4)-alkoxy, cyano, (C1-C4)-alkylthio, (C1-C4)-alkylsulphonyl, (C1-C4)-alkylsulphonyl, (C1-C4)-alkoxycarbonyl or (C1-C4)-alkylcarbonyl; +RD5 is hydrogen, (C1-C6)-alkyl, (C3-C6)-cycloalkyl, (C2-C6)-alkenyl, (C2-C6)-alkynyl, (C5-C6)-cycloalkenyl, phenyl or 3- to 6-membered heterocyclyl which contains a vD heteroatom selected from the group consisting of nitrogen, oxygen and sulphur, wherein the (C2-C6)-alkenyl, (C2-C6)-alkynyl, or the phenyl or 3- to 6-membered heterocyclyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C6)-alkoxy, (C1-C6)-haloalkoxy, (C1-C2)-alkylsulphonyl, (C1-C2)-alkylsulphonyl, (C3-C6)-cycloalkyl, (C1-C4)-alkoxycarbonyl, alkylcarbonyl and phenyl, and wherein the (C3-C6)-cycloalkyl, (C5-C6)-cycloalkenyl, or the phenyl or 3- to 6-membered heterocyclyl is substituted by a vD heteroatom selected from the group consisting of nitrogen, oxygen, sulphur, (C1-C4)-alkyl and (C1-C4)-haloalkyl; +RD6 is hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl, wherein the (C1-C6-alkyl, (C2-C6)-alkenyl or (C2-C6)-alkynyl is substituted by a vD radical selected from the group consisting of halogen, hydroxy, (C1-C4)-alkyl, (C1-C4)-alkoxy and (C1-C4)-alkylthio, or +RD5 and RD6 together with the nitrogen atom carrying them form a pyrrolidinyl or piperidinyl radical; +RD7 is hydrogen, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, (C1-C6)-alkyl, or (C3-C6)-cycloalkyl; wherein the (C1-C6)-alkyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy and (C1-C4)-alkylthio; and wherein the (C3-C6)-cycloalkyl is substituted by a vD substituent selected from the group consisting of halogen, (C1-C4)-alkoxy, halo-(C1-C6)-alkoxy, (C1-C4)-alkylthio, (C1-C4)-alkyl, and (C1-C4)-haloalkyl; +nD is 0, 1 or 2; +mD is 1 or 2; +vD is 0, 1, 2 or 3; +S5, an active compound selected from the class of the hydroxyaromatics or aromatic-aliphatic carboxylic acid derivatives; +S6, an active compound selected from the class of the 1,2-dihydroquinoxalin-2-ones; +S7, a compound having the formula of + + +embedded image + +wherein +RE1, RE2 independently of one another are halogen, (C1-C4)-alkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkyl, (C1-C4)-alkylamino, di-(C1-C4)-alkylamino, or nitro; +AE is COORE3 or COSRE4 +RE3, RE4 independently of one another are hydrogen, (C1-C4)-alkyl, (C2-C6)-alkenyl, (C2-C4)-alkynyl, cyanoalkyl, (C1-C4)-haloalkyl, phenyl, nitrophenyl, benzyl, halobenzyl, pyridinylalkyl or alkylammonium, +nE1 is 0 or 1; +nE2, nE3 independently of one another are 0, 1 or 2; +S8, a compound having the formula of + + +embedded image + +wherein +XF is CH or N, +nF is, if XF═N, an integer from 0 to 4 and +is, if XF═CH, an integer from 0 to 5, + +RF1 is halogen, (C1-C4)-alkyl, (C1-C4)-haloalkyl, (C1-C4)-alkoxy, (C1-C4)-haloalkoxy, nitro, (C1-C4)-alkylthio, (C1-C4)-alkylsulphonyl, or (C1-C4)-alkoxycarbonyl, or optionally substituted phenyl, or optionally substituted phenoxy, +RF2 is hydrogen or (C1-C4)-alkyl, +RF3 is hydrogen, (C1-C8)-alkyl, (C2-C4)-alkenyl, (C2-C4)-alkynyl or aryl, where each of the carbon-containing radicals mentioned above is unsubstituted or substituted by one or more, identical or different radicals selected from the group consisting of halogen and alkoxy and salts thereof; +S9, an active compound selected from the class of the 3-(5-tetrazolylcarbonyl)-2-quinolones; +S10, a compound having the formula of (S10a) or (S10b): + + +embedded image + +wherein +RG1 is halogen, (C1-C4)-alkyl, methoxy, nitro, cyano, CF3, OCF3 +YG, ZG independently of one another are O or S, +nG is an integer from 0 to 4, +RG2 is (C1-C16)-alkyl, (C2-C6)-alkenyl, (C3-C6)-cycloalkyl, aryl; benzyl, or halobenzyl, +RG3 is hydrogen or (C1-C6)-alkyl; + +S11, an oxyimino compound; +S12, an isothiochromanone compound; +S13, at least one compound selected from the group consisting of naphthalic anhydride, fenclorim, flurazole, CL-304415 (CAS Reg. No.: 31541-57-8), MG-191 (CAS Reg. No.: 96420-72-3), MG-838 (CAS Reg. No.: 133993-74-5), disulfoton, dietholate and mephenate; and +S14, at least one compound selected from the group consisting of S-1-methyl-1-phenylethyl piperidine-1-carbothioate, 1-(1-methyl-1-phenylethyl)-3-p-tolylurea, 3-(2-chlorophenylmethyl)-1-(1-methyl-1-phenylethyl)urea, 3,3′-dimethyl-4-methoxybenzophenone and 1-bromo-4-(chloromethylsulphonyl)benzene, + +separately in close temporal succession to the plants or their surroundings. + + +19. A compound of the formula (II) + +embedded image + +in which +A, B, X, Y, Z and R8 have the meanings given in claim 1. + + + +20. A compound of the formula (XIII) + +embedded image + +in which +A, B, X, Y, and Z have the meanings given in claim 1. + + + +21. A compound of the formula (XIV) + +embedded image + +in which +A, B, X, Y, Z, R8 and R8′ have the meanings given in claim 1. + + + +22. A compound of the formula (XIX) + +embedded image + +in which +X, Y, Z and Hal have the meanings given in the table: + + + + + + + + + + + + + + + + + +Hal +X +Y +Z + + + + + + + + + +Cl +C2H5 +CH3 +CH3 + + + +Cl +OCH3 +CH3 +C2H5 + + + +Cl +cyclopropyl +CH3 +C2H5 + + + +Br +cyclopropyl +CH3 +C2H5 + + + + + + + +
+ + + + +23. A composition comprising +at least one compound of the formula (I) according to claim 1 or a composition according to claim 12 and +at least one salt of the formula (III′) + + +embedded image + +in which +D represents nitrogen or phosphorus, +R26, R27, R28 and R29 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene, the substituents being selectable from halogen, nitro and cyano, +n represents 1, 2, 3 or 4, and +R30 represents an inorganic or organic anion. + + + +24. A composition according to claim 23 further comprising at least one penetrant. + + +25. A method for increasing the activity of pesticides and/or herbicides comprising a ready-to-use composition that comprises an active compound of the formula (I) according to claim 1 or a composition according to claim 12, said method comprises preparing the ready-to-use composition further comprising a salt of the formula (III′) + +embedded image + + +in which +D represents nitrogen or phosphorus, +R26, R27, R28, R29 independently of one another represent hydrogen or in each case optionally substituted C1-C8-alkyl or mono- or polyunsaturated, optionally substituted C1-C8-alkylene, the substituents being selectable from halogen, nitro and cyano, +n represents 1, 2, 3 or 4, and +R30 represents an inorganic or organic anion. + + + +26. The method according to claim 25, wherein said ready-to-use composition further comprises a penetrant. + + + diff --git a/tests/data/uspto/ipa20180000016.xml b/tests/data/uspto/ipa20180000016.xml new file mode 100644 index 00000000..ddab5793 --- /dev/null +++ b/tests/data/uspto/ipa20180000016.xml @@ -0,0 +1,723 @@ + + + + + + +US +20180000016 +A1 +20180104 + + + + +US +15634401 +20170627 + + +15 + + +JP +2016-128835 +20160629 + + + + +20060101 +A +
A
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A
+01 +G +1 +00 +L +I +20180104 +US +B +H + + +20060101 +A +
A
+01 +G +31 +00 +L +I +20180104 +US +B +H + + +20100101 +A +
H
+01 +L +33 +50 +L +I +20180104 +US +B +H + + + + + +20130101 +
A
+01 +G +7 +045 +F +I +20180104 +US +B +H +C + + + + +20130101 +
H
+01 +L +33 +504 +L +I +20180104 +US +B +H +C + + +20130101 +
A
+01 +G +1 +001 +L +I +20180104 +US +B +H +C + + +20130101 +
A
+01 +G +31 +00 +L +I +20180104 +US +B +H +C + + + +LIGHT EMITTING DEVICE AND PLANT CULTIVATION METHOD + + + + +NICHIA CORPORATION +
+Anan-shi +JP +
+ + +JP + + + + + + +AMIYA +Mika +
+Naruto-shi +JP +
+ + + + +FUJIO +Kazushige +
+Tokushima-shi +JP +
+ + + + +SUZUKI +Tomokazu +
+Tokushima-shi +JP +
+ + + + + + + +NICHIA CORPORATION +03 +
+Anan-shi, Tokushima +JP +
+ + + + + +

Provided is a light emitting device that includes a light emitting element having a light emission peak wavelength ranging from 380 nm to 490 nm, and a fluorescent material excited by light from the light emitting element and emitting light having at a light emission peak wavelength ranging from 580 nm or more to less than 680 nm. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B ranging from 2.0 to 4.0 and a ratio R/FR of the photon flux density R to a photon flux density FR ranging from 0.7 to 13.0, the photon flux density R being in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B being in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR being in a wavelength range of 700 nm or more and 780 nm or less.

+ + +
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+ + + +CROSS-REFERENCE TO RELATED APPLICATION +

The application claims benefit of Japanese Patent Application No. 2016-128835 filed on Jun. 29, 2016, the entire disclosure of which is hereby incorporated by reference in its entirety.

+BACKGROUND +Technical Field +

The present disclosure relates to a light emitting device and a plant cultivation method.

+Description of Related Art +

With environmental changes due to climate change and other artificial disruptions, plant factories are expected to increase production efficiency of vegetables and be capable of adjusting production in order to make it possible to stably supply vegetables. Plant factories that are capable of artificial management can stably supply clean and safe vegetables to markets, and therefore are expected to be the next-generation industries.

+

Plant factories that are completely isolated from external environment make it possible to artificially control and collect various data such as growth method, growth rate data, yield data, depending on classification of plants. Based on those data, plant factories are able to plan production according to the balance between supply and demand in markets, and supply plants such as vegetables without depending on surrounding conditions such as climatic environment. Particularly, an increase in food production is indispensable with world population growth. If plants can be systematically produced without the influence by surrounding conditions such as climatic environment, vegetables produced in plant factories can be stably supplied within a country, and additionally can be exported abroad as viable products.

+

In general, vegetables that are grown outdoors get sunlight, grow while conducting photosynthesis, and are gathered. On the other hand, vegetables that are grown in plant factories are required to be harvested in a short period of time, or are required to grow in larger than normal sizes even in an ordinary growth period.

+

In plant factories, the light source used in place of sunlight affect a growth period, growth of plants. LED lighting is being used in place of conventional fluorescent lamps, from a standpoint of power consumption reduction.

+

For example, Japanese Unexamined Patent Publication No. 2009-125007 discloses a plant growth method. In this method, the plants is irradiated with light emitted from a first LED light emitting element and/or a second LED light emitting element at predetermined timings using a lighting apparatus including the first LED light emitting element emitting light having a wavelength region of 625 to 690 nm and the second LED light emitting element emitting light having a wavelength region of 420 to 490 nm in order to emit lights having sufficient intensities and different wavelengths from each other.

+SUMMARY +

However, even though plants are merely irradiated with lights having different wavelengths as in the plant growth method disclosed in Japanese Unexamined Patent Publication No. 2009-125007, the effect of promoting plant growth is not sufficient. Further improvement is required in promotion of plant growth.

+

Accordingly, an object of the present disclosure is to provide a light emitting device capable of promoting growth of plants and a plant cultivation method.

+

Means for solving the above problems are as follows, and the present disclosure includes the following embodiments.

+

A first embodiment of the present disclosure is a light emitting device including a light emitting element having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less, and a fluorescent material that is excited by light from the light emitting element and emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of a photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less.

+

A second embodiment of the present disclosure is a plant cultivation method including irradiating plants with light from the light emitting device.

+

According to embodiments of the present disclosure, a light emitting device capable of promoting growth of plants and a plant cultivation method can be provided.

+ + + +BRIEF DESCRIPTION OF THE DRAWINGS +

FIG. 1 is a schematic cross sectional view of a light emitting device according to an embodiment of the present disclosure.

+

FIG. 2 is a diagram showing spectra of wavelengths and relative photon flux densities of exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting devices.

+

FIG. 3 is a graph showing fresh weight (edible part) at the harvest time of each plant grown by irradiating the plant with light from exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting device.

+

FIG. 4 is a graph showing nitrate nitrogen content in each plant grown by irradiating the plant with light from exemplary light emitting devices according to embodiments of the present disclosure and a comparative light emitting device.

+ + + +DETAILED DESCRIPTION +

A light emitting device and a plant cultivation method according to the present invention will be described below based on an embodiment. However, the embodiment described below only exemplifies the technical concept of the present invention, and the present invention is not limited to the light emitting device and plant cultivation method described below. In the present specification, the relationship between the color name and the chromaticity coordinate, the relationship between the wavelength range of light and the color name of monochromatic light follows JIS Z8110.

+Light Emitting Device +

An embodiment of the present disclosure is a light emitting device including a light emitting element having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less (hereinafter sometimes referred to as a “region of from near ultraviolet to blue color”), and a first fluorescent material emitting light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by being excited by light from the light emitting element. The light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of the photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less.

+

An example of the light emitting device according to one embodiment of the present disclosure is described below based on the drawings. FIG. 1 is a schematic cross sectional view showing a light emitting device 100 according to an embodiment of the present disclosure.

+

The light emitting device 100 includes a molded article 40, a light emitting element 10 and a fluorescent member 50, as shown in FIG. 1. The molded article 40 includes a first lead 20 and a second lead 30 that are integrally molded with a resin portion 42 containing a thermoplastic resin or a thermosetting resin. The molded article 40 forms a depression having a bottom and sides, and the light emitting element 10 is placed on the bottom of the depression. The light emitting element 10 has a pair of an anode and a cathode, and the anode and the cathode are electrically connected to the first lead 20 and the second lead 30 respectively through the respective wires 60. The light emitting element 10 is covered with the fluorescent member 50. The fluorescent member 50 includes, for example, a fluorescent material 70 performing wavelength conversion of light from the light emitting element 10, and a resin. The fluorescent material 70 includes a first fluorescent material 71 and a second fluorescent material 72. A part of the first lead 20 and the second lead 30 that are connected to a pair of the anode and the cathode of the light emitting element 10 is exposed toward outside a package constituting the light emitting element 100. The light emitting device 100 can emit light by receiving electric power supply from the outside through the first lead 20 and the second lead 30.

+

The fluorescent member 50 not only performs wavelength conversion of light emitted from the light emitting element 10, but functions as a member for protecting the light emitting element 10 from the external environment. In FIG. 1, the fluorescent material 70 is localized in the fluorescent member 50 in the state that the first fluorescent material 71 and the second fluorescent material 72 are mixed with each other, and is arranged adjacent to the light emitting element 10. This constitution can efficiently perform the wavelength conversion of light from the light emitting element 10 in the fluorescent material 70, and as a result, can provide a light emitting device having excellent light emission efficiency. The arrangement of the fluorescent member 50 containing the fluorescent material 70, and the light emitting element 10 is not limited to the embodiment that the fluorescent material 70 is arranged adjacent to the light emitting element 10 as shown in FIG. 1, and considering the influence of heat generated from the light emitting element 10, the fluorescent material 70 can be arranged separated from the light emitting element 10 in the fluorescent member 50. Furthermore, light having suppressed color unevenness can be emitted from the light emitting device 100 by arranging the fluorescent material 70 almost evenly in the fluorescent member 50. In FIG. 1, the fluorescent material 70 is arranged in the state that the first fluorescent material 71 and the second fluorescent material 72 are mixed with each other. However, for example, the first fluorescent material 71 may be arranged in a layer state and the second fluorescent material 72 may be arranged thereon in another layer state. Alternatively, the second fluorescent material 72 may be arranged in a layer state and the first fluorescent material 71 may be arranged thereon in another layer state.

+

The light emitting device 100 includes the first fluorescent material 71 having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by being excited by light from the light emitting element 10, and preferably further includes the second fluorescent material 72 having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by being excited by light from the light emitting element 10.

+

The first fluorescent material 71 and the second fluorescent material 72 are contained in, for example, the fluorescent member 50 covering the light emitting element 10. The light emitting device 100 in which the light emitting element 10 has been covered with the fluorescent member 50 containing the first fluorescent material 71 and the second fluorescent material 72 emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm by a part of light emission of the light emitting element 10 that is absorbed in the first fluorescent material 71. Furthermore, the light emitting device 100 emits light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by a part of light emission of the light emitting element 10 that is absorbed in the second fluorescent material 72.

+

Plants grow when a pigment (chlorophyll a and chlorophyll b) present in chlorophyll thereof absorbs light and additionally takes carbon dioxide gas and water therein, and these are converted to carbohydrates (saccharides) by photosynthesis. Chlorophyll a and chlorophyll b used in growth promotion of plants particularly have absorption peaks in a red region of 625 nm or more and 675 nm or less and a blue region of 425 nm or more and 475 nm or less. The action of photosynthesis by chlorophylls of plants mainly occurs in a wavelength range of 400 nm or more and 700 nm or less, but chlorophyll a and chlorophyll b further have local absorption peaks in a region of 700 nm or more and 800 nm or less.

+

For example, when plants are irradiated with light having longer wavelength than and absorption peak (in the vicinity of 680 nm) in a red region of chlorophyll a, a phenomenon called red drop, in which activity of photosynthesis rapidly decreases, occurs. However, it is known that when plants are irradiated with light containing near infrared region together with light of red region, photosynthesis is accelerated by a synergistic effect of those two kinds of lights. This phenomenon is called the Emerson effect.

+

Intensity of light with which plants are irradiated is represented by photon flux density. The photon flux density (μmol·m−2·s−1) is the number of photons reaching a unit area per unit time. The amount of photosynthesis depends on the number of photons, and therefore does not depend on other optical characteristics if the photon flux density is the same. However, wavelength dependency activating photosynthesis differs depending on photosynthetic pigment. Intensity of light necessary for photosynthesis of plants is sometimes represented by Photosynthetic Photon Flux Density (PPFD).

+

The light emitting device 100 emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of the photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, where the photon flux density R is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 620 nm or more and less than 700 nm, the photon flux density B is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 380 nm or more and 490 nm or less, and the photon flux density FR is the number of light quanta (μmol·m−2·g−1) incident per unit time and unit area in a wavelength range of 700 nm or more and 780 nm or less.

+

It is estimated that in plants, which are irradiated with light containing the photon flux density FR from the light emitting device 100, photosynthesis is activated by Emerson effect, and as a result, growth of plants can be promoted. Furthermore, when plants are irradiated with light containing the photon flux density FR, growth of the plants can be promoted by a reversible reaction between red light irradiation, to which chlorophyll as chromoprotein contained in plants has participated, and far infrared light irradiation.

+

Examples of nutrients necessary for growth of plants include nitrogen, phosphoric acid, and potassium. Of those nutrients, nitrogen is absorbed in plants as nitrate nitrogen (nitrate ion: NO3−). The nitrate nitrogen changes into nitrite ion (NO2−) by a reduction reaction, and when the nitrite ion is further reacted with fatty acid amine, nitrosoamine is formed. It is known that nitrite ion acts to hemoglobin in blood, and it is known that a nitroso compound sometimes affects health of a human body. Mechanism of converting nitrate nitrogen into nitrite ion in vivo is complicated, and the relationship between the amount of intake of nitrate nitrogen and the influence to health of a human body is not clarified. However, it is desired that the content of nitrate nitrogen having a possibility of affecting health of a human body is smaller.

+

For the above reasons, nitrogen is one of nutrients necessary for growth of plants, but it is preferred that the content of nitrate nitrogen in food plants be reduced to a range that does not disturb the growth of plants.

+

It is preferred that the light emitting device 100 further include the second fluorescent material 72 having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less by being excited by light from the light emitting element 10, wherein the R/FR ratio is within a range of 0.7 or more and 5.0 or less. The R/FR ratio is more preferably within a range of 0.7 or more and 2.0 or less.

+Light Emitting Element +

The light emitting element 10 is used as an excitation light source, and is a light emitting element emitting light having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less. As a result, a stable light emitting device having high efficiency, high linearity of output to input and strong mechanical impacts can be obtained.

+

The range of the light emission peak wavelength of the light emitting element 10 is preferably in a range of 390 nm or more and 480 nm or less, more preferably in a range of 420 nm or more and 470 nm or less, and still more preferably in a range of 440 nm or more and 460 nm or less, and particularly preferably in a range of 445 nm or more and 455 nm or less. A light emitting element including a nitride semiconductor (InxAlyGa1-x-yN, 0≦X, 0≦Y and X+Y≦1) is preferably used as the light emitting element 10.

+

The half value width of emission spectrum of the light emitting element 10 can be, for example, 30 nm or less.

+Fluorescent Member +

The fluorescent member 50 used in the light emitting device 100 preferably includes the first fluorescent material 71 and a sealing material, and more preferably further includes the second fluorescent material 72. A thermoplastic resin and a thermosetting resin can be used as the sealing material. The fluorescent member 50 may contain other components such as a filler, a light stabilizer and a colorant, in addition to the fluorescent material and the sealing material. Examples of the filler include silica, barium titanate, titanium oxide and aluminum oxide.

+

The content of other components other than the fluorescent material 70 and the sealing material in the fluorescent member 50 is preferably in a range of 0.01 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the sealing material.

+

The total content of the fluorescent material 70 in the fluorescent member 50 can be, for example, 5 parts by mass or more and 300 parts by mass or less, per 100 parts by mass of the sealing material. The total content is preferably 10 parts by mass or more and 250 parts by mass or less, more preferably 15 parts by mass or more and 230 parts by mass or less, and still more preferably 15 parts by mass or more and 200 parts by mass or less. When the total content of the fluorescent material 70 in the fluorescent member 50 is within the above range, the light emitted from the light emitting element 10 can be efficiently subjected to wavelength conversion in the fluorescent material 70.

+First Fluorescent Material +

The first fluorescent material 71 is a fluorescent material that is excited by light from the light emitting element 10 and emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm. Examples of the first fluorescent material 71 include an Mn4+-activated fluorogermanate fluorescent material, an Eu2+-activated nitride fluorescent material, an Eu2+-activated alkaline earth sulfide fluorescent material and an Mn4+-activated halide fluorescent material. The first fluorescent material 71 may use one selected from those fluorescent materials and may use a combination of two or more thereof. The first fluorescent material preferably contains an Eu2+-activated nitride fluorescent material and an Mn4+-activated fluorogermanate fluorescent material.

+

The Eu2+-activated nitride fluorescent material is preferably a fluorescent material that has a composition including at least one element selected from Sr and Ca, and Al and contains silicon nitride that is activated by Eu2+, or a fluorescent material that has a composition including at least one element selected from the group consisting of alkaline earth metal elements and at least one element selected from the group consisting of alkali metal elements and contains aluminum nitride that is activated by Eu2+.

+

The halide fluorescent material that is activated by Mn4+ is preferably a fluorescent material that has a composition including at least one element or ion selected from the group consisting of alkali metal elements and an ammonium ion (NH4+) and at least one element selected from the group consisting of Group 4 elements and Group 14 elements and contains a fluoride that is activated by Mn4+.

+

Examples of the first fluorescent material 71 specifically include fluorescent materials having any one composition of the following formulae (I) to (VI).

+

+
+(i−j)MgO.(j/2)Sc2O3.kMgF2.mCaF2.(1−n)GeO2.(n/2)Mt2O3:zMn4+  (I) +

+

wherein Mt is at least one selected from the group consisting of Al, Ga, and In, and j, k, m, n, and z are numbers satisfying 2≦i≦4, 0≦j<0.5, 0<k<1.5, 0≦m<1.5, 0<n<0.5, and 0<z<0.05, respectively.

+

+
+(Ca1-p-qSrpEuq)AlSiN3  (II) +

+

wherein p and q are numbers satisfying 0≦p≦1.0, 0<q<1.0, and p+q<1.0.

+

+
+MavMbwMcfAl3-gSigNh  (III) +

+

wherein Ma is at least one element selected from the group consisting of Ca, Sr, Ba, and Mg, Mb is at least one element selected from the group consisting of Li, Na, and K, Mc is at least one element selected from the group consisting of Eu, Ce, Tb, and Mn, v, w, f, g, and h are numbers satisfying 0.80≦v≦1.05, 0.80≦w≦1.05, 0.001<f≦0.1, 0≦g≦0.5, and 3.0≦h≦5.0, respectively.

+

+
+(Ca1-r-s-tSrrBasEut)2Si5N8  (IV) +

+

wherein r, s, and t are numbers satisfying 0≦r≦1.0, 0≦s≦1.0, 0<t<1.0, and r+s+t≦1.0.

+

+
+(Ca,Sr)S:Eu  (V) +

+

+
+A2[M11-uMn4+uF6]  (VI) +

+

wherein A is at least one selected from the group consisting of K, Li, Na, Rb, Cs, and NH4+, M1 is at least one element selected from the group consisting of Group 4 elements and Group 14 elements, and u is the number satisfying 0<u<0.2.

+

The content of the first fluorescent material 71 in the fluorescent member 50 is not particularly limited as long as the R/B ratio is within a range of 2.0 or more and 4.0 or less. The content of the first fluorescent material 71 in the fluorescent member 50 is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and more preferably 8 parts by mass or more, per 100 parts by mass of the sealing material, and is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less, per 100 parts by mass of the sealing material. When the content of the first fluorescent material 71 in the fluorescent member 50 is within the aforementioned range, the light emitted from the light emitting element 10 can be efficiently subjected to wavelength conversion, and light capable of promoting growth of plant can be emitted from the light emitting device 100.

+

The first fluorescent material 71 preferably contains at least two fluorescent materials, and in the case of containing at least two fluorescent materials, the first fluorescent material preferably contains a fluorogermanate fluorescent material that is activated by Mn4+ (hereinafter referred to as “MGF fluorescent material”), and a fluorescent material that has a composition including at least one element selected from Sr and Ca, and Al, and contains silicon nitride that is activated by Eu2+ (hereinafter referred to as “CASN fluorescent material”).

+

In the case where the first fluorescent material 71 contains at least two fluorescent materials and two fluorescent materials are a MGF fluorescent material and a CASN fluorescent material, where a compounding ratio thereof (MGF fluorescent material:CASN fluorescent material) is preferably in a range of 50:50 or more and 99:1 or less, more preferably in a range of 60:40 or more and 97:3 or less, and still more preferably in a range of 70:30 or more and 96:4 or less, in mass ratio. In the case where the first fluorescent material contains two fluorescent materials, when those fluorescent materials are a MGF fluorescent material and a CASN fluorescent material and the mass ratio thereof is within the aforementioned range, the light emitted from the light emitting element 10 can be efficiently subjected to wavelength conversion in the first fluorescent material 71. In addition, the R/B ratio can be adjusted to within a range of 2.0 or more and 4.0 or less, and the R/FR ratio is easy to be adjusted to within a range of 0.7 or more and 13.0 or less.

+Second Fluorescent Material +

The second fluorescent material 72 is a fluorescent material that is excited by the light from the light emitting element 10 and emits light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less.

+

The second fluorescent material 72 used in the light emitting device according to one embodiment of the present disclosure is a fluorescent material that contains a first element Ln containing at least one element selected from the group consisting of rare earth elements excluding Ce, a second element M containing at least one element selected from the group consisting of Al, Ga, In, Ce, and Cr, and has a composition of an aluminate fluorescent material. When a molar ratio of the second element M is taken as 5, it is preferred that a molar ratio of Ce be a product of a value of a parameter x and 3, and a molar ratio of Cr be a product of a value of a parameter y and 3, wherein the value of the parameter x is in a range of exceeding 0.0002 and less than 0.50, and the value of the parameter y is in a range of exceeding 0.0001 and less than 0.05.

+

The second fluorescent material 72 is preferably a fluorescent material having the composition represented by the following formula (1):

+

+
+(Ln1-x-yCexCry)3M5O12  (1) +

+

wherein Ln is at least one rare earth element selected from the group consisting of rare earth elements excluding Ce, M is at least one element selected from the group consisting of Al, Ga, and In, and x and y are numbers satisfying 0.0002<x<0.50 and 0.0001<y<0.05, respectively.

+

In this case, the second fluorescent material 72 has a composition constituting a garnet structure, and therefore is tough against heat, light, and water, has an absorption peak wavelength of excited absorption spectrum in the vicinity of 420 nm or more and 470 nm or less, and sufficiently absorbs the light from the light emitting element 10, thereby enhancing light emitting intensity of the second fluorescent material 72, which is preferred. Furthermore, the second fluorescent material 72 is excited by light having light emission peak wavelength in a range of 380 nm or more and 490 nm or less and emits light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less.

+

In the second fluorescent material 72, from the standpoint of stability of a crystal structure, Ln is preferably at least one rare earth element selected from the group consisting of Y, Gd, Lu, La, Tb, and Pr, and M is preferably Al or Ga.

+

In the second fluorescent material 72, the value of the parameter x is more preferably in a range of 0.0005 or more and 0.400 or less (0.0005≦x≦0.400), and still more preferably in a range of 0.001 or more and 0.350 or less (0.001≦x≦0.350).

+

In the second fluorescent material 72, the value of the parameter y is preferably in a range of exceeding 0.0005 and less than 0.040 (0.0005<y<0.040), and more preferably in a range of 0.001 or more and 0.026 or less (0.001≦y≦0.026).

+

The parameter x is an activation amount of Ce and the value of the parameter x is in a range of exceeding 0.0002 and less than 0.50 (0.0002<x<0.50), and the parameter y is an activation amount of Cr. When the value of the parameter y is in a range of exceeding 0.0001 and less than 0.05 (0.0001<y<0.05), the activation amount of Ce and the activation amount of Cr that are light emission centers contained in the crystal structure of the fluorescent material are within optimum ranges, the decrease of light emission intensity due to the decrease of light emission center can be suppressed, the decrease of light emission intensity due to concentration quenching caused by the increase of the activation amount can be suppressed, and light emission intensity can be enhanced.

+Production Method of Second Fluorescent Material +

A method for producing the second fluorescent material 72 includes the following method.

+

A compound containing at least one rare earth element Ln selected from the group consisting of rare earth elements excluding Ce, a compound containing at least one element M selected from the group consisting of Al, Ga, and In, a compound containing Ce and a compound containing Cr are mixed such that, when the total molar composition ratio of the M is taken as 5 as the standard, in the case where the total molar composition ratio of Ln, Ce, and Nd is 3, the molar ratio of Ce is a product of 3 and a value of a parameter x, and the molar ratio of Cr is a product of 3 and a value of a parameter y, the value of the parameter x is in a range of exceeding 0.0002 and less than 0.50 and the value of the parameter y is in a range of exceeding 0.0001 and less than 0.05, thereby obtaining a raw material mixture, the raw material mixture is heat-treated, followed by classification and the like, thereby obtaining the second fluorescent material.

+Compound Containing Rare Earth Element Ln +

Examples of the compound containing rare earth element Ln include oxides, hydroxides, nitrides, oxynitrides, fluorides, and chlorides, that contain at least one rare earth element Ln selected from the group consisting of rare earth elements excluding Ce. Those compounds may be hydrates. At least a part of the compounds containing rare earth element may use a metal simple substance or an alloy containing rare earth element. The compound containing rare earth element is preferably a compound containing at least one rare earth element Ln selected from the group consisting of Y, Gd, Lu, La, Tb, and Pr. The compound containing rare earth element may be used alone or may be used as a combination of at least two compounds containing rare earth element.

+

The compound containing rare earth element is preferably an oxide that does not contain elements other than the target composition, as compared with other materials. Examples of the oxide specifically include Y2O3, Gd2O3, Lu2O3, La2O3, Tb4O7 and Pr6O11.

+Compound Containing M +

Examples of the compound containing at least one element M selected from the group consisting of Al, Ga, and In include oxides, hydroxides, nitrides, oxynitrides, fluorides, and chlorides, that contain Al, Ga, or In. Those compounds may be hydrates. Furthermore, Al metal simple substance, Ga metal simple substance, In metal simple substance, Al alloy, Ga alloy or In alloy may be used, and metal simple substance or an alloy may be used in place of at least a part of the compound. The compound containing Al, Ga, or In may be used alone or may be used as a combination of two or more thereof. The compound containing at least one element selected from the group consisting of Al, Ga, and In is preferably an oxide. The reason for this is that an oxide that does not contain elements other than the target composition, as compared with other materials, and a fluorescent material having a target composition are easy to be obtained. When a compound containing elements other than the target composition has been used, residual impurity elements are sometimes present in the fluorescent material obtained. The residual impurity element becomes a killer factor in light emission, leading to the possibility of remarkable decrease of light emission intensity.

+

Examples of the compound containing Al, Ga, or In specifically include Al2O3, Ga2O3, and In2O3.

+Compound Containing Ce and Compound Containing Cr +

Examples of the compound containing Ce or the compound containing Cr include oxides, hydroxides, nitrides, fluorides, and chlorides, that contain cerium (Ce) or chromium (Cr). Those compounds may be hydrates. Ce metal simple substance, Ce alloy, Cr metal simple substance, or Cr alloy may be used, and a metal simple substance or an alloy may be used in place of a part of the compound. The compound containing Ce or the compound containing Cr may be used alone or may be used as a combination of two or more thereof. The compound containing Ce or the compound containing Cr is preferably an oxide. The reason for this is that an oxide that does not contain elements other than the target composition, as compared with other materials, and a fluorescent material having a target composition are easy to be obtained. When a compound containing elements other than the target composition has been used, residual impurity elements are sometimes present in the fluorescent material obtained. The residual impurity element becomes a killer factor in light emission, leading to the possibility of remarkable decrease of light emission intensity.

+

Example of the compound containing Ce specifically includes CeO2, and example of the compound containing Cr specifically includes Cr2O3.

+

The raw material mixture may contain a flux such as a halide, as necessary. When a flux is contained in the raw material mixture, reaction of raw materials with each other is accelerated, and a solid phase reaction is easy to proceed further uniformly. It is considered that a temperature for heat-treating the raw material mixture is almost the same as a formation temperature of a liquid phase of a halide used as a flux or is a temperature higher than the formation temperature, and, as a result, the reaction is accelerated.

+

Examples of the halide include fluorides, chlorides of rare earth metals, alkali earth metals, and alkali metals. When a halide of rare earth metal is used as the flux, the flux can be added as a compound so as to achieve a target composition. Examples of the flux specifically include BaF2 and CaF2. Of those, BaF2 is preferably used. When barium fluoride is used as the flux, a garnet crystal structure is stabilized and a composition of a garnet crystal structure is easy to be formed.

+

When the raw material mixture contains a flux, the content of the flux is preferably 20 mass % or less, and more preferably 10 mass % or less, and is preferably 0.1 mass % or more, on the basis of the raw material mixture (100 mass %). When the flux content is within the aforementioned range, the problem that it is difficult to form a garnet crystal structure due to the insufficiency of particle growth by small amount of the flux is prevented, and furthermore, the problem that it is difficult to form a garnet crystal structure due to too large amount of the flux is prevented.

+

The raw material mixture is prepared, for example, as follows. Each of raw materials is weighed so as to be a compounding ratio. Thereafter, the raw materials are subjected to mixed grinding using a dry grinding machine such as ball mill, are subjected to mixed grinding using a mortar and a pestle, are subjected to mixing using a mixing machine such as a ribbon blender, for example, or are subjected to mixed grinding using both a dry grinding machine and a mixing machine. As necessary, the raw material mixture may be classified using a wet separator such as a setting tank generally used industrially, or a dry classifier such as a cyclone. The mixing may be conducted by dry mixing or may be conducted by wet mixing by adding a solvent. The mixing is preferably dry mixing. The reason for this is that dry mixing can shorten a processing time as compared with wet drying, and this leads to the improvement of productivity.

+

The raw material mixture after mixing each raw material is dissolved in an acid, the resulting solution is co-precipitated in oxalic acid, a product formed by the co-precipitation is baked to obtain an oxide, and the oxide may be used as the raw material mixture.

+

The raw material mixture can be heat-treated by placing it in a crucible, a boat made of a carbon material (such as graphite), boron nitride (BN), aluminum oxide (alumina), tungsten (W) or molybdenum (Mo).

+

From the standpoint of stability of a crystal structure, the temperature for heat-treating the raw material mixture is preferably in a range of 1,000° C. or higher and 2,100° C. or lower, more preferably in a range of 1,100° C. or higher and 2,000° C. or lower, still more preferably in a range of 1,200° C. or higher and 1,900° C. or lower, and particularly preferably in a range of 1,300° C. or higher and 1,800° C. or lower. The heat treatment can use an electric furnace or a gas furnace.

+

The heat treatment time varies depending on a temperature rising rate, a heat treatment atmosphere. The heat treatment time after reaching the heat treatment temperature is preferably 1 hour or more, more preferably 2 hours or more, and still more preferably 3 hours or more, and is preferably 20 hours or less, more preferably 18 hours or less and still more preferably 15 hours or less.

+

The atmosphere for heat-treating the raw material mixture is an inert atmosphere such as argon or nitrogen, a reducing atmosphere containing hydrogen, or an oxidizing atmosphere such as the air. The raw material mixture may be subjected to a two-stage heat treatment of a first heat treatment of heat-treating in the air or a weakly reducing atmosphere from the standpoint of, for example, prevention of blackening, and a second heat treatment of heat-treating in a reducing atmosphere from the standpoint of enhancing absorption efficiency of light having a specific light emission peak wavelength. The fluorescent material constituting a garnet structure is that reactivity of the raw material mixture is improved in an atmosphere having high reducing power such as a reducing atmosphere. Therefore, the fluorescent material can be heat-treated under the atmospheric pressure without pressurizing. For example, the heat treatment can be conducted by the method disclosed in Japanese Patent Application No. 2014-260421.

+

The fluorescent material obtained may be subjected to post-treatment steps such as a solid-liquid separation by a method such as cleaning or filtration, drying by a method such as vacuum drying, and classification by dry sieving. After those post-treatment steps, a fluorescent material having a desired average particle diameter is obtained.

+Other Fluorescent Materials +

The light emitting device 100 may contain other kinds of fluorescent materials, in addition to the first fluorescent material 71.

+

Examples of other kinds of fluorescent materials include a green fluorescent material emitting green color by absorbing a part of the light emitted from the light emitting element 10, a yellow fluorescent material emitting yellow color, and a fluorescent material having a light emission peak wavelength in a wavelength range exceeding 680 nm.

+

Examples of the green fluorescent material specifically include fluorescent materials having any one of compositions represented by the following formulae (i) to (iii).

+

+
+M118MgSi4O16X11:Eu  (i) +

+

wherein M11 is at least one selected from the group consisting of Ca, Sr, Ba, and Zn, and X11 is at least one selected from the group consisting of F, Cl, Br, and I.

+

+
+Si6-bAlbObN8-b:Eu  (ii) +

+

wherein b satisfies 0<b<4.2.

+

+
+M13Ga2S4:Eu  (iii) +

+

wherein M13 is at least one selected from the group consisting of Mg, Ca, Sr, and

+

Ba.

+

Examples of the yellow fluorescent material specifically include fluorescent materials having any one of compositions represented by the following formulae (iv) to (v).

+

+
+M14c/dSi12-(c+d)Al(c+d)OdN(16-d):Eu  (iv) +

+

wherein M14 is at least one selected from the group consisting of Sr, Ca, Li, and Y. A value of a parameter c is in a range of 0.5 to 5, a value of a parameter d is in a range of 0 to 2.5, and the parameter d is an electrical charge of M14.

+

+
+M153Al5O12:Ce  (v) +

+

wherein M15 is at least one selected from the group consisting of Y and Lu.

+

Examples of the fluorescent material having light emission peak wavelength in a wavelength range exceeding 680 nm specifically include fluorescent materials having any one of compositions represented by the following formulae (vi) to (x).

+

+
+Al2O3:Cr  (vi) +

+

+
+CaYAlO4:Mn  (vii) +

+

+
+LiAlO2:Fe  (viii) +

+

+
+CdS:Ag  (ix) +

+

+
+GdAlO3:Cr  (x) +

+

The light emitting device 100 can be utilized as a light emitting device for plant cultivation that can activate photosynthesis of plants and promote growth of plants so as to have favorable form and weight.

+Plant Cultivation Method +

The plant cultivation method of one embodiment of the present disclosure is a method for cultivating plants, including irradiating plants with light emitted from the light emitting device 100. In the plant cultivation method, plants can be irradiated with light from the light emitting device 100 in plant factories that are completely isolated from external environment and make it possible for artificial control. The kind of plants is not particularly limited. However, the light emitting device 100 of one embodiment of the present disclosure can activate photosynthesis of plants and promote growth of plants such that a stem, a leaf, a root, a fruit have favorable form and weight, and therefore is preferably applied to cultivation of vegetables, flowers that contain much chlorophyll performing photosynthesis. Examples of the vegetables include lettuces such as garden lettuce, curl lettuce, Lamb's lettuce, Romaine lettuce, endive, Lollo Rosso, Rucola lettuce, and frill lettuce; Asteraceae vegetables such as “shungiku” (chrysanthemum coronarium); morning glory vegetables such as spinach; Rosaceae vegetables such as strawberry; and flowers such as chrysanthemum, gerbera, rose, and tulip.

+EXAMPLES +

The present invention is further specifically described below by Examples and Comparative Examples.

+Examples 1 to 5 +First Fluorescent Material +

Two fluorescent materials of fluorogarmanate fluorescent material that is activated by Mn4+, having a light emission peak at 660 nm and fluorescent material containing silicon nitride that are activated by Eu2+, having a light emission peak at 660 nm were used as the first fluorescent material 71. In the first fluorescent material 71, a mass ratio of a MGF fluorescent material to a CASN fluorescent material (MGF:CASN) was 95:5.

+Second Fluorescent Material +

Fluorescent material that is obtained by the following production method was used as the second fluorescent material 72.

+

55.73 g of Y2O3 (Y2O3 content: 100 mass %), 0.78 g of CeO2 (CeO2 content: 100 mass %), 0.54 g of Cr2O3 (Cr2O3 content: 100 mass %,) and 42.95 g of Al2O3 (Al2O3 content: 100 mass %) were weighed as raw materials, and 5.00 g of BaF2 as a flux was added to the mixture. The resulting raw materials were dry mixed for 1 hour by a ball mill. Thus, a raw material mixture was obtained.

+

The raw material mixture obtained was placed in an alumina crucible, and a lid was put on the alumina crucible. The raw material mixture was heat-treated at 1,500° C. for 10 hours in a reducing atmosphere of H2: 3 vol % and N2: 97 vol %. Thus, a calcined product was obtained. The calcined product was passed through a dry sieve to obtain a second fluorescent material. The second fluorescent material obtained was subjected to composition analysis by ICP-AES emission spectrometry using an inductively coupled plasma emission analyzer (manufactured by Perkin Elmer). The composition of the second fluorescent material obtained was (Y0.977Ce0.009Cr0.014)3Al5O12 (hereinafter referred to as “YAG: Ce, Cr”).

+Light Emitting Device +

Nitride semiconductor having a light emission peak wavelength of 450 nm was used as the light emitting element 10 in the light emitting device 100.

+

Silicone resin was used as a sealing material constituting the fluorescent member 50, the first fluorescent material 71 and/or the second fluorescent material 72 was added to 100 parts by mass of the silicone resin in the compounding ratio (parts by mass) shown in Table 1, and 15 parts by mass of silica filler were further added thereto, followed by mixing and dispersing. The resulting mixture was degassed to obtain a resin composition constituting a fluorescent member. In each of resin compositions of Examples 1 to 5, the compounding ratio of the first fluorescent material 71 and the second fluorescent material 72 was adjusted as shown in Table 1, and those materials are compounded such that the R/B ratio is within a range of 2.0 or more and 2.4 or less, and the R/FR ratio is within a range of 1.4 or more and 6.0 or less.

+

The resin composition was poured on the light emitting element 10 of a depressed portion of the molded article 40 to fill the depressed portion, and heated at 150° C. for 4 hours to cure the resin composition, thereby forming the fluorescent member 50. Thus, the light emitting device 100 as shown in FIG. 1 was produced in each of Examples 1 to 5.

+Comparative Example 1 +

A light emitting device X including a semiconductor light emitting element having a light emission peak wavelength of 450 nm and a light emitting device Y including a semiconductor light emitting element having a light emission peak length of 660 nm were used, and the R/B ratio was adjusted to 2.5.

+Evaluation +Photon Flux Density +

Photon flux densities of lights emitted from the light emitting device 100 used in Examples 1 to 5 and the light emitting devices X and Y used in Comparative Example 1 were measured using a photon measuring device (LI-250A, manufactured by Li-COR). The photon flux density B, the photon flux density R, and the photon flux density FR of lights emitted from the light emitting devices used in each of the Examples and Comparative Example; the R/B ratio; and the R/FR ratio are shown in Table 1. FIG. 2 shows spectra showing the relationship between a wavelength and a relative photon flux density, in the light emitting devices used in each Example and Comparative Example.

+Plant Cultivation Test +

The plant cultivation method includes a method of conducting by “growth period by RGB light source (hereinafter referred to as a first growth period)” and “growth period by light source for plant growth (hereinafter referred to as a second growth period)” using a light emitting device according to an embodiment of the present disclosure as a light source.

+

The first growth period uses RGB light source, and RGB type LED generally known can be used as the RGB light source. The reason for irradiating plants with RGB type LED in the initial stage of the plant growth is that length of a stem and the number and size of true leaves in the initial stage of plant growth are made equal, thereby clarifying the influence by the difference of light quality in the second growth period.

+

The first growth period is preferably about 2 weeks. In the case where the first growth period is shorter than 2 weeks, it is necessary to confirm that two true leaves develop and a root reaches length that can surely absorb water in the second growth period. In the case where the first growth period exceeds 2 weeks, variation in the second growth period tends to increase. The variation is easy to be controlled by RGB light source by which stem extension is inhibitory, rather than a fluorescent lamp by which stem extension is easy to occur.

+

After completion of the first growth period, the second growth period immediately proceeds. It is preferred that plants are irradiated with light emitted from a light emitting device according to an embodiment of the present disclosure. Photosynthesis of plants is activated by irradiating plants with light emitted from the light emitting device according to an embodiment of the present disclosure, and the growth of plants can be promoted so as to have favorable form and weight.

+

The total growth period of the first growth period and the second growth period is about 4 to 6 weeks, and it is preferred that shippable plants can be obtained within the period.

+

The cultivation test was specifically conducted by the following method.

+

Romaine lettuce (green romaine, produced by Nakahara Seed Co., Ltd.) was used as cultivation plant.

+First Growth Period +

Urethane sponges (salad urethane, manufactured by M Hydroponic Research Co., Ltd.) having Romaine lettuce seeded therein were placed side by side on a plastic tray, and were irradiated with light from RGB-LED light source (manufactured by Shibasaki Inc.) to cultivate plants. The plants were cultivated for 16 days under the conditions of room temperature: 22 to 23° C., humidity: 50 to 60%, photon flux density from light emitting device: 100 μmol·m−2·s−1 and daytime hour: 16 hours/day. Only water was given until germination, and after the germination (about 4 days later), a solution obtained by mixing Otsuka House #1 (manufactured by Otsuka Chemical Co., Ltd.) and Otsuka House #2 (manufactured by Otsuka Chemical Co., Ltd.) in a mass ratio of 3:2 and dissolving the mixture in water was used as a nutrient solution (Otsuka Formulation A). Conductivity of the nutrient was 1.5 ms·cm−1.

+Second Growth Period +

After the first growth period, the plants were irradiated with light from the light emitting devices of Examples 1 to 5 and Comparative Example 1, and were subjected to hydroponics.

+

The plants were cultivated for 19 days under the conditions of room temperature: 22 to 24° C., humidity: 60 to 70%, CO2 concentration: 600 to 700 ppm, photon flux density from light emitting device: 125 μmol·m−2·s−1 and daytime hour: 16 hours/day. Otsuka Formulation A was used as the nutrient solution. Conductivity of the nutrient was 1.5 ms·cm−1. The values of the R/B and R/FR ratios of light for plant irradiation from each light emitting device in the second growth period are shown in Table 1.

+Measurement of Fresh Weight (Edible Part) +

The plants after cultivation were harvested, and wet weights of a terrestrial part and a root were measured. The wet weight of a terrestrial part of each of 6 cultivated plants having been subjected to hydroponics by irradiating with light from the light emitting devices of Examples 1 to 5 and Comparative Example 1 was measured as a fresh weight (edible part) (g). The results obtained are shown in Table 1 and FIG. 3.

+Measurement of Nitrate Nitrogen Content +

The edible part (about 20 g) of each of the cultivated plants, from which a foot about 5 cm had been removed, was frozen with liquid nitrogen and crushed with a juice mixer (laboratory mixer LM-PLUS, manufactured by Osaka Chemical Co., Ltd.) for 1 minute. The resulting liquid was filtered with Miracloth (manufactured by Milipore), and the filtrate was centrifuged at 4° C. and 15,000 rpm for 5 minutes. The nitrate nitrogen content (mg/100 g) in the cultivated plant in the supernatant was measured using a portable reflection photometer system (product name: RQ flex system, manufactured by Merck) and a test paper (product name: Reflectoquant (registered trade mark), manufactured by Kanto Chemical Co., Inc.). The results are shown in Table 1 and FIG. 4.

+

+ + + + + + + + + + + +TABLE 1 + + + + + + + + + +Fluorescent material + + + + + + +(parts by mass) +Photon flux +Ratio of + + + + + + + + + + + + + + +First fluorescent +Second fluorescent +density +photon +Fresh weight +Nitrate nitrogen + + + +material +material +(μmol · m−2 · s−1) +flux densities +(Edible part) +content + + + + + + + + + + + + + + + + + +(MGF/CASN = 95:5) +(YAG: Ce, Cr) +B +R +FR +R/B +R/FR +(g) +(mg/100 g) + + + + + + + + + + + + + + + + + + + + +Comparative +— +— +35.5 +88.8 +0.0 +2.5 +— +26.2 +361.2 + + +Example 1 + + +Example 1 +60 +— +31.5 +74.9 +12.6 +2.4 +6.0 +35.4 +430.8 + + +Example 2 +50 +10 +28.5 +67.1 +21.7 +2.4 +3.1 +34.0 +450.0 + + +Example 3 +40 +20 +25.8 +62.0 +28.7 +2.4 +2.2 +33.8 +452.4 + + +Example 4 +30 +30 +26.8 +54.7 +33.5 +2.0 +1.6 +33.8 +345.0 + + +Example 5 +25 +39 +23.4 +52.8 +38.1 +2.3 +1.4 +28.8 +307.2 + + + + + + +
+ +

+

As shown in Table 1, for the light emitting devices in Examples 1 to 5, the R/B ratios are within a range of 2.0 or more and 4.0 or less and the R/FR ratios are within the range of 0.7 or more and 13.0 or less. For Romaine lettuce cultivated by irradiating with light from the light emitting device in Examples 1 to 5, the fresh weight (edible part) was increased as compared with Romaine lettuce cultivated by irradiating with light from the light emitting device used in Comparative Example 1. Therefore, cultivation of plants was promoted, as shown in Table 1 and FIG. 3.

+

As shown in FIG. 2, the light emitting device 100 in Example 1 had at least one maximum value of the relative photon flux density in a range of 380 nm or more and 490 nm or less and in a range of 580 nm or more and less than 680 nm. The light emitting devices 100 in Examples 2 to 5 had at least one maximum value of relative photon flux density in a range of 380 nm or more and 490 nm or less, in a range of 580 nm or more and less than 680 nm and in a range of 680 nm or more and 800 nm or less, respectively. The maximum value of the relative photon flux density in a range of 380 nm or more and 490 nm or less is due to the light emission of the light emitting element having light emission peak wavelength in a range of 380 nm or more and 490 nm or less, the maximum value of the relative photon flux density in a range of 580 nm or more and less than 680 nm is due to the first fluorescent material emitting the light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm, and the maximum value of the relative photon flux density in a range of 680 nm or more and 800 nm or less is due to the second fluorescent material emitting the light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less.

+

As shown in Table 1, for the light emitting devices 100 in Examples 4 and 5, the R/B ratios are 2.0 and 2.3, respectively, and the R/FR ratios are 1.6 and 1.4, respectively. The R/B ratios are within a range of 2.0 or more and 4.0 or less, and the R/FR ratios are within a range of 0.7 or more and 2.0 or less. For Romaine lettuces cultivated by irradiating with lights from the light emitting devices 100, the nitrate nitrogen content is decreased as compared with Comparative Example 1. Plants, in which the nitrate nitrogen content having the possibility of adversely affecting health of human body had been reduced to a range that does not inhibit the cultivation of plants, could be cultivated, as shown in Table 1 and FIG. 4.

+

The light emitting device according to an embodiment of the present disclosure can be utilized as a light emitting device for plant cultivation that can activate photosynthesis and is capable of promoting growth of plants. Furthermore, the plant cultivation method, in which plants are irradiated with the light emitted from the light emitting device according to an embodiment of the present disclosure, can cultivate plants that can be harvested in a relatively short period of time and can be used in a plant factory.

+

Although the present disclosure has been described with reference to several exemplary embodiments, it shall be understood that the words that have been used are words of description and illustration, rather than words of limitation. Changes may be made within the purview of the appended claims, as presently stated and as amended, without departing from the scope and spirit of the disclosure in its aspects. Although the disclosure has been described with reference to particular examples, means, and embodiments, the disclosure may be not intended to be limited to the particulars disclosed; rather the disclosure extends to all functionally equivalent structures, methods, and uses such as are within the scope of the appended claims.

+

One or more examples or embodiments of the disclosure may be referred to herein, individually and/or collectively, by the term “disclosure” merely for convenience and without intending to voluntarily limit the scope of this application to any particular disclosure or inventive concept. Moreover, although specific examples and embodiments have been illustrated and described herein, it should be appreciated that any subsequent arrangement designed to achieve the same or similar purpose may be substituted for the specific examples or embodiments shown. This disclosure may be intended to cover any and all subsequent adaptations or variations of various examples and embodiments. Combinations of the above examples and embodiments, and other examples and embodiments not specifically described herein, will be apparent to those of skill in the art upon reviewing the description.

+

In addition, in the foregoing Detailed Description, various features may be grouped together or described in a single embodiment for the purpose of streamlining the disclosure. This disclosure may be not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter may be directed to less than all of the features of any of the disclosed embodiments. Thus, the following claims are incorporated into the Detailed Description, with each claim standing on its own as defining separately claimed subject matter.

+

The above disclosed subject matter shall be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments which fall within the true spirit and scope of the present disclosure. Thus, to the maximum extent allowed by law, the scope of the present disclosure may be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.

+ + +What is claimed is: + + +1. A light emitting device comprising: +a light emitting element having a light emission peak wavelength in a range of 380 nm or more and 490 nm or less; and +a fluorescent material that is excited by light from the light emitting element and emits light having at least one light emission peak wavelength in a range of 580 nm or more and less than 680 nm, wherein +the light emitting device emits light having a ratio R/B of a photon flux density R to a photon flux density B within a range of 2.0 or more and 4.0 or less, and a ratio R/FR of the photon flux density R to a photon flux density FR within a range of 0.7 or more and 13.0 or less, wherein +the photon flux density R is in a wavelength range of 620 nm or more and less than 700 nm, +the photon flux density B is in a wavelength range of 380 nm or more and 490 nm or less, and +the photon flux density FR is in a wavelength range of 700 nm or more and 780 nm or less. + + + + + +2. The light emitting device according to claim 1, further comprising another fluorescent material that is excited by light from the light emitting element and emits light having at least one light emission peak wavelength in a range of 680 nm or more and 800 nm or less, wherein the ratio R/FR is within a range of 0.7 or more and 5.0 or less. + + +3. The light emitting device according to claim 2, wherein the ratio R/FR is within a range of 0.7 or more and 2.0 or less. + + +4. The light emitting device according to claim 2, wherein +the another fluorescent material contains a first element Ln containing at least one element selected from the group consisting of rare earth elements excluding Ce, a second element M containing at least one element selected from the group consisting of Al, Ga and In, Ce, and Cr, and has a composition of an aluminate fluorescent material, and +when a molar ratio of the second element M is taken as 5, a molar ratio of Ce is a product of a value of a parameter x and 3, and a molar ratio of Cr is a product of a value of a parameter y and 3, the value of the parameter x being in a range of exceeding 0.0002 and less than 0.50, and the value of the parameter y being in a range of exceeding 0.0001 and less than 0.05. + + + +5. The light emitting device according to claim 2, wherein the another fluorescent material has the composition represented by the following formula (I): + +
+(Ln1-x-yCexCry)3M5O12  (I) + +wherein Ln is at least one rare earth element selected from the group consisting of rare earth elements excluding Ce, +M is at least one element selected from the group consisting of Al, Ga, and In, and +x and y are numbers satisfying 0.0002<x<0.50 and 0.0001<y<0.05. + + + +6. The light emitting device according to claim 2, the light emitting device being used in plant cultivation. + + +7. The light emitting device according to claim 1, wherein the fluorescent material is at least one selected from the group consisting of: +a fluorogermanate fluorescent material that is activated by Mn4+, +a fluorescent material that has a composition containing at least one element selected from Sr and Ca, and Al, and contains silicon nitride that is activated by Eu2+, +a fluorescent material that has a composition containing at least one element selected from the group consisting of alkaline earth metal elements and at least one element selected from the group consisting of alkali metal elements, and contains aluminum nitride that is activated by Eu2+, +a fluorescent material containing a sulfide of Ca or Sr that is activated by Eu2+, and +a fluorescent material that has a composition containing at least one element or ion selected from the group consisting of alkali metal elements, and an ammonium ion (NH4+), and at least one element selected from the group consisting of Group 4 elements and Group 14 elements, and contains a fluoride that is activated by Mn4+. + + + +8. The light emitting device according to claim 1, wherein the fluorescent material contains: +a fluorogermanate fluorescent material that is activated by Mn4+, and +a fluorescent material that has a composition containing at least one element selected from Sr and Ca, and Al, and contains silicon nitride that is activated by Eu2+, wherein +the compounding ratio between the fluorogermanate fluorescent material and the fluorescent material containing silicon nitride (fluorogermanate fluorescent material:fluorescent material containing silicon nitride) is in a range of 50:50 or more and 99:1 or less. + + + + +9. The light emitting device according to claim 1, the light emitting device being used in plant cultivation. + + +10. A plant cultivation method comprising irradiating plants with light emitted from the light emitting device according to claim 1. + + +11. A plant cultivation method comprising irradiating plants with light emitted from the light emitting device according to claim 2. + + + \ No newline at end of file diff --git a/tests/data/uspto/ipa20200022300.xml b/tests/data/uspto/ipa20200022300.xml new file mode 100644 index 00000000..c31a141f --- /dev/null +++ b/tests/data/uspto/ipa20200022300.xml @@ -0,0 +1,456 @@ + + + + + + +US +20200022300 +A1 +20200123 + + + + +US +16039511 +20180719 + + +16 + + +20060101 +A +
A
+01 +B +63 +32 +F +I +20200123 +US +B +H + + +20060101 +A +
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F
+15 +B +21 +00 +L +I +20200123 +US +B +H + + +20060101 +A +
F
+15 +B +11 +10 +L +I +20200123 +US +B +H + + + + + +20130101 +
A
+01 +B +63 +32 +F +I +20200123 +US +B +H +C + + + + +20130101 +
A
+01 +C +5 +062 +L +I +20200123 +US +B +H +C + + +20130101 +
A
+01 +C +5 +068 +L +I +20200123 +US +B +H +C + + +20130101 +
A
+01 +B +63 +008 +L +I +20200123 +US +B +H +C + + +20130101 +
F
+15 +B +2211 +8616 +L +A +20200123 +US +B +H +C + + +20130101 +
F
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F
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F
+15 +B +2211 +7053 +L +A +20200123 +US +B +H +C + + +20130101 +
F
+15 +B +21 +008 +L +I +20200123 +US +B +H +C + + + +SYSTEM FOR CONTROLLING THE OPERATION OF AN ACTUATOR MOUNTED ON A SEED PLANTING IMPLEMENT + + + + +CNH Industrial Canada, Ltd. +
+Saskatoon +CA +
+ + +CA + + + + + + +Gervais +Joel John Octave +
+Saskatoon +CA +
+ + + + +Paulson +Ian William Patrick +
+Saskatoon +CA +
+ + + + + + +

In one aspect, a system for controlling an operation of an actuator mounted on a seed planting implement may include an actuator configured to adjust a position of a row unit of the seed planting implement relative to a toolbar of the seed planting implement. The system may also include a flow restrictor fluidly coupled to a fluid chamber of the actuator, with the flow restrictor being configured to reduce a rate at which fluid is permitted to exit the fluid chamber in a manner that provides damping to the row unit. Furthermore, the system may include a valve fluidly coupled to the flow restrictor in a parallel relationship such that the valve is configured to permit the fluid exiting the fluid chamber to flow through the flow restrictor and the fluid entering the fluid chamber to bypass the flow restrictor.

+ + +
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+ + + +FIELD +

The present disclosure generally relates to seed planting implements and, more particularly, to systems for controlling the operation of an actuator mounted on a seed planting implement in a manner that provides damping to one or more components of the seed planting implement.

+BACKGROUND +

Modern farming practices strive to increase yields of agricultural fields. In this respect, seed planting implements are towed behind a tractor or other work vehicle to deposit seeds in a field. For example, seed planting implements typically include one or more ground engaging tools or openers that form a furrow or trench in the soil. One or more dispensing devices of the seed planting implement may, in turn, deposit seeds into the furrow(s). After deposition of the seeds, a packer wheel may pack the soil on top of the deposited seeds.

+

In certain instances, the packer wheel may also control the penetration depth of the furrow. In this regard, the position of the packer wheel may be moved vertically relative to the associated opener(s) to adjust the depth of the furrow. Additionally, the seed planting implement includes an actuator configured to exert a downward force on the opener(s) to ensure that the opener(s) is able to penetrate the soil to the depth set by the packer wheel. However, the seed planting implement may bounce or chatter when traveling at high speeds and/or when the opener(s) encounters hard or compacted soil. As such, operators generally operate the seed planting implement with the actuator exerting more downward force on the opener(s) than is necessary in order to prevent such bouncing or chatter. Operation of the seed planting implement with excessive down pressure applied to the opener(s), however, reduces the overall stability of the seed planting implement.

+

Accordingly, an improved system for controlling the operation of an actuator mounted on s seed planting implement to enhance the overall operation of the implement would be welcomed in the technology.

+BRIEF DESCRIPTION +

Aspects and advantages of the technology will be set forth in part in the following description, or may be obvious from the description, or may be learned through practice of the technology.

+

In one aspect, the present subject matter is directed to a system for controlling an operation of an actuator mounted on a seed planting implement. The system may include a toolbar and a row unit adjustably mounted on the toolbar. The system may also include a fluid-driven actuator configured to adjust a position of the row unit relative to the toolbar, with the fluid-driven actuator defining first and second fluid chambers. Furthermore, the system may include a flow restrictor fluidly coupled to the first fluid chamber, with the flow restrictor being configured to reduce a rate at which fluid is permitted to exit the first fluid chamber in a manner that provides viscous damping to the row unit. Additionally, the system may include a valve fluidly coupled to the first fluid chamber. The valve may further be fluidly coupled to the flow restrictor in a parallel relationship such that the valve is configured to permit the fluid exiting the first fluid chamber to flow through the flow restrictor and the fluid entering the first fluid chamber to bypass the flow restrictor.

+

In another aspect, the present subject matter is directed to a seed planting implement including a toolbar and a plurality of row units adjustably coupled to the toolbar. Each row unit may include a ground engaging tool configured to form a furrow in the soil. The seed planting implement may also include plurality of fluid-driven actuators, with each fluid-driven actuator being coupled between the toolbar and a corresponding row unit of the plurality of row units. As such, each fluid-driven actuator may be configured to adjust a position of the corresponding row unit relative to the toolbar. Moreover, each fluid-driven actuator may define first and second fluid chambers. Furthermore, the seed planting implement may include a flow restrictor fluidly coupled to the first fluid chamber of a first fluid-driven actuator of the plurality of fluid-driven actuators. The flow restrictor may be configured to reduce a rate at which fluid is permitted to exit the first fluid chamber of the first fluid-driven actuator in a manner that provides viscous damping to the corresponding row unit. Additionally, the seed planting implement may include a valve fluidly coupled to the first fluid chamber of the first fluid-driven actuator. The valve further may be fluidly coupled to the flow restrictor in a parallel relationship such that the valve is configured to permit the fluid exiting the first fluid chamber to flow through the flow restrictor and the fluid entering the first fluid chamber to bypass the flow restrictor.

+

In a further aspect, the present subject matter is directed to a system for providing damping to a row unit of a seed planting implement. The system may include a toolbar, a row unit adjustably mounted on the toolbar, and a fluid-driven actuator configured to adjust a position of the row unit relative to the toolbar. As such, the fluid-driven actuator may define a fluid chamber. The system may also include a flow restrictor fluidly coupled to the fluid chamber. The flow restrictor may define an adjustable throat configured to reduce a rate at which fluid is permitted to exit the fluid chamber. In this regard, the throat may be adjustable between a first size configured to provide a first damping rate to the row unit and a second size configured to provide a second damping rate to the row unit, with the first and second damping rates being different.

+

These and other features, aspects and advantages of the present technology will become better understood with reference to the following description and appended claims. The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the technology and, together with the description, serve to explain the principles of the technology.

+ + + +BRIEF DESCRIPTION OF THE DRAWINGS +

A full and enabling disclosure of the present technology, including the best mode thereof, directed to one of ordinary skill in the art, is set forth in the specification, which makes reference to the appended figures, in which:

+

FIG. 1 illustrates a perspective view of one embodiment of a seed planting implement in accordance with aspects of the present subject matter;

+

FIG. 2 illustrates a side view of one embodiment of a row unit suitable for use with a seed planting implement in accordance with aspects of the present subject matter;

+

FIG. 3 illustrates a schematic view of one embodiment of a system for controlling the operation of an actuator mounted on a seed planting implement in accordance with aspects of the present subject matter;

+

FIG. 4 illustrates a cross-sectional view of one embodiment of a flow restrictor suitable for use in the system shown in FIG. 3, particularly illustrating the flow restrictor defining a throat having a fixed size in accordance with aspects of the present subject matter;

+

FIG. 5 illustrates a cross-sectional view of another embodiment of a flow restrictor suitable for use in the system shown in FIG. 3, particularly illustrating the flow restrictor defining a throat having an adjustable size in accordance with aspects of the present subject matter;

+

FIG. 6 illustrates a simplified cross-sectional view of the flow restrictor shown in FIG. 5, particularly illustrating the throat having a first size configured to provide a first damping rate in accordance with aspects of the present subject matter;

+

FIG. 7 illustrates a simplified cross-sectional view of the flow restrictor shown in FIG. 5, particularly illustrating the throat having a second size configured to provide a second damping rate in accordance with aspects of the present subject matter;

+

FIG. 8 illustrates a cross-sectional view of another embodiment of a system for controlling the operation of an actuator mounted on a seed planting implement in accordance with aspects of the present subject matter, particularly illustrating the system including a fluidly actuated check valve; and

+

FIG. 9 illustrates a cross-sectional view of a further embodiment of a system for controlling the operation of an actuator mounted on a seed planting implement in accordance with aspects of the present subject matter, particularly illustrating the system including an electrically actuated check valve.

+ + + +

Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present technology.

+DETAILED DESCRIPTION +

Reference now will be made in detail to embodiments of the invention, one or more examples of which are illustrated in the drawings. Each example is provided by way of explanation of the invention, not limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope or spirit of the invention. For instance, features illustrated or described as part of one embodiment can be used with another embodiment to yield a still further embodiment. Thus, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents.

+

In general, the present subject matter is directed to systems for controlling the operation of an actuator mounted on a seed planting implement. Specifically, the disclosed systems may be configured to control the operation of the actuator in a manner that provides damping to one or more components of the seed planting implement. For example, in several embodiments, the seed planting implement may include a toolbar and one or more row units adjustably coupled to the toolbar. One or more fluid-driven actuators of the seed planting implement may be configured to control and/or adjust the position of the row unit(s) relative to the toolbar. Furthermore, a flow restrictor may be fluidly coupled to a fluid chamber of the actuator and configured to reduce the rate at which fluid is permitted to exit the fluid chamber so as to provide viscous damping to the row unit(s). In this regard, when the row unit(s) moves relative to the toolbar (e.g., when the row unit contacts a rock or other impediment in the soil), the flow restrictor may be configured to reduce the relative speed and/or displacement of such movement, thereby damping the movement of the row unit(s) relative to the toolbar.

+

In one embodiment, the flow restrictor may be configured to provide a variable damping rate to the component(s) of the seed planting implement. Specifically, in such embodiment, the flow restrictor may be configured as an adjustable valve having one or more components that may be adjusted to change the size of a fluid passage or throat defined by the valve. In this regard, changing the throat size of the valve varies the rate at which the fluid may exit the fluid chamber of the actuator, thereby adjusting the damping rate provided by the disclosed system. For example, adjusting the valve so as to increase the size of the throat may allow the fluid to exit the fluid chamber more quickly, thereby reducing the damping rate of the system. Conversely, adjusting the valve so as to decrease the size of the throat may allow the fluid to exit the fluid chamber more slowly, thereby increasing the damping rate of the system.

+

In accordance with aspects of the present subject matter, the system may further include a check valve fluidly coupled to the fluid chamber of the actuator. Specifically, in several embodiments, the check valve may also be fluidly coupled to the flow restrictor in a parallel relationship. As such, the check valve may be configured to direct the fluid exiting the fluid chamber of the actuator (e.g., when one of the row units hits a rock) to flow through the flow restrictor, thereby reducing the relative speed and/or displacement between the row unit(s) in the toolbar. Furthermore, the check valve may be configured to permit the fluid entering the fluid chamber to bypass the flow restrictor. For example, the fluid may return to the fluid chamber as the row unit(s) returns to its initial position following contact with the rock. In this regard, allowing the returning fluid to bypass the flow restrictor may increase the rate at which the fluid flows back into the fluid chamber, thereby further increasing the damping provided by the disclosed system.

+

Referring now to FIG. 1, a perspective view of one embodiment of a seed planting implement 10 is illustrated in accordance with aspects of the present subject matter. As shown in FIG. 1, the implement 10 may include a laterally extending toolbar or frame assembly 12 connected at its middle to a forwardly extending tow bar 14 to allow the implement 10 to be towed by a work vehicle (not shown), such as an agricultural tractor, in a direction of travel (e.g., as indicated by arrow 16). The toolbar 12 may generally be configured to support a plurality of tool frames 18. Each tool frame 18 may, in turn, be configured to support a plurality of row units 20. As will be described below, each row unit 20 may include one or more ground engaging tools configured to excavate a furrow or trench in the soil.

+

It should be appreciated that, for purposes of illustration, only a portion of the row units 20 of the implement 10 have been shown in FIG. 1. In general, the implement 10 may include any number of row units 20, such as six, eight, twelve, sixteen, twenty-four, thirty-two, or thirty-six row units. In addition, it should be appreciated that the lateral spacing between row units 20 may be selected based on the type of crop being planted. For example, the row units 20 may be spaced approximately thirty inches from one another for planting corn, and approximately fifteen inches from one another for planting soybeans.

+

It should also be appreciated that the configuration of the implement 10 described above and shown in FIG. 1 is provided only to place the present subject matter in an exemplary field of use. Thus, it should be appreciated that the present subject matter may be readily adaptable to any manner of implement configuration.

+

Referring now to FIG. 2, a side view of one embodiment of a row unit 20 is illustrated in accordance with aspects of the present subject matter. As shown, the row unit 20 is configured as a hoe opener row unit. However, it should be appreciated that, in alternative embodiments, the row unit 20 may be configured as a disc opener row unit or any other suitable type of seed planting unit. Furthermore, it should be appreciated that, although the row unit 20 will generally be described in the context of the implement 10 shown in FIG. 1, the row unit 20 may generally be configured to be installed on any suitable seed planting implement having any suitable implement configuration.

+

As shown, the row unit 20 may be adjustably coupled to one of the tool frames 18 of the implement 10 by a suitable linkage assembly 22. For example, in one embodiment, the linkage assembly 22 may include a mounting bracket 24 coupled to the tool frame 18. Furthermore, the linkage assembly 22 may include first and second linkage members 26, 28. One end of each linkage member 26, 28 may be pivotably coupled to the mounting bracket 24, while an opposed end of each linkage member 26, 28 may be pivotally coupled to a support member 30 of the row unit 20. In this regard, the linkage assembly 22 may form a four bar linkage with the support member 30 that permits relative pivotable movement between the row unit 20 and the associated tool frame 18. However, it should be appreciated that, in alternative embodiments, the row unit 20 may be adjustably coupled to the tool frame 18 or the toolbar 12 via any other suitable linkage assembly. Furthermore, it should be appreciated that, in further embodiments the linkage assembly 22 may couple the row unit 20 directly to the toolbar 12.

+

Furthermore, the support member 30 may be configured to support one or more components of the row unit 20. For example, in several embodiments, a ground engaging shank 32 may be mounted or otherwise supported on support member 22. As shown, the shank 32 may include an opener 34 configured to excavate a furrow or trench in the soil as the implement 10 moves in the direction of travel 12 to facilitate deposition of a flowable granular or particulate-type agricultural product, such as seed, fertilizer, and/or the like. Moreover, the row unit 20 may include a packer wheel 36 configured to roll along the soil and close the furrow after deposition of the agricultural product. In one embodiment, the packer wheel 36 may be coupled to the support member 30 by an arm 38. It should be appreciated that, in alternative embodiments, any other suitable component(s) may be supported on or otherwise coupled to the support member 30. For example, the row unit 20 may include a ground engaging disc opener (not shown) in lieu of the ground engaging shank 32.

+

Additionally, in several embodiments, a fluid-driven actuator 102 of the implement 10 may be configured to adjust the position of one or more components of the row unit 20 relative to the tool frame 18. For example, in one embodiment, a rod 104 of the actuator 102 may be coupled to the shank 32 (e.g., the end of the shank 32 opposed from the opener 34), while a cylinder 106 of the actuator 102 may be coupled to the mounting bracket 24. As such, the rod 104 may be configured to extend and/or retract relative to the cylinder 106 to adjust the position of the shank 32 relative to the tool frame 18, which, in turn, adjusts the force being applied to the shank 32. However, it should be appreciated that, in alternative embodiments, the rod 104 may be coupled to the mounting bracket 24, while the cylinder 106 may be coupled to the shank 32. Furthermore, it should be appreciated that, in further embodiments, the actuator 102 may be coupled to any other suitable component of the row unit 20 and/or directly to the toolbar 12.

+

Moreover, it should be appreciated that the configuration of the row unit 20 described above and shown in FIG. 2 is provided only to place the present subject matter in an exemplary field of use. Thus, it should be appreciated that the present subject matter may be readily adaptable to any manner of seed planting unit configuration.

+

Referring now to FIG. 3, a schematic view of one embodiment of a system 100 for controlling the operation of an actuator mounted on a seed planting implement is illustrated in accordance with aspects of the present subject matter. In general, the system 100 will be described herein with reference to the seed planting implement 10 and the row unit 20 described above with reference to FIGS. 1 and 2. However, it should be appreciated by those of ordinary skill in the art that the disclosed system 100 may generally be utilized with seed planting implements having any other suitable implement configuration and/or seed planting units having any other suitable unit configuration.

+

As shown in FIG. 3, the system 100 may include a fluid-driven actuator, such as the actuator 102 of the row unit 20 described above with reference to FIG. 2. As shown, the actuator 102 may correspond to a hydraulic actuator. Thus, in several embodiments, the actuator 102 may include a piston 108 housed within the cylinder 106. One end of the rod 104 may be coupled to the piston 108, while an opposed end of the rod 104 may extend outwardly from the cylinder 106. Additionally, the actuator 102 may include a cap-side chamber 110 and a rod-side chamber 112 defined within the cylinder 106. As is generally understood, by regulating the pressure of the fluid supplied to one or both of the cylinder chambers 110, 112, the actuation of the rod 104 may be controlled. However, it should be appreciated that, in alternative embodiments, the actuator 102 may be configured as any other suitable type of actuator, such as a pneumatic actuator. Furthermore, it should be appreciated that, in further embodiments, the system 100 may include any other suitable number of fluid-driven actuators, such as additional actuators 102 mounted on the implement 10.

+

Furthermore, the system 100 may include various components configured to provide fluid (e.g., hydraulic oil) to the cylinder chambers 110, 112 of the actuator 102. For example, in several embodiments, the system 100 may include a fluid reservoir 114 and first and second fluid conduits 116, 118. As shown, a first fluid conduit 116 may extend between and fluidly couple the reservoir 114 and the rod-side chamber 112 of the actuator 102. Similarly, a second fluid conduit 118 may extend between and fluidly couple the reservoir 114 and the cap-side chamber 110 of the actuator 102. Additionally, a pump 115 and a remote switch 117 or other valve(s) may be configured to control the flow of the fluid between the reservoir 114 and the cylinder chambers 110, 112 of the actuator 102. In one embodiment, the reservoir 114, the pump 115, and the remote switch 117 may be mounted on the work vehicle (not shown) configured to tow the implement 10. However, it should be appreciated that, in alternative embodiments, the reservoir 114, the pump 115, and/or the remote switch 117 may be mounted on the implement 10. Furthermore, it should be appreciated that the system 100 may include any other suit component(s) configured to control the flow of fluid between the reservoir and the actuator 102.

+

In several embodiments, the system 100 may also include a flow restrictor 120 that is fluidly coupled to the cap-side chamber 110. As such, the flow restrictor 120 may be provided in series with the second fluid conduit 118. As will be described below, the flow restrictor 120 may be configured to reduce the flow rate of the fluid exiting the cap-side chamber 110 in a manner that provides damping to one or more components of the implement 10. However, it should be appreciated that, in alternative embodiments, the flow restrictor 120 may be fluidly coupled to the rod-side chamber 120 such that the flow restrictor 120 is provided in series with the first fluid conduit 116.

+

Additionally, in several embodiments, the system 100 may include a check valve 122 that is fluidly coupled to the cap-side chamber 110 and provided in series with the second fluid conduit 118. As shown, the check valve 122 may be fluidly coupled to the flow restrictor 120 in parallel. In this regard, the check valve 122 may be provided in series with a first branch 124 of the second fluid conduit 118, while the flow restrictor 120 may be provided in series with a second branch 126 of the second fluid conduit 118. As such, the check valve 122 may be configured to allow the fluid to flow through the first branch 124 of the second fluid conduit 118 from the reservoir 114 to the cap-side chamber 110. However, the check valve 122 may be configured to occlude or prevent the fluid from flowing through the first branch 124 of the second fluid conduit 118 from the cap-side chamber 110 to the reservoir 114. In this regard, the check valve 122 directs all of the fluid exiting the cap-side chamber 110 into the flow restrictor 120. Conversely, the check valve 122 permits the fluid flowing to the cap-side chamber 110 to bypass the flow restrictor 120. As will be described below, such configuration facilitates damping of one or more components of the implement 10. However, it should be appreciated that, in alternative embodiments, the check valve 122 may be fluidly coupled to the rod-side chamber 112 in combination with the flow restrictor 120 such that the check valve 122 is provided in series with the first fluid conduit 116.

+

As indicated above, the system 100 may generally be configured to provide viscous damping to one or more components of the implement 10. For example, when a ground engaging tool of the implement 10, such as the shank 32, contacts a rock or other impediment in the soil, the corresponding row unit 20 may pivot relative to the corresponding tool frame 18 and/or the toolbar 12 against the down pressure load applied to the row unit 20 by the corresponding actuator 102. In several embodiments, such movement may cause the rod 104 of the actuator 102 to retract into the cylinder 106, thereby moving the piston 108 in a manner that decreases the volume of the cap-side chamber 110. In such instances, some of the fluid present within the cap-side chamber 110 may exit and flow into the second fluid conduit 118 toward the reservoir 114. The check valve 122 may prevent the fluid exiting the cap-side chamber 110 from flowing through the first branch 124 of the second fluid conduit 118. As such, all fluid exiting the cap-side chamber 110 may be directed into the second branch 126 and through the flow restrictor 120. As indicated above, the flow restrictor 120 reduces or limits the rate at which the fluid may flow through the second fluid conduit 118 so as to reduce the rate at which the fluid may exit the cap-side chamber 110. In this regard, the speed at which and/or the amount that the rod 104 retracts into the cylinder 106 when the shank 32 contacts a soil impediment may be reduced (e.g., because of the reduced rate at which the fluid is discharged from the cap-side chamber 110), thereby damping the movement of the row unit 20 relative to the corresponding tool frame 18 and/or the toolbar 12. Furthermore, after the initial retraction of the rod 104 into the cylinder 106, the piston 108 may then move in a manner that increases the volume of the cap-side chamber 110, thereby extending the rod 104 from the cylinder 106. In such instances, fluid present within the reservoir 114 and the second fluid conduit 118 may be drawn back into the cap-side chamber 110. As indicated above, the check valve 122 may permit the fluid within the second fluid conduit 118 to bypass the flow restrictor 120 and flow unobstructed through the first branch 124, thereby maximizing the rate at which the fluid returns to the cap-side chamber 110. Increasing the rate at which the fluid returns to the cap-side chamber 110 may decrease the time that the row unit 20 is displaced relative to the tool frame 18, thereby further damping of the row unit 20 relative to the corresponding tool frame 18 and/or the toolbar 12.

+

Referring now to FIG. 4, a cross-sectional view of one embodiment of the flow restrictor 120 is illustrated in accordance with aspects of the present subject matter. For example, in the illustrated embodiment, the flow restrictor 120 may include a restrictor body 128 coupled to the second branch 126 of the second fluid conduit 118, with the restrictor body 128, in turn, defining a fluid passage 130 extending therethrough. Furthermore, the flow restrictor 120 may include an orifice plate 132 extending inward from the restrictor body 128 into the fluid passage 130. As shown, the orifice plate 132 may define a central aperture or throat 134 extending therethrough. In general, the size (e.g., the area, diameter, etc.) of the throat 134 may be smaller than the size of the fluid passage 130 so as to reduce the flow rate of the fluid through the flow restrictor 120. It should be appreciated that, in the illustrated embodiment, the throat 134 has a fixed size such that the throat 134 provides a fixed or constant backpressure for a given fluid flow rate. In this regard, in such embodiment, a fixed or constant damping rate is provided by the system 100. However, it should be appreciated that, in alternative embodiments, the flow restrictor 120 may have any other suitable configuration that reduces the flow rate of the fluid flowing therethrough.

+

Referring now to FIG. 5, a cross-sectional view of another embodiment of the flow restrictor 120 is illustrated in accordance with aspects of the present subject matter. As shown, the flow restrictor 120 may generally be configured the same as or similar to that described above with reference to FIG. 4. For instance, the flow restrictor 120 may define the throat 134, which is configured to reduce the flow rate of the fluid through the flow restrictor 120. However, as shown in FIG. 5, unlike the above-describe embodiment, the size (e.g., the area, diameter, etc.) of the throat 134 is adjustable. For example, in such embodiment, the flow restrictor 120 may be configured as an adjustable valve 136. As shown, the valve 136 may include a valve body 138 coupled to the second branch 126 of the second fluid conduit 118, a shaft 140 rotatably coupled to the valve body 138, a disc 142 coupled to the shaft 140, and an actuator 144 (e.g., a suitable electric motor) coupled to the shaft 140. As such, the actuator 144 may be configured to rotate the shaft 140 and the disc 142 relative to the valve body 138 (e.g., as indicated by arrow 146 in FIG. 5) to change the size of the throat 134 defined between the disc 142 and the valve body 138. Although the valve 136 is configured as a butterfly valve in FIG. 5, it should be appreciated that, in alternative embodiments, the valve 136 may be configured as any other suitable type of valve or adjustable flow restrictor. For example, in one embodiment, the valve 136 may be configured as a suitable ball valve.

+

In accordance with aspects of the present disclosure, by adjusting the size of the throat 134, the system 100 may be able to provide variable damping rates. In general, the size of the throat 134 may be indicative of the amount of damping provided by the system 100. For example, in several embodiments, the disc 142 may be adjustable between a first position shown in FIG. 6 and a second position shown in FIG. 7. More specifically, when the disc 142 is at the first position, the throat 134 defines a first size (e.g., as indicated by arrow 148 in FIG. 6), thereby providing a first damping rate. Conversely, when the disc 142 is at the second position, the throat 134 defines a second size (e.g., as indicated by arrow 150 in FIG. 7), thereby providing a second damping rate. As shown in FIGS. 6 and 7, the first distance 148 is larger than the second distance 150. In such instance, the system 100 provides greater damping when the throat 134 is adjusted to the first size than when the throat 134 is adjusted to the second size. It should be appreciated that, in alternative embodiments, the disc 142 may be adjustable between any other suitable positions that provide any other suitable damping rates. For example, the disc 142 may be adjustable to a plurality of different positions defined between the fully opened and fully closed positions of the valve, thereby providing for a corresponding number of different damping rates. Furthermore, it should be appreciated that the disc 142 may be continuously adjustable or adjustable between various discrete positions.

+

Referring back to FIG. 5, a controller 152 of the system 100 may be configured to electronically control the operation of one or more components of the valve 138, such as the actuator 144. In general, the controller 152 may comprise any suitable processor-based device known in the art, such as a computing device or any suitable combination of computing devices. Thus, in several embodiments, the controller 152 may include one or more processor(s) 154 and associated memory device(s) 156 configured to perform a variety of computer-implemented functions. As used herein, the term “processor” refers not only to integrated circuits referred to in the art as being included in a computer, but also refers to a controller, a microcontroller, a microcomputer, a programmable logic controller (PLC), an application specific integrated circuit, and other programmable circuits. Additionally, the memory device(s) 156 of the controller 152 may generally comprise memory element(s) including, but not limited to, a computer readable medium (e.g., random access memory (RAM)), a computer readable non-volatile medium (e.g., a flash memory), a floppy disk, a compact disc-read only memory (CD-ROM), a magneto-optical disk (MOD), a digital versatile disc (DVD) and/or other suitable memory elements. Such memory device(s) 156 may generally be configured to store suitable computer-readable instructions that, when implemented by the processor(s) 154, configure the controller 152 to perform various computer-implemented functions. In addition, the controller 152 may also include various other suitable components, such as a communications circuit or module, one or more input/output channels, a data/control bus and/or the like.

+

It should be appreciated that the controller 152 may correspond to an existing controller of the implement 10 or associated work vehicle (not shown) or the controller 152 may correspond to a separate processing device. For instance, in one embodiment, the controller 152 may form all or part of a separate plug-in module that may be installed within the implement 10 or associated work vehicle to allow for the disclosed system and method to be implemented without requiring additional software to be uploaded onto existing control devices of the implement 10 or associated work vehicle.

+

Furthermore, in one embodiment, a user interface 158 of the system 100 may be communicatively coupled to the controller 152 via a wired or wireless connection to allow feedback signals (e.g., as indicated by dashed line 160 in FIG. 5) to be transmitted from the controller 152 to the user interface 158. More specifically, the user interface 158 may be configured to receive an input from an operator of the implement 10 or the associated work vehicle, such as an input associated with a desired damping characteristic(s) to be provided by the system 100. As such, the user interface 158 may include one or more input devices (not shown), such as touchscreens, keypads, touchpads, knobs, buttons, sliders, switches, mice, microphones, and/or the like. In addition, some embodiments of the user interface 158 may include one or more one or more feedback devices (not shown), such as display screens, speakers, warning lights, and/or the like, which are configured to communicate such feedback from the controller 152 to the operator of the implement 10. However, in alternative embodiments, the user interface 158 may have any suitable configuration.

+

Moreover, in one embodiment, one or more sensors 162 of the system 100 may be communicatively coupled to the controller 152 via a wired or wireless connection to allow sensor data (e.g., as indicated by dashed line 164 in FIG. 5) to be transmitted from the sensor(s) 162 to the controller 152. For example, in one embodiment, the sensor(s) 162 may include a location sensor, such as a GNSS-based sensor, that is configured to detect a parameter associated with the location of the implement 10 or associated work vehicle within the field. In another embodiment, the sensor(s) 162 may include a speed sensor, such as a Hall Effect sensor, that is configured to detect a parameter associated with the speed at which the implement 10 is moved across the field. However, it should be appreciated that, in alternative embodiments, the sensor(s) 162 may include any suitable sensing device(s) configured to detect any suitable operating parameter of the implement 10 and/or the associated work vehicle.

+

In several embodiments, the controller 152 may be configured to control the operation of the valve 136 based on the feedback signals 160 received from the user interface 158 and/or the sensor data 164 received from the sensor(s) 162. Specifically, as shown in FIG. 5, the controller 152 may be communicatively coupled to the actuator 144 of the valve 136 via a wired or wireless connection to allow control signals (e.g., indicated by dashed lines 166 in FIG. 5) to be transmitted from the controller 152 to the actuator 144. Such control signals 166 may be configured to regulate the operation of the actuator 144 to adjust the position of the disc 142 relative to the valve body 138, such as by moving the disc 142 along the direction 146 between the first position (FIG. 6) and the second position (FIG. 7). For example, the feedback signals 116 received by the controller 152 may be indicative that the operator desires to adjust the damping provided by the system 100. Furthermore, upon receipt of the sensor data 164 (e.g., data indicative of the location and/or speed of the implement 10), the controller 152 may be configured to determine that the damping rate of the system 100 should be adjusted. In either instance, the controller 152 may be configured to transmit the control signals 166 to the actuator 144, with such control signals 166 being configured to control the operation of the actuator 144 to adjust the position of the disc 142 to provide the desired damping rate. However, it should be appreciated that, in alternative embodiments, the controller 152 may be configured to control the operation of the valve 136 based on any other suitable input(s) and/or parameter(s).

+

Referring now to FIG. 8, a schematic view of another embodiment of the system 100 is illustrated in accordance with aspects of the present subject matter. As shown, the system 100 may generally be configured the same as or similar to that described above with reference to FIG. 3. For instance, the system 100 may include the flow restrictor 120 and the check valve 122 fluidly coupled to the cap-side chamber 110 of the actuator 102 via the second fluid conduit 118. Furthermore, the flow restrictor 120 and the check valve 122 may be fluidly coupled together in parallel. However, as shown in FIG. 8, unlike the above-describe embodiment, the check valve 122 may be configured as a pilot-operated or fluid actuated three-way valve that is fluidly coupled to the first fluid conduit 116 by a pilot conduit 168.

+

In general, when the row unit 20 is lifted from an operational position relative to the ground to a raised position relative to the ground, it may be desirable for fluid to exit the cap-side chamber 110 without its flow rate being limited by the flow restrictor 120. For example, permitting such fluid to bypass the flow restrictor 120 may reduce the time required to lift the row unit 20 from the operational position to the raised position. More specifically, when lifting the row unit 20 from the operational position to the raised position, a pump (not shown) may pump fluid through the first fluid conduit 116 from the reservoir 114 to the rod-side chamber 112 of the actuator 102, thereby retracting the rod 104 into the cylinder 106. This may, in turn, discharge fluid from the cap-side chamber 110 into the second fluid conduit 118. As described above, the check valve 122 may generally be configured to direct all fluid exiting the cap-side chamber 110 into the flow restrictor 120. However, in the configuration of the system 100 shown in FIG. 8, when lifting the row unit 20 to the raised position, the pilot conduit 168 supplies fluid flowing through the first fluid conduit 116 to the check valve 122. The fluid received from the pilot conduit 168 may, in turn, actuate suitable component(s) of the check valve 122 (e.g., a diaphragm(s), a spring(s), and/or the like) in a manner that causes the check valve 122 to open, thereby permitting the fluid exiting the cap-side chamber 110 to bypass the flow restrictor 120 and flow unobstructed through the check valve 122 toward the reservoir 114. Conversely, when the row unit 20 is at the operational position, the check valve 122 may be closed, thereby directing all fluid exiting the cap-side chamber 110 into the flow restrictor 120.

+

Referring now to FIG. 9, a schematic view of a further embodiment of the system 100 is illustrated in accordance with aspects of the present subject matter. As shown, the system 100 may generally be configured the same as or similar to that described above with reference to FIGS. 3 and 8. For instance, the system 100 may include the flow restrictor 120 and the check valve 122 fluidly coupled to the cap-side chamber 110 of the actuator 102 via the second fluid conduit 118. Furthermore, the flow restrictor 120 and the check valve 122 may be fluidly coupled together in parallel. However, as shown in FIG. 9, unlike the above-describe embodiments, the check valve 122 may be configured as an electrically actuated valve. Specifically, as shown, the controller 152 may be communicatively coupled to the check valve 122 via a wired or wireless connection to allow control signals (e.g., indicated by dashed lines 170 in FIG. 9) to be transmitted from the controller 152 to the check valve 122. In this regard, when the row unit 20 is lifted from the operational position to the raised position, the control signals 170 may be configured to instruct the check valve 122 to open in a manner that permits the fluid exiting the cap-side chamber 110 to bypass the flow restrictor 120 and flow unobstructed through the check valve 122 toward the reservoir 114. Conversely, when the row unit 20 is at the operational position, the control signals 170 may be configured to instruct the check valve 122 to close, thereby directing all fluid exiting the cap-side chamber 110 into the flow restrictor 120.

+

This written description uses examples to disclose the technology, including the best mode, and also to enable any person skilled in the art to practice the technology, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the technology is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they include structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.

+ + +What is claimed is: + + +1. A system for controlling an operation of an actuator mounted on a seed planting implement, the system comprising: +a toolbar; +a row unit adjustably mounted on the toolbar; +a fluid-driven actuator configured to adjust a position of the row unit relative to the toolbar, the fluid-driven actuator defining first and second fluid chambers; +a flow restrictor fluidly coupled to the first fluid chamber, the flow restrictor being configured to reduce a rate at which fluid is permitted to exit the first fluid chamber in a manner that provides damping to the row unit; and +a valve fluidly coupled to the first fluid chamber, the valve further being fluidly coupled to the flow restrictor in a parallel relationship such that the valve is configured to permit the fluid exiting the first fluid chamber to flow through the flow restrictor and the fluid entering the first fluid chamber to bypass the flow restrictor. + + + +2. The system of claim 1, wherein, when fluid is supplied to the second fluid chamber, the valve is configured to permit fluid exiting the first fluid chamber to bypass the flow restrictor. + + +3. The system of claim 1, wherein the valve is fluidly actuated. + + +4. The system of claim 3, further comprising: +a fluid line configured to supply the fluid to the second fluid chamber, the fluid line being fluidly coupled to the valve such that, when the fluid flows through the fluid line to the second fluid chamber, the valve opens in a manner that permits the fluid exiting first fluid chamber to bypass the flow restrictor. + + + +5. The system of claim 1, wherein the valve is electrically actuated. + + +6. The system of claim 1, wherein the flow restrictor defines a throat having a fixed size. + + +7. The system of claim 1, wherein the flow restrictor defines a throat having an adjustable size. + + +8. A seed planting implement, comprising: +a toolbar; +a plurality of row units adjustably coupled to the toolbar, each row unit including a ground engaging tool configured to form a furrow in the soil; +a plurality of fluid-driven actuators, each fluid-driven actuator being coupled between the toolbar and a corresponding row unit of the plurality of row units, each fluid-driven actuator being configured to adjust a position of the corresponding row unit relative to the toolbar, each fluid-driven actuator defining first and second fluid chambers; +a flow restrictor fluidly coupled to the first fluid chamber of a first fluid-driven actuator of the plurality of fluid-driven actuators, the flow restrictor being configured to reduce a rate at which fluid is permitted to exit the first fluid chamber of the first fluid-driven actuator in a manner that provides damping to the corresponding row unit; and +a valve fluidly coupled to the first fluid chamber of the first fluid-driven actuator, the valve further being fluidly coupled to the flow restrictor in a parallel relationship such that the valve is configured to permit the fluid exiting the first fluid chamber to flow through the flow restrictor and the fluid entering the first fluid chamber to bypass the flow restrictor. + + + +9. The seed planting implement of claim 8, wherein, when fluid is supplied to the second fluid chamber of the first fluid-driven actuator, the valve is configured to permit fluid exiting the first fluid chamber of the first fluid-driven actuator to bypass the flow restrictor. + + +10. The seed planting implement of claim 8, wherein the valve is fluidly actuated. + + +11. The seed planting implement of claim 10, further comprising: +a fluid line configured to supply fluid to the second fluid chamber of the first fluid-driven actuator, the fluid line being fluidly coupled to the valve such that, when fluid flows through the fluid line to the second fluid chamber of the first fluid-driven actuator, the valve opens in a manner that permits the fluid exiting first fluid chamber of the first fluid-driven actuator to bypass the flow restrictor. + + + +12. The seed planting implement of claim 8, wherein the valve is electrically actuated. + + +13. The seed planting implement of claim 8, wherein the flow restrictor defines a throat having a fixed size. + + +14. The seed planting implement of claim 8, wherein the flow restrictor defines a throat having an adjustable size. + + +15. A system for providing damping to a row unit of a seed planting implement, the system comprising: +a toolbar; +a row unit adjustably mounted on the toolbar; +a fluid-driven actuator configured to adjust a position of the row unit relative to the toolbar, the fluid-driven actuator defining a fluid chamber; and +a flow restrictor fluidly coupled to the fluid chamber, the flow restrictor defining an adjustable throat configured to reduce a rate at which fluid is permitted to exit the fluid chamber, the throat being adjustable between a first size configured to provide a first damping rate to the row unit and a second size configured to provide a second damping rate to the row unit, the first and second damping rates being different. + + + +16. The system of claim 15, wherein the throat is adjustable between the first and second damping rates based on an operator input. + + +17. The system of claim 15, wherein the throat is adjustable between the first and second damping rates based on data received from one or more sensors on the seed planting implement. + + +18. The system of claim 15, further comprising: +a valve fluidly coupled to the fluid chamber, the valve being configured to selectively occlude the flow of fluid such that fluid exiting the fluid chamber flows through the flow restrictor and fluid entering the fluid chamber bypasses the flow restrictor. + + + +19. The system of claim 18, wherein the flow restrictor and the valve are fluidly coupled in a parallel relationship. + + + \ No newline at end of file diff --git a/tests/data/uspto/ipg07997973.xml b/tests/data/uspto/ipg07997973.xml new file mode 100644 index 00000000..b2287aa2 --- /dev/null +++ b/tests/data/uspto/ipg07997973.xml @@ -0,0 +1,4468 @@ + + + + + + +US +07997973 +B2 +20110816 + + + + +US +12512730 +20090730 + + +12 + + +This patent is subject to a terminal disclaimer. + + + + +20060101 +A +
G
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No. 11/675,182, Apr. 13, 2010 (12 pages). + +cited by other + + + +International Preliminary Report on Patentability for International Application No. PCT/US08/54128, Aug. 19, 2009 (6 pages). + +cited by other + + + +Australian Examination Report for Application No. 2008216057, Jun. 28, 2010 (2 pages). + +cited by other + + + +U.S. Appl. No. 11/675,182, filed Feb. 15, 2007, Alderucci et al. + +cited by other + + + +Michael Friedman, Bet on Poker? Bodog takes bets on the 2005 WSOP, dated Jun. 24, 2005, http://www.pokernews.com/news/2005/06/bet-on-poker-bodog-wsop.htm. + +cited by other + + + +USPTO Pre-Brief Appeal Conference Decision for U.S. Appl. No. 11/680,764, Sep. 27, 2010 (2 pages). + +cited by other + + + +USPTO Office Action for U.S. Appl. No. 11/733,902, Oct. 6, 2010 (13 pages). + +cited by other + + + +U.S. Appl. No. 12/897,954, filed Oct. 5, 2010, Inventor: Howard W. Lutnick for “Secondary Game” (126 pages). + +cited by other + + +28 +1 + + +US +463 16- 25 +unstructured + + +US +273274 + + +US +273292 + + + +9 +9 + + + + + + +US +11470250 +20060905 + + + +US +7585217 + + + + + +US +12512730 + + + + + + +US +20090291732 +A1 +20091126 + + + + + + + +Lutnick +Howard W. +
+New York +NY +US +
+ + +omitted + + +US + + + + +Alderucci +Dean P. +
+Westpoint +CT +US +
+ + +omitted + + +US + + + + +Gelman +Geoffrey M. +
+Brooklyn +NY +US +
+ + +omitted + + +US + + + + + + +Miller +Mark A. +
+unknown +
+ + + + + + + +CFPH, LLC +02 +
+New York +NY +US +
+ + + + + +Laneau +Ronald +3714 + + + + +

Various embodiments of amusement devices and methods for various games are described. In some embodiments, a secondary player may engage in a game started by a first player. Various additional methods and apparatus are described.

+ + +
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+ + + +RELATED APPLICATION +

This application is a continuation of U.S. patent application Ser. No. 11/470,250, filed Sep. 5, 2006, now U.S. Pat. No. 7,585,217 which is incorporated herein by reference.

+ + +BRIEF DESCRIPTION OF THE DRAWINGS +

FIG. 1 shows a system according to some embodiments.

+

FIG. 2 shows a casino server according to some embodiments.

+

FIG. 3 shows a terminal for use by a secondary player, according to some embodiments.

+

FIG. 4 shows a gaming device according to some embodiments.

+

FIG. 5 shows a monitoring device (e.g., camera, card reader) according to some embodiments.

+

FIG. 6 shows a database entry including various information about a game (e.g., date, time, outcome, player, bet amount)

+

FIG. 7 shows a database entry including various games played by a player.

+

FIG. 8 shows a touch screen display for entering betting information and tracking the progress of a game, according to some embodiments.

+

FIG. 9 shows a touch screen display for entering betting information and tracking the progress of a game, according to some embodiments.

+ + +DETAILED DESCRIPTION +

The following sections I-IX provide a guide to interpreting the present application.

+I. Terms +

The term “product” means any machine, manufacture and/or composition of matter, unless expressly specified otherwise.

+

The term “process” means any process, algorithm, method or the like, unless expressly specified otherwise.

+

Each process (whether called a method, algorithm or otherwise) inherently includes one or more steps, and therefore all references to a “step” or “steps” of a process have an inherent antecedent basis in the mere recitation of the term ‘process’ or a like term. Accordingly, any reference in a claim to a ‘step’ or ‘steps’ of a process has sufficient antecedent basis.

+

The term “invention” and the like mean “the one or more inventions disclosed in this application”, unless expressly specified otherwise.

+

The terms “an embodiment”, “embodiment”, “embodiments”, “the embodiment”, “the embodiments”, “one or more embodiments”, “some embodiments”, “certain embodiments”, “one embodiment”, “another embodiment” and the like mean “one or more (but not all) embodiments of the disclosed invention(s)”, unless expressly specified otherwise.

+

The term “variation” of an invention means an embodiment of the invention, unless expressly specified otherwise.

+

A reference to “another embodiment” in describing an embodiment does not imply that the referenced embodiment is mutually exclusive with another embodiment (e.g., an embodiment described before the referenced embodiment), unless expressly specified otherwise.

+

The terms “including”, “comprising” and variations thereof mean “including but not limited to”, unless expressly specified otherwise.

+

The terms “a”, “an” and “the” mean “one or more”, unless expressly specified otherwise.

+

The term “plurality” means “two or more”, unless expressly specified otherwise.

+

The term “herein” means “in the present application, including anything which may be incorporated by reference”, unless expressly specified otherwise.

+

The phrase “at least one of”, when such phrase modifies a plurality of things (such as an enumerated list of things), means any combination of one or more of those things, unless expressly specified otherwise. For example, the phrase “at least one of a widget, a car and a wheel” means either (i) a widget, (ii) a car, (iii) a wheel, (iv) a widget and a car, (v) a widget and a wheel, (vi) a car and a wheel, or (vii) a widget, a car and a wheel. The phrase “at least one of”, when such phrase modifies a plurality of things, does not mean “one of each of” the plurality of things.

+

Numerical terms such as “one”, “two”, etc. when used as cardinal numbers to indicate quantity of something (e.g., one widget, two widgets), mean the quantity indicated by that numerical term, but do not mean at least the quantity indicated by that numerical term. For example, the phrase “one widget” does not mean “at least one widget”, and therefore the phrase “one widget” does not cover, e.g., two widgets.

+

The phrase “based on” does not mean “based only on”, unless expressly specified otherwise. In other words, the phrase “based on” describes both “based only on” and “based at least on”. The phrase “based at least on” is equivalent to the phrase “based at least in part on”.

+

The term “represent” and like terms are not exclusive, unless expressly specified otherwise. For example, the term “represents” do not mean “represents only”, unless expressly specified otherwise. In other words, the phrase “the data represents a credit card number” describes both “the data represents only a credit card number” and “the data represents a credit card number and the data also represents something else”.

+

The term “whereby” is used herein only to precede a clause or other set of words that express only the intended result, objective or consequence of something that is previously and explicitly recited. Thus, when the term “whereby” is used in a claim, the clause or other words that the term “whereby” modifies do not establish specific further limitations of the claim or otherwise restricts the meaning or scope of the claim.

+

The term “e.g.” and like terms mean “for example”, and thus does not limit the term or phrase it explains. For example, in the sentence “the computer sends data (e.g., instructions, a data structure) over the Internet”, the term “e.g.” explains that “instructions” are an example of “data” that the computer may send over the Internet, and also explains that “a data structure” is an example of “data” that the computer may send over the Internet. However, both “instructions” and “a data structure” are merely examples of “data”, and other things besides “instructions” and “a data structure” can be “data”.

+

The term “i.e.” and like terms mean “that is”, and thus limits the term or phrase it explains. For example, in the sentence “the computer sends data (i.e., instructions) over the Internet”, the term “i.e.” explains that “instructions” are the “data” that the computer sends over the Internet.

+

Any given numerical range shall include whole and fractions of numbers within the range. For example, the range “1 to 10” shall be interpreted to specifically include whole numbers between 1 and 10 (e.g., 1, 2, 3, 4, . . . 9) and non-whole numbers (e.g., 1.1, 1.2, . . . 1.9).

+II. Determining +

The term “determining” and grammatical variants thereof (e.g., to determine a price, determining a value, determine an object which meets a certain criterion) is used in an extremely broad sense. The term “determining” encompasses a wide variety of actions and therefore “determining” can include calculating, computing, processing, deriving, investigating, looking up (e.g., looking up in a table, a database or another data structure), ascertaining and the like. Also, “determining” can include receiving (e.g., receiving information), accessing (e.g., accessing data in a memory) and the like. Also, “determining” can include resolving, selecting, choosing, establishing, and the like.

+

The term “determining” does not imply certainty or absolute precision, and therefore “determining” can include estimating, extrapolating, predicting, guessing and the like.

+

The term “determining” does not imply that mathematical processing must be performed, and does not imply that numerical methods must be used, and does not imply that an algorithm or process is used.

+

The term “determining” does not imply that any particular device must be used. For example, a computer need not necessarily perform the determining.

+III. Indication +

The term “indication” is used in an extremely broad sense. The term “indication” may, among other things, encompass a sign, symptom, or token of something else.

+

The term “indication” may be used to refer to any indicia and/or other information indicative of or associated with a subject, item, entity, and/or other object and/or idea.

+

As used herein, the phrases “information indicative of” and “indicia” may be used to refer to any information that represents, describes, and/or is otherwise associated with a related entity, subject, or object.

+

Indicia of information may include, for example, a code, a reference, a link, a signal, an identifier, and/or any combination thereof and/or any other informative representation associated with the information.

+

In some embodiments, indicia of information (or indicative of the information) may be or include the information itself and/or any portion or component of the information. In some embodiments, an indication may include a request, a solicitation, a broadcast, and/or any other form of information gathering and/or dissemination.

+IV. Forms of Sentences +

Where a limitation of a first claim would cover one of a feature as well as more than one of a feature (e.g., a limitation such as “at least one widget” covers one widget as well as more than one widget), and where in a second claim that depends on the first claim, the second claim uses a definite article “the” to refer to the limitation (e.g., “the widget”), this does not imply that the first claim covers only one of the feature, and this does not imply that the second claim covers only one of the feature (e.g., “the widget” can cover both one widget and more than one widget).

+

When an ordinal number (such as “first”, “second”, “third” and so on) is used as an adjective before a term, that ordinal number is used (unless expressly specified otherwise) merely to indicate a particular feature, such as to distinguish that particular feature from another feature that is described by the same term or by a similar term. For example, a “first widget” may be so named merely to distinguish it from, e.g., a “second widget”. Thus, the mere usage of the ordinal numbers “first” and “second” before the term “widget” does not indicate any other relationship between the two widgets, and likewise does not indicate any other characteristics of either or both widgets. For example, the mere usage of the ordinal numbers “first” and “second” before the term “widget” (1) does not indicate that either widget comes before or after any other in order or location; (2) does not indicate that either widget occurs or acts before or after any other in time; and (3) does not indicate that either widget ranks above or below any other, as in importance or quality. In addition, the mere usage of ordinal numbers does not define a numerical limit to the features identified with the ordinal numbers. For example, the mere usage of the ordinal numbers “first” and “second” before the term “widget” does not indicate that there must be no more than two widgets.

+

When a single device or article is described herein, more than one device/article (whether or not they cooperate) may alternatively be used in place of the single device/article that is described. Accordingly, the functionality that is described as being possessed by a device may alternatively be possessed by more than one device/article (whether or not they cooperate).

+

Similarly, where more than one device or article is described herein (whether or not they cooperate), a single device/article may alternatively be used in place of the more than one device or article that is described. For example, a plurality of computer-based devices may be substituted with a single computer-based device. Accordingly, the various functionality that is described as being possessed by more than one device or article may alternatively be possessed by a single device/article.

+

The functionality and/or the features of a single device that is described may be alternatively embodied by one or more other devices which are described but are not explicitly described as having such functionality/features. Thus, other embodiments need not include the described device itself, but rather can include the one or more other devices which would, in those other embodiments, have such functionality/features.

+V. Disclosed Examples and Terminology are Not Limiting +

Neither the Title (set forth at the beginning of the first page of the present application) nor the Abstract (set forth at the end of the present application) is to be taken as limiting in any way as the scope of the disclosed invention(s). An Abstract has been included in this application merely because an Abstract of not more than 150 words is required under 37 C.F.R. §1.72(b).

+

The title of the present application and headings of sections provided in the present application are for convenience only, and are not to be taken as limiting the disclosure in any way.

+

Numerous embodiments are described in the present application, and are presented for illustrative purposes only. The described embodiments are not, and are not intended to be, limiting in any sense. The presently disclosed invention(s) are widely applicable to numerous embodiments, as is readily apparent from the disclosure. One of ordinary skill in the art will recognize that the disclosed invention(s) may be practiced with various modifications and alterations, such as structural, logical, software, and electrical modifications. Although particular features of the disclosed invention(s) may be described with reference to one or more particular embodiments and/or drawings, it should be understood that such features are not limited to usage in the one or more particular embodiments or drawings with reference to which they are described, unless expressly specified otherwise.

+

The present disclosure is not a literal description of all embodiments of the invention(s). Also, the present disclosure is not a listing of features of the invention(s) which must be present in all embodiments.

+

Devices that are described as in communication with each other need not be in continuous communication with each other, unless expressly specified otherwise. On the contrary, such devices need only transmit to each other as necessary or desirable, and may actually refrain from exchanging data most of the time. For example, a machine in communication with another machine via the Internet may not transmit data to the other machine for long period of time (e.g., weeks at a time). In addition, devices that are in communication with each other may communicate directly or indirectly through one or more intermediaries.

+

A description of an embodiment with several components or features does not imply that all or even any of such components/features are required. On the contrary, a variety of optional components are described to illustrate the wide variety of possible embodiments of the present invention(s). Unless otherwise specified explicitly, no component/feature is essential or required.

+

Although process steps, algorithms or the like may be described in a particular sequential order, such processes may be configured to work in different orders. In other words, any sequence or order of steps that may be explicitly described does not necessarily indicate a requirement that the steps be performed in that order. The steps of processes described herein may be performed in any order practical. Further, some steps may be performed simultaneously despite being described or implied as occurring non-simultaneously (e.g., because one step is described after the other step). Moreover, the illustration of a process by its depiction in a drawing does not imply that the illustrated process is exclusive of other variations and modifications thereto, does not imply that the illustrated process or any of its steps are necessary to the invention(s), and does not imply that the illustrated process is preferred.

+

Although a process may be described as including a plurality of steps, that does not imply that all or any of the steps are preferred, essential or required. Various other embodiments within the scope of the described invention(s) include other processes that omit some or all of the described steps. Unless otherwise specified explicitly, no step is essential or required.

+

Although a process may be described singly or without reference to other products or methods, in an embodiment the process may interact with other products or methods. For example, such interaction may include linking one business model to another business model. Such interaction may be provided to enhance the flexibility or desirability of the process.

+

Although a product may be described as including a plurality of components, aspects, qualities, characteristics and/or features, that does not indicate that any or all of the plurality are preferred, essential or required. Various other embodiments within the scope of the described invention(s) include other products that omit some or all of the described plurality.

+

An enumerated list of items (which may or may not be numbered) does not imply that any or all of the items are mutually exclusive, unless expressly specified otherwise. Likewise, an enumerated list of items (which may or may not be numbered) does not imply that any or all of the items are comprehensive of any category, unless expressly specified otherwise. For example, the enumerated list “a computer, a laptop, a PDA” does not imply that any or all of the three items of that list are mutually exclusive and does not imply that any or all of the three items of that list are comprehensive of any category.

+

An enumerated list of items (which may or may not be numbered) does not imply that any or all of the items are equivalent to each other or readily substituted for each other.

+

All embodiments are illustrative, and do not imply that the invention or any embodiments were made or performed, as the case may be.

+VI. Computing +

It will be readily apparent to one of ordinary skill in the art that the various processes described herein may be implemented by, e.g., appropriately programmed general purpose computers, special purpose computers and computing devices. Typically a processor (e.g., one or more microprocessors, one or more microcontrollers, one or more digital signal processors) will receive instructions (e.g., from a memory or like device), and execute those instructions, thereby performing one or more processes defined by those instructions.

+

A “processor” means one or more microprocessors, central processing units (CPUs), computing devices, microcontrollers, digital signal processors, or like devices or any combination thereof.

+

Thus a description of a process is likewise a description of an apparatus for performing the process. The apparatus that performs the process can include, e.g., a processor and those input devices and output devices that are appropriate to perform the process.

+

Further, programs that implement such methods (as well as other types of data) may be stored and transmitted using a variety of media (e.g., computer readable media) in a number of manners. In some embodiments, hard-wired circuitry or custom hardware may be used in place of, or in combination with, some or all of the software instructions that can implement the processes of various embodiments. Thus, various combinations of hardware and software may be used instead of software only.

+

The term “computer-readable medium” refers to any medium, a plurality of the same, or a combination of different media, that participate in providing data (e.g., instructions, data structures) which may be read by a computer, a processor or a like device. Such a medium may take many forms, including but not limited to, non-volatile media, volatile media, and transmission media. Non-volatile media include, for example, optical or magnetic disks and other persistent memory. Volatile media include dynamic random access memory (DRAM), which typically constitutes the main memory. Transmission media include coaxial cables, copper wire and fiber optics, including the wires that comprise a system bus coupled to the processor. Transmission media may include or convey acoustic waves, light waves and electromagnetic emissions, such as those generated during radio frequency (RF) and infrared (IR) data communications. Common forms of computer-readable media include, for example, a floppy disk, a flexible disk, hard disk, magnetic tape, any other magnetic medium, a CD-ROM, DVD, any other optical medium, punch cards, paper tape, any other physical medium with patterns of holes, a RAM, a PROM, an EPROM, a FLASH-EEPROM, any other memory chip or cartridge, a carrier wave as described hereinafter, or any other medium from which a computer can read.

+

Various forms of computer readable media may be involved in carrying data (e.g. sequences of instructions) to a processor. For example, data may be (i) delivered from RAM to a processor; (ii) carried over a wireless transmission medium; (iii) formatted and/or transmitted according to numerous formats, standards or protocols, such as Ethernet (or IEEE 802.3), SAP, ATP, Bluetooth™, and TCP/IP, TDMA, CDMA, and 3G; and/or (iv) encrypted to ensure privacy or prevent fraud in any of a variety of ways well known in the art.

+

Thus a description of a process is likewise a description of a computer-readable medium storing a program for performing the process. The computer-readable medium can store (in any appropriate format) those program elements which are appropriate to perform the method.

+

Just as the description of various steps in a process does not indicate that all the described steps are required, embodiments of an apparatus include a computer/computing device operable to perform some (but not necessarily all) of the described process.

+

Likewise, just as the description of various steps in a process does not indicate that all the described steps are required, embodiments of a computer-readable medium storing a program or data structure include a computer-readable medium storing a program that, when executed, can cause a processor to perform some (but not necessarily all) of the described process.

+

Where databases are described, it will be understood by one of ordinary skill in the art that (i) alternative database structures to those described may be readily employed, and (ii) other memory structures besides databases may be readily employed. Any illustrations or descriptions of any sample databases presented herein are illustrative arrangements for stored representations of information. Any number of other arrangements may be employed besides those suggested by, e.g., tables illustrated in drawings or elsewhere. Similarly, any illustrated entries of the databases represent exemplary information only; one of ordinary skill in the art will understand that the number and content of the entries can be different from those described herein. Further, despite any depiction of the databases as tables, other formats (including relational databases, object-based models and/or distributed databases) could be used to store and manipulate the data types described herein. Likewise, object methods or behaviors of a database can be used to implement various processes, such as the described herein. In addition, the databases may, in a known manner, be stored locally or remotely from a device which accesses data in such a database.

+

Various embodiments can be configured to work in a network environment including a computer that is in communication (e.g., via a communications network) with one or more devices. The computer may communicate with the devices directly or indirectly, via any wired or wireless medium (e.g. the Internet, LAN, WAN or Ethernet, Token Ring, a telephone line, a cable line, a radio channel, an optical communications line, commercial on-line service providers, bulletin board systems, a satellite communications link, a combination of any of the above). Each of the devices may themselves comprise computers or other computing devices, such as those based on the Intel® Pentium® or Centrino™ processor, that are adapted to communicate with the computer. Any number and type of devices may be in communication with the computer.

+

In an embodiment, a server computer or centralized authority may not be necessary or desirable. For example, the present invention may, in an embodiment, be practiced on one or more devices without a central authority. In such an embodiment, any functions described herein as performed by the server computer or data described as stored on the server computer may instead be performed by or stored on one or more such devices.

+

Where a process is described, in an embodiment the process may operate without any user intervention. In another embodiment, the process includes some human intervention (e.g., a step is performed by or with the assistance of a human).

+VII. Continuing Applications +

The present disclosure provides, to one of ordinary skill in the art, an enabling description of several embodiments and/or inventions. Some of these embodiments and/or inventions may not be claimed in the present application, but may nevertheless be claimed in one or more continuing applications that claim the benefit of priority of the present application. Applicants intend to file additional applications to pursue patents for subject matter that has been disclosed and enabled but not claimed in the present application.

+VIII. 35 U.S.C. §112, Paragraph 6 +

In a claim, a limitation of the claim which includes the phrase “means for” or the phrase “step for” means that 35 U.S.C. §112, paragraph 6, applies to that limitation.

+

In a claim, a limitation of the claim which does not include the phrase “means for” or the phrase “step for” means that 35 U.S.C. §112, paragraph 6 does not apply to that limitation, regardless of whether that limitation recites a function without recitation of structure, material or acts for performing that function. For example, in a claim, the mere use of the phrase “step of” or the phrase “steps of” in referring to one or more steps of the claim or of another claim does not mean that 35 U.S.C. §112, paragraph 6, applies to that step(s).

+

With respect to a means or a step for performing a specified function in accordance with 35 U.S.C. §112, paragraph 6, the corresponding structure, material or acts described in the specification, and equivalents thereof, may perform additional functions as well as the specified function.

+

Computers, processors, computing devices and like products are structures that can perform a wide variety of functions. Such products can be operable to perform a specified function by executing one or more programs, such as a program stored in a memory device of that product or in a memory device which that product accesses. Unless expressly specified otherwise, such a program need not be based on any particular algorithm, such as any particular algorithm that might be disclosed in the present application. It is well known to one of ordinary skill in the art that a specified function may be implemented via different algorithms, and any of a number of different algorithms would be a mere design choice for carrying out the specified function.

+

Therefore, with respect to a means or a step for performing a specified function in accordance with 35 U.S.C. §112, paragraph 6, structure corresponding to a specified function includes any product programmed to perform the specified function. Such structure includes programmed products which perform the function, regardless of whether such product is programmed with (i) a disclosed algorithm for performing the function, (ii) an algorithm that is similar to a disclosed algorithm, or (iii) a different algorithm for performing the function.

+IX. Prosecution History +

In interpreting the present application (which includes the claims), one of ordinary skill in the art shall refer to the prosecution history of the present application, but not to the prosecution history of any other patent or patent application, regardless of whether there are other patent applications that are considered related to the present application.

+X. Embodiments of the Invention +Terms +

As used herein, the term “viewing window” includes an area of a gaming device at which symbols or outcomes are visible. The area may, for instance, include a pane of glass or other transparent material situated over reels of the gaming device. Thus, only the portion of the reels under the transparent material may be visible to the player. A viewing window may include a display screen, in some embodiments. The symbols or outcomes visible in the viewing window may include the symbols or outcomes that determine the player's winnings.

+

FIG. 1 shows a system according to some embodiments. According to some embodiments, Casino A and Casino B may represent facilities where participation in games of chance or in other contests is permitted. In various embodiments, in Casinos A and B, players may place bets on games or contests, and/or may win or lose money based on games or contests. The system of FIG. 1 may permit secondary players in Casino A and secondary players in Casino B to participate in the games of primary players who are at Casino A. Further, the system of FIG. 1 may permit a secondary player outside of Casinos A or B to participate in games of primary players at casino A. Further, the system of FIG. 1 may permit regulators to track various data related to the games of primary players played at Casino A, to the participation in games by secondary players who are at Casino A, to the participation in games by secondary players who are at Casino B, and to the participation in games by secondary players who are at neither Casino A nor Casino B. According to some embodiments, Casino A may include a server 110. The server may be in communication with a gaming device 130, a monitoring device 160, and a terminal of secondary player X 140, each of which may lie within the premises of Casino A. Server 110 may further be in communication with server 120 of Casino B, with a server of a regulator 170, and with a device of a secondary player Z 190, where the secondary player device 190 is not located on the premises of Casino A nor Casino B. Communication between server 110 and the device 190 may occur through an external network 180, e.g., through the Internet. Casino B may include a server 120 which is in communication with server 110, with the server of a regulator 170, and with a terminal of secondary player Y 150, which may lie within the premises of Casino B.

+

In some embodiments, the server of Casino A 110 may receive data about a game from gaming device 130 or from monitoring device 160. A monitoring device may include a device such as a camera or microphone which may monitor a game at Casino A and transmit data about the game to the server of Casino A. The server of Casino A may transmit data received from gaming device 130 or monitoring device 160 to the terminal of a secondary player X 140 so as to allow the terminal 140 to recreate the game, to accept bets from secondary player X on the game, and to pay winnings to secondary player X based on the game.

+

The server of Casino A 110 may further transmit received data about a game to the server of Casino B 120. The server of Casino B may, in turn, transmit such data to the terminal of a secondary player Y 150 so as to allow the terminal 150 to recreate the game, to accept bets from secondary player Y on the game, and to pay winnings to secondary player Y based on the game.

+

The server of Casino A 110 may further transmit received data about a game to the device of secondary player Z 190, e.g., through the Internet. The device of secondary player Z 190 may, in turn, recreate the game for secondary player Z, receive bets on the game from secondary player Z, and/or credit winnings to secondary player Z based on the game.

+

The server of Casino A 110 may further transmit received data about a game to the server of the regulator 170. Such data may allow the regulator to monitor the fairness of games, to watch for illegal gaming, to track taxable income of the casino, or to perform any other desired function.

+

In various embodiments, the terminal of secondary player X 140 may transmit to the server of Casino A 110 data about the activities of secondary player X at the terminal. Further, the terminal of secondary player Y 150 may transmit to the server of Casino B 120 data about the activities of secondary player Y at the terminal. The server of Casino B 120 may transmit such data to the server of Casino A 110. Further, the device of secondary player Z 150 may transmit to the server of Casino A 110 data about the activities of secondary player Z at the device. Data received by the server of Casino A 110 from terminals 140 and 150, and from device 190 may allow the server of Casino A to tracking winnings and losses of secondary players X, Y, and Z; to determine which data (e.g., data about which games) to transmit to the terminals or device; to determine an amount owed to Casino A by Casino B for use of data from Casino A; and so on. Further, data received by the server of Casino A 110 from terminals 140 and 150, and from device 190 may be forwarded to the server of the regulator 170. The regulator may use such data to track the bets of secondary players, to check for illegal gambling, to monitor the fairness of games, etc.

+

It should be appreciated that the system of FIG. 1 represents a system according to some embodiments, and that other servers, devices, terminals, networks, and communication links may be present in various embodiments.

+

FIG. 2 shows the Casino A server according to some embodiments. In various embodiments a similar server may constitute the Casino B server, or the server of any other casino. The storage device 230 may store program data. The program data may be used to direct the processor 210 to execute algorithms in accordance with various embodiments. The storage device 230 may store other types of data. Such data may include data received from the play of games; data that can be used to recreate games; data describing bets, wins, and loss of primary and secondary players; data describing the current locations or activities of primary or secondary players; data describing amounts owed to a casino; and so on. Communication port 220 may be used to transmit and/or to receive data. Communication port 220 may include an antenna, a wireless transmitter, a signal generator, a router, or any other communication device. Any data transmitted or received may be stored, at least at some point, in storage device 230.

+

FIG. 3 shows a gaming device 130 according to some embodiments. The storage device 330 may store program data. The program data may be used to direct the processor 310 to execute algorithms in accordance with various embodiments. Program data may include data used to generate graphics, to determine game outcomes, to compute winnings, and so on. The storage device 330 may store other types of data. Such data may include data describing bets, wins, and losses by a primary player at gaming device 130. Input device 340 may include sensors, buttons, touch screens, microphones, bill validators, coin acceptors, card readers, and any other means by which a primary player or other party may interact with gaming device 130. For example, the input device 340 may include a “bet” button.

+

The output device 350 may include display screens, microphones, lights, coin dispensers, buzzers, and any other means by which a gaming device may provide a signal to the secondary player. The communication port 320 may be used to transmit and/or to receive data.

+

FIG. 4 shows a terminal 140 for use by a secondary player, according to some embodiments. The storage device 430 may store program data. The program data may be used to direct the processor 410 to execute algorithms in accordance with various embodiments. Program data may include data used to a recreate games or depictions of games based on data received about original games. Program data may include data used to generate graphics, to display game outcomes, to compute winnings, and so on. The storage device 430 may store other types of data. Such data may include data describing bets, wins, and losses by a secondary player at terminal 140. Input device 340 may include sensors, buttons, touch screens, microphones, bill validators, coin acceptors, card readers, and any other means by which a secondary player or other party may interact with terminal 130. For example, the input device 340 may include a “bet” button.

+

The output device 350 may include display screens, microphones, lights, coin dispensers, buzzers, and any other means by which terminal 140 may provide a signal to the secondary player. The communication port 320 may be used to transmit and/or to receive data.

+

FIG. 5 shows a monitoring device 160 according to some embodiments. The monitoring device may receive data about a game via input device 530. The input device 530 may include a camera, microphone, pressure sensor, bar code scanner, sensor, button, and so on. For example, an input device may include a camera that is pointed at a table where a game of blackjack is being played. For example, an input device may include a camera that is pointed at the viewing window of a slot machine. Communication port 520 may be used to transmit data received by the input device to e.g., a casino server. In various embodiments, the monitoring device may serve multiple purposes, some of which may not involve receiving data about a game. For example, a monitoring device may include a camera which also serves security purposes at casinos.

+

FIG. 6 shows a database entry 600 including various information about a game. The database entry may store various aspects of a game played by primary player (e.g., by Jane Smith). Such data may later be used to allow a secondary player to participate in the game.

+

FIG. 7 shows a database entry 700 including various games played by a player. The player may be a primary player. The data in database entry 700 may allow a secondary player to examine historical data about the games of a primary player (e.g., about the games of Sam Hunter), including statistics about the games (e.g., the profits made in the last 100 games).

+

FIG. 8 shows a display screen for entering betting information and tracking the progress of a game, according to some embodiments. The display screen may be sensitive and/or responsive to touch and may thereby function as a touch screen, in some embodiments. One area of the display screen lists the favored primary players of the secondary player currently viewing the display. Presumably, the secondary player has logged in or otherwise identified himself to the terminal or device to which the display belongs. The secondary player may have previously indicated his favored primary players. The casino may thus track the whereabouts of the favored primary players and alert the secondary player when a favored primary player begins play.

+

Another area of the display screen includes an announcements area. The casino may make announcements to the secondary player. Such announcements may include promotional announcements. For example, such announcements may include announcements of discounts at casino or other restaurants, announcements of discounts on shows, announcements about upcoming concerts or boxing matches, announcements about discounts on hotel rooms, and so on. Announcements may include promotions for other products, such as automobiles, toothpaste, or plane flights to the Caribbean. Announcements may further include announcements about primary players in which the secondary player may be interested. For example, an announcement may indicate that a favored primary player of the secondary player has just begun play.

+

Another area of the display screen includes a list of primary players that are available in the sense that the secondary player may participate in the games of these primary players. This display area may identify the primary player, either by real name or by an alias, such as “TeeBone”. The alias may allow a primary player to maintain some anonymity or privacy. This display area may further indicate a game which the primary player is playing (and thus the game the secondary player would be participating in), a minimum bet required of the secondary player to participate in the game, and one or more statistics related to the primary players. For example, statistics may indicate a number of consecutive games won by the primary players. This display area may further include areas where a secondary player can touch in order to begin participating in the games of a primary player. For example, by touching an area labeled “select” next to primary player Robert Clements, the secondary player may begin participating in the games of Robert Clemens.

+

Another area of the display screen includes windows where a secondary player may track the progress of games in which he is participating. FIG. 8 depicts a first window where the secondary player can follow the game of primary player “TeeBone”, in whose game the secondary player is participating. The game is blackjack, and the secondary player has a bet of $5 riding on the game. The game is currently in progress. FIG. 8 depicts a second window where the secondary player can follow the game of primary player Sue Baker. The game is a slot machine game. The game has just finished with an outcome of “cherry-bar-cherry”. The secondary player has just won $6 on the game. Now, the secondary player has the opportunity to place bets on the next game, as indicated by the status “open for bets”.

+

Another area of the display screen includes a display of the credit balance of the secondary player. These credits may be used to bet on games in which the secondary player is participating. Each credit may correspond, for example, to $0.25 in value. The secondary player may place bets using the betting areas of the display screen, including a “Bet 25¢” area, a “Bet $1” area, a “Bet $5” area, a “Repeat Last Bet” area, and an “Auto Bet” area. When touched, such areas may apply to only the game which has a status of “Open for Bets”. For example, touching the “Bet 1” may cause a bet of $1 to be placed on the game of Sue Baker, since it is that game which has the status of “Open for Bets”. In this way, there need not be a separate set of betting buttons for every game in which the secondary player is participating. The “Repeat Last Bet” area may allow the secondary player to easily repeat a prior bet that may take extra effort to enter using the other betting areas. For example, rather than touching the “Bet $1” area 4 times to enter a $4 bet, the secondary player might simply touch the “Repeat Last Bet” area to repeat a prior bet of $4. The “Auto Bet” area may allow the secondary player to continue making the same bet on each new game, for example, without having to always enter a bet. In some embodiments, the secondary player may program in a particular betting strategy and then touch the “Auto Bet” area to have the strategy executed automatically by the terminal of the secondary player. The “Lock Game” area may allow the secondary player to prevent access to the terminal by other secondary players while he steps away for a break. The “Order Drinks” area may allow the secondary player to order drinks or other items and have them delivered to his terminal without ever leaving.

+

As will be appreciated, the various areas of the touch screen that allow touch interaction may also be implemented using ordinary buttons or any other interactive technology.

+

It should be appreciated that the figures do not necessarily show everything that might be included in a system, object, machine, device, etc. For example, although not shown in FIG. 3, gaming device 130 may include a coin hopper. +

    +
  • 1. One player bets on the outcome of a game of another player. For example, one player bets on whether a winning outcome will be achieved in the game of another player. For example, one player bets on whether another player will win. In various embodiments, one player may place a bet and either win or lose money based on the results of a game played by another player. As used herein, “primary player”, “primary players”, and the like, may refer to a player or players who most directly participate in a game, such as a casino game. A primary player may, for example, be physically located at a slot machine and may participate in a game at the slot machine by inserting a coin, indicating a bet amount, and pulling a handle of the slot machine. A primary player may also be physically located at a table game, such as a game of blackjack with a live dealer. In various embodiments, a primary player directly initiates a game in which he participates, e.g., by pulling the handle of slot machine or physically placing a bet at a table game and motioning to a dealer that he is interested in playing. In various embodiments, a particular game would not occur but for the actions of the primary player.
    • +
  •  As used herein, “secondary player”, “secondary players”, and the like, may refer to a player or players who participate or may come to participate in games played by primary players or by other secondary players. For example, a secondary player places a bet on a game in which a primary player is involved. The secondary player wins if the primary player wins, and the secondary player loses if the primary player loses. In another example, a secondary player places a bet for a game that has already occurred. When placing the bet, the secondary player does not know the outcome of the game. Once the secondary player has placed the bet, the outcome of the game may be revealed to the secondary player, and the secondary player may be paid if the outcome is a winning outcome. In another embodiment, secondary player A places a $10 bet on secondary player B, betting that secondary player B will win a game on which secondary player B has placed a $20 bet. If secondary player B wins the $20 bet, then secondary player A will win the $10 bet. In various embodiments, the secondary player does not initiate the game in which he participates. In various embodiments, a game in which the secondary player participates would occur whether or not the secondary player chose to bet on the game. The game in which a secondary player participates may be initiated by a primary player or may be initiated automatically, e.g., by a computer program.
    • +
  •  Where ever data is used herein, it should be understood that such data may be stored, such as in a database or in any other suitable medium, format, or data structure. Data may be stored in either a fixed location or throughout distributed locations. Data may be stored either in a single location or in multiple locations (e.g., in multiple redundant locations). The data may be retrieved as needed from its storage location. When data is generated but not immediately needed, such data may be stored for later retrieval. Data may be accessible by reference to any part of the data, including any tag or label associated with the data. For example, if some data elements of a set of data elements are known, the remaining data elements from the set of data elements may be retrieved based on the known data elements. For example, the known data elements may serve as a search key for finding the remaining data elements in the set of data elements.
    • +
  •  In all applicable embodiments described herein, any data generated, transmitted, stored, retrieved, or used may also be stored for auditing purposes. Such data may be made available to regulators to casinos (e.g., to casinos generating the data; e.g., to casinos using the data), or to any other relevant party. Data that may be stored may include data describing the size of a bet made by a primary player on a game, the type of bet made by a primary player on a game, intermediate events that occurred during a game (e.g., rolls prior to the final roll in a game of craps), the date of a game, the decision options that were available in a game (e.g., hit, stand in blackjack), the decisions that were made in a game, the outcome of a game, the amount paid to the winner of a game, and so on.
    • +
  •  In various embodiments, data may be collected and stored relating to any searches of game related data. For example, suppose a secondary player searches for all games in which a payout of more than 100 coins was won. Accordingly, data indicating the search criteria may be stored so that it may be possible to determine in the future that a secondary player searched for all games in which a payout of more than 100 coins was won. Further data describing the results of a search may be stored. For example, if the search by the secondary player yielded 1218 games, then this fact may be stored. Further identifiers for each game identified by the search may be stored. +
      +
    • 1.1. One player places bets on a game in which another player participates. In various embodiments, a secondary player may place a bet on the outcome of a game itself. For example, a secondary player may place a bet on the outcome of a slot machine game. If the outcome “bar-bar-bar” occurs in the game, then the secondary player may receive ten times his bet. The secondary player need not, in various embodiments, place the same type of bet as does the primary player. For example, the primary player may initiate a craps game with a “pass” bet. The secondary player may bet on the same craps game, but may place a “don't pass” bet. Thus, though the secondary player and the primary player have placed bets on the same game, the primary player may lose and the secondary player may win.
      • +
    • 1.2. One player places bets on how another player will do. In various embodiments, a secondary player may place a bet on what will happen to a primary player in a game. The secondary player does not, in various embodiments, bet on the outcome of the game itself, but only on how the outcome of the game effects the primary player given the primary player's bet on the game. For example, the secondary player may bet that the primary player will win the game. If the primary player wins, then the secondary player's bet may be a winning bet and the secondary player may receive a payment. If, however, the primary player loses, then the secondary player may lose.
      • +
    •  In various embodiments, the secondary player may bet that the primary player will lose. The secondary player may thus receive a payment for a winning bet if the primary player loses, but the secondary player may lose his bet if the primary player wins.
      • +
    •  It should be noted that often, a bet placed by a primary player will provide the house or casino with an advantage. This is how the house may make money, on average. Thus, if a secondary player is permitted to place a bet against a primary player, then the secondary player may enjoy the same advantage as the house. In various embodiments, the secondary player may be charged a fee for betting against the primary player. The fee may provide the house with an advantage in a bet that might otherwise favor the secondary player. The fee may be a flat fee. The fee may be a percentage of the secondary player's bet. The fee may be taken only from payments of winnings received by the secondary player. For example, if the secondary player wins a payment of $10 based on a $10 bet placed, 50 cents may be deducted from the payment and kept by the house.
      • +
    •  In various embodiments a fee charged to the secondary player may be set at an amount which provides to the house the same advantage as the house had against the primary player. As used herein, a “house advantage” or “house edge” may be defined as a ratio of the expected amount won by a casino to the initial amount bet by a player. Suppose that a house advantage on a game is 1.41%. Thus, a primary player who bets $1 could expect to receive $0.98.59 back, on average. Further, suppose that a primary player initially bets $1 and may receive back $0 (for a net loss of $1) or may receive back $2 (for a net gain of $1). An exemplary such bet would be a $1 pass bet in the game of craps. The secondary player, in this example, may bet $1 against the primary player. The secondary player would then expect to receive back $1.01.41, on average. In order to give the house the same advantage against the secondary player that it had against the primary player, the secondary player may be charged a fee of $0.02.82. This fee may be rounded to $0.03, or may be varied over a large number of secondary player bets so as to average out to $0.02.82. With the fee taken into account, the secondary player might expect to receive $0.98.59 back per dollar bet, providing the house with the same advantage against the secondary player as it had against the primary player.
      • +
    •  In various embodiments, the secondary player may not be allowed to take exactly the opposite position as does the primary (e.g., where all wins for the primary player are losses for the secondary player, and vice versa). In various embodiments, an outcome that causes the primary player to lose may not result in a win for the secondary player, even though the secondary player has bet against the primary player. For example, an outcome of “plum-orange-cherry” may cause the primary player to lose, but may also cause the secondary player to lose. In various embodiments, an outcome that caused the primary player to lose may result in a push or tie for the secondary player. In this way, the house may maintain an edge against the secondary player even if the house also had an edge against the primary player. In various embodiments, the outcomes which are losing for the primary player and not winning for the secondary player may be chosen in such a way that the house is given the same advantage over the secondary player that it had over the primary player. For example, suppose that a particular game provides the primary player with the potential to either win $1 net, or lose $1 net. Suppose further that the game has a 2% house edge. Suppose further that outcomes X and Y in the game are both losing outcomes for the primary player. Outcome X occurs with probability 0.03, and outcome Y occurs with probability 0.01. With a bet of $1 against the primary player, the secondary player would ordinarily expect to win $1.02, for an average net profit of $0.02. However, in various embodiments, outcomes X and Y may also be counted as ties for the secondary player. The secondary player's expected payment is then reduced by the probability of X times the amount that would have been won (beyond the bet amount) upon the occurrence of X, plus the probability of Y times the amount that would have been won (beyond the bet amount) upon the occurrence of Y. This reduction is equal to 0.03×$1+0.01×$1=$0.04. The secondary player's expected winnings have thus been brought down from $1.02 to $0.98. This reduction provides the house with the same 2% edge against the secondary player as it had in the original game against the primary player.
      • +
    •  In various embodiments, the secondary player may bet against an outcome that would ordinarily be winning in a game. For example, in a game of blackjack, the secondary player may bet that the dealer will win. In various embodiments, the house may then alter the probabilities of various outcomes in the game so as to return an edge to the house. For example, if a secondary player bets on the dealer in a game of blackjack, the house may remove cards with low point values from the deck. This may reduce the probability of a dealer win, and thus may reduce the probability that the secondary player may win when betting on the dealer. In various embodiments, a game where the secondary player bets on the house may not be a game that was actually played by a primary player. Rather, the game may be a game that is or was simulated by the house with probabilities of various outcomes altered from the standard probabilities of the game.
      • +
    •  In various embodiments, a secondary player may take the house's position, or approximately the house's position, and bet against a primary player. The secondary player may thereby lose whatever the primary player wins, and win whatever the primary player loses. For example, if the primary player loses his bet of $1, then the secondary player may win $1. However, if the primary player wins $10, the secondary loses $10. In order that the house may be sure of collecting $10 from the secondary player in the event that the primary player wins $10, the house may require the secondary player to place a sufficient deposit with the house to cover possible losses of the secondary player. The deposit might come in the form of a credit balance that the secondary player has accumulated (e.g., as a result of inserting bills, or as a result of winning bets), in the form of a financial account that the house is free to charge in order to collect on the secondary player's obligations (e.g., the secondary player may provide a credit card number), in the form of a check that the secondary player has provided to the house, or in any other suitable form. In various embodiments, the house may require a deposit or other commitment from the secondary player equal to the maximum possible payout that may be received by the primary player. For example, suppose the primary player participates in a game in which the primary player may win up to $100. If the secondary player bets against the primary player, then the secondary player may risk losing up to $100 in a game. The house may thus require the secondary player to have a credit balance of as much as $100 in order to bet against the primary player. In various embodiments, the house may require the secondary player to confirm (e.g., by pressing a button) that the secondary player is aware he has the potential to lose up to X amount, where X is the maximum the secondary player might lose from participating in a game.
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    •  In various embodiments, a secondary player may bet against a primary player while not mirroring the payouts of the primary player. For example, the secondary player may bet $1 on a game in which the secondary player bets that the primary player will lose. If the primary player does lose the game, the secondary player may receive $1.25, for a net profit of $0.25. If, the primary player wins, the secondary player may lose his bet of $1, for a net loss of $1. The secondary player may lose $1 regardless of the amount that the primary player wins. For example, the secondary player may lose $1 whether the primary player wins $1 or whether the primary player wins $100.
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    •  In various embodiments, the secondary player may bet that a primary player will win a certain multiple of the primary player's bet in a given game. For example, the secondary player may bet $5 that the primary player will win at least triple the primary player's bet of $2 in a game. The secondary player may win $20 if the primary player wins at least $6. Otherwise, the secondary player may lose his bet of $5.
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    •  In various embodiments, the secondary player may be paid according to a table or function that maps every possible result of a primary player to a payment for the secondary player. For example, the secondary player may receive $3 if the primary player wins $0, $5 if the primary player wins $1, $0 if the primary player wins $2, $0 if the primary player wins $3, $1 if the primary player wins $4, and so on. As will be understood, the function need not perform a linear or continuous mapping.
      • +
    •  In various embodiments, a secondary player may be forbidden and/or prevented from placing a bet that would provide the secondary player with an edge. For example, a secondary player may be prevented from betting against a primary player, where the house had an edge versus the primary player.
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    • 1.3. A player places bets for games from the past. In various embodiments, a secondary player may place a bet on a game that has occurred in the past. With respect to the game, at least one of the following may have occurred in the past (e.g., before the secondary player placed a bet on the game): (a) the game's start; (b) the game's conclusion; (c) collection of a bet from the primary player who played the game; and (d) payment of winnings to the primary player who played the game.
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    •  When a game is originally played, a record of the game may be created. The record may include data sufficient to recreate all or part of the game. Such data may include: (a) one or more seeds or random numbers used to generate outcomes for the game; (b) one or more outcomes of the game (e.g., “cherry-bell-lemon”; e.g., a sequence of five cards, such as cards constituting a poker hand; e.g., a set of hands of cards, such as a player hand and dealer hand, or such as a player hand and hands of the player's opponent; e.g., the number or numbers showing on one or more dice, such as in a game of craps; e.g., a sequence of numbers showing on a sequence of dice rolls; e.g., a set of numbers in a game of keno; e.g., the payouts achieved in a bonus round; e.g., the level achieved in a bonus round); (c) one or more symbols comprising an outcome of the game; (d) one or more cards; (e) reel positions for one or more reels of a slot machine; (f) a number of decks used; (g) a decision made by a primary player of the game; (h) one or more algorithms used to generate an outcome of the game; (i) an identifier for the gaming device used in the game; (j) a pay table used for the game; (k) a make, model, or year for the gaming device used in the game; (l) a date or time when the game was played; (m) a location where the game was played; (n) a dealer involved in the game; (o) a position of the primary player at a table used in playing the game; (p) an identifier (e.g., a name) for the primary player who played the game; (q) an identifier of another player in the game (e.g., another player at a blackjack table where the game was played); (r) a bet made by a primary player of the game; (s) winnings received by the primary player in the game; (t) video footage of the game; (u) audio footage of the game; and (v) an order of cards dealt from a deck of cards. Video footage of the game may include video footage from various perspectives. In some embodiments, video footage may show or focus on cards, dice, or reels, or other items which determine and/or reveal the outcome of a game. Video footage may include footage of actions in a game, such as footage of a player making bets, making decision, and/or collecting winnings. Such video footage may focus on a player's hands, for example. In some embodiments, video footage may show or focus on a dealer or other casino representative in charge of a game. In some embodiments, video footage may show or focus on a player's face or body. For example, video footage may show a player's facial expressions or body language during a game. In some embodiments, video footage may focus on spectators. In some embodiments, video footage is recorded from a live game. In some embodiments, video footage is generated. Video footage may be generated based on stored data about a game.
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    •  Video footage may be generated in a number of ways. In some embodiments, video footage may be generated by assembling stock video clips. For example, one stock video clip may show a primary player (e.g., an actor acting as a primary player) making a bet. Another stock video clip may show a primary player rolling the dice. There may be stock video clips of every possible outcome in a game. For example, there may be a stock video clip showing the every possible roll of two dice. To assemble video footage of a complete game, the casino may e.g., put together a video clip of a bet being made, a video clip of an outcome being rolled corresponding to the outcome that actually occurred in the original game the secondary player is betting on, and a video clip of a player collecting his winnings. In some embodiments, stock video footage may include video footage of entire games. Should a similar game later occur, the same video footage may be used for the similar game when the secondary player is participating in the similar game.
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    •  In some embodiments, video footage is generated using computer algorithms. For example, computer algorithms may generate footage showing a simulated primary player placing a bet and rolling dice, the dice bouncing and landing, a simulated croupier paying winnings, and so on. In various embodiments, video may be generated so as to be true, as much as practicable, to the data of the game. For example, video may be generated to show a video or animated depiction of an outcome that actually occurred in a game of a primary player.
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    •  In various embodiments, video may be generated based on data about a game. Data indicating the bet amount of a primary player may be used to generate video of a primary player (e.g., a simulated primary player) making a bet of the same bet amount. Data indicating an outcome of a game may be used to generate video showing the same outcome being generated. Data indicating intermediate symbols or indicia that appear during a game may be used to generate video showing those same intermediate symbols or indicia. For example, data indicating that a particular position at a blackjack table was dealt the seven of hearts may be used to generate video showing the simulated dealing of the seven of hearts on a simulated blackjack table. Data indicating the identity of a primary player may be used to generate video. For example, based on a stored photo of a primary player, the casino may generate cartoon caricatures of the primary player playing a game. Data indicating the age or other demographic of a primary player may be used to generate video. For example, if the primary player is a 60 year-old female, the casino may generate a cartoon caricature of a 60 year-old female playing a game. In some embodiments, demographic data about a player may be used to retrieve stock footage of a player with similar characteristics. For example, stock footage of a 60 year-old female player may be retrieved.
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    •  The record of the game may be stored by a gaming device, casino server, third party server, or other device. Subsequently, a secondary player may place a bet on the game, or on some aspect of the game. Once the secondary player has placed a bet, data stored in the record may be used to recreate the game, or to recreate some aspect of the game. For example, video footage of the game may be shown to the secondary player. In some embodiments, the outcome of the game may simply be displayed for the secondary player.
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    •  Based on the outcome of the game, and based on the bet placed by the secondary player, the secondary player may lose his bet, lose a portion of his bet, break even, or be paid winnings. For example, if the outcome of the game is a winning outcome, then the secondary player may be paid based on the standard rules of the game. For example, if the secondary player bets $10 on a game of blackjack, and the primary player in the game received 20 points to the dealer's 19, then the secondary player may win $10 in addition to keeping his bet.
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    •  If the secondary player has placed a bet on what would happen to the primary player, then the winnings and/or losses of the primary player may be revealed to the secondary player. For example, if the secondary player bet against the primary player, and the primary player lost, the secondary player may win. If the secondary player made a bet whereby the secondary player receives twice the winnings of the primary player, and the primary player wins $20, then the secondary player may receive $40
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    • 1.4. A primary player on which a secondary player was betting is no longer available. In various embodiments, a secondary player may participate in one or more games played by a primary player. For example, the secondary player may place bets on the games played by the primary player. The primary player may, at some point, terminate his playing session. The secondary player may, on the other hand, wish to continue his participation in the games of the primary player, and may thus find himself deprived of opportunities to make bets on the games of the primary player. +
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      • 1.4.1. A primary player is asked to stay. In various embodiments, the primary player may signal his intention to terminate a playing session. For example, the primary player may stand up, cash out, refrain from placing a bet even though he is at a table game, and so on. The secondary player may signal his desire to continue participating. For example, the secondary player may press a button labeled “continue session” on a betting interface. The secondary player may communicate his desire verbally (e.g., to a casino representative), via text (e.g., via a text message sent to a casino representative) or in any other manner. Regardless of whether the secondary player actually signals his desire to continue participating, the primary player may be contacted. For example, a representative of the casino may contact the primary player. Such a representative may include a waitress, pit boss, dealer, etc. The primary player may be asked to stay and to continue playing. The primary player may be offered a benefit for staying, such as cash, goods or services, a free meal, show tickets, improved odds, comp points, and so on. The primary player may be informed that there is a secondary player who appreciates the results of the primary player and wishes for the primary player to remain.
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      •  In some embodiments, a primary player who has signaled an intent to leave may be asked to stay only if one or more criteria are satisfied. For example, the primary player may be asked to stay only if at least three secondary players have been participating in the games of the primary player. Other criteria may include: (a) there are at least X secondary players watching the games of the primary player; (b) there are at least X secondary players who are interested in participating in the games of the primary player; (c) there has been at least X dollar amount of bets placed by secondary players on each game of the primary player; (d) there has been a total of at least X dollar amount of bets placed by secondary players on games of the primary player during a particular period of time, number of games, particular playing session, etc.; (e) the casino has made at least X dollars of profit from secondary players having participated in the games of the primary player; (f) the casino has made at least X dollars of theoretical win or profits from secondary players having participated in the games of the primary player; and so on. It will be appreciated that a casino may require any combination of the above criteria to be met in order for a primary player to be asked to stay. There may be multiple ways of meeting the above criteria, including by partially satisfying two or more of the criteria. It will further be appreciated that there may be other criteria that a casino may use based on whose satisfaction the casino may ask a primary player to continue with a playing session.
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      •  In various embodiments, a casino may offer a primary player an opportunity to play a fair game (i.e., where the primary player's expected winnings accounting for the cost of betting are exactly 0), if the primary player will continue to play.
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      • 1.4.2. The casino plays automatically. In some embodiments, when a primary player terminates a playing session, the casino or house may play in place of the primary player. For example, a dealer at a blackjack table may continue to deal a hand to the position where the primary player had been. The dealer may make decisions for the hand, such as hit or stand decisions. The decisions may be made according to optimum strategy. The decisions may also be made based on inputs from the secondary player. Another representative of the casino may also stand in for the primary player. For example, the other representative may sit at the table or slot machine where the primary player had been, and may resume play.
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      •  In some embodiments, game outcomes may be generated automatically once the primary player leaves. For example, a slot machine that the primary player has left may continue to generate outcomes. The secondary player may thus continue to place bets on the outcomes.
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      •  In some embodiments, a computer algorithm may make decisions in a game. The computer algorithm may substitute in for a primary player in a game so that a secondary player may participate in the game without the presence of a human primary player. In some embodiments a computer algorithm may act as a primary player even when a secondary player had not been participating in games of a prior human primary player. In other words, a computer algorithm need not necessarily substitute in for a primary player, but may serve as a simulated or artificial primary player from the get go. A computer algorithm may make decisions in a game. The computer algorithm may make decisions of how much to bet; decisions of what types of bets to make (e.g., the computer algorithm may decide whether or not to make an insurance get in a game of blackjack); decisions of whether to check, bet, raise, call, or fold (e.g., in a game of poker); decisions about whether or not to receive additional cards (e.g., in games of blackjack or video poker); and any other decisions that may be made in a game. The computer algorithm may refer to a stored set of rules for making decisions in a game. For example, the computer algorithm may refer to a table which lists one or more possible situations which might arise in a game and which lists a corresponding decision that should be made should that situation arise. The computer algorithm may also include procedures, logic, or other computational methods for computing a decision given a game state. For example, in a game of video poker, a computer algorithm may compute expected winnings given each of several possible decisions. The computer may determine which of the decisions leads to the highest expected winnings and make that decision.
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      •  In various embodiments, a computer algorithm may be programmed to make decisions which yield the highest expected winnings, payouts, and/or profits in a game. In various embodiments, a computer algorithm may be programmed to approximate the play of a human player. The computer algorithm may be programmed to, at least occasionally, favor strategies with emotional or intuitive appeal over those that are optimal. For example, a computer algorithm may be programmed to pursue a high paying hand in a game of video poker even when expected winnings would be optimized by pursuing a lower paying but more certain hand. In various embodiments, computer algorithms may be programmed with different personalities. Some might be programmed to take big risks in the strategies they use. Some might be programmed to play conservatively. Some computer algorithms may be programmed to bet frequently (e.g., in games of poker). Some computer algorithms may be programmed to bet infrequently, and only with very good hands (e.g., in games of poker).
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      • 1.4.3. An interrupted session of the primary player is resumed when primary player returns. In some embodiments, when a primary player leaves, the session of the secondary player may be put on hold. That is, for the time being, the secondary player may not have the opportunity of placing bets and participating in games played by the primary player. However, the secondary player may have the opportunity to resume playing when the primary player returns and initiates new games. +
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        • 1.4.3.1. An alert is given to the secondary player when primary player returns. In some embodiments, the secondary player may be sent an alert when the primary player has returned, or when the primary player is soon to return, or when the primary player is likely to return. The alert may take the form of a phone call, email, text message, verbal alert by a casino representative, and so on.
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        +
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      • 1.4.4. In some embodiments, a secondary player may indicate a primary player in whose games the secondary player may be interested in participating. The secondary player may thereby “tag” or “bookmark” the primary player as a player in whose games the secondary player may wish to participate. In various embodiments, the casino may allow the secondary player to easily determine when a bookmarked primary player is playing (e.g., is seated at a gaming device or gaming table; e.g., has inserted a player tracking card at a gaming device or gaming table; e.g., has played one or more games in the recent past). For example, a secondary player may peruse a list of bookmarked primary player. The secondary player may select one of the primary players from the list and may then be shown whether or not the primary player is currently playing, what game the primary player is playing, where the primary player is playing, or any other information of interest. In some embodiments, the casino may alert the secondary player anytime a bookmarked primary player has begun playing. In some embodiments, the casino may keep track of various statistics related to primary players that the secondary player has bookmarked. The casino may report such statistics to the secondary player when the secondary player makes contact with the casino (e.g., sits at terminal from which the secondary player may participate in games of the primary player), or at any other time. Statistics may include statistics about recent games played, recent wins, recent losses, recent large payouts, recent profits, and so on. Statistics need not necessarily be recent, but may be recent if the secondary player has previously learned of older statistics about the primary player. In various embodiments, if a secondary player is ready to begin participating in the games of a primary player, the secondary player may be offered (e.g., by default) the opportunity to participate in games of a bookmarked primary player. The secondary player may be offered the opportunity to participate in the games of a first bookmarked primary player (e.g., a primary player that is first on the secondary player's list of favorite primary players). If the secondary player declines, the secondary player may be offered the opportunity to participate in games of a second bookmarked primary player (e.g., a primary player that is second on the secondary player's list of favorite primary players), and so on. In various embodiments, secondary players may share tags or bookmarks of primary players amongst themselves. For example, a secondary player may publish a list of whom he thinks are “lucky” primary players. Other secondary players may view the list and decide to participate in the games of the listed primary players.
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      • 1.4.5. An expected value is paid to the secondary player. In various embodiments, a secondary player may have placed a bet on results of a primary player spanning more than one game. For example, the secondary player may have bet that a primary player would be ahead monetarily after one hour of play. If, however, the primary player leaves prior to completing one hour of play, there is the potential that the secondary player's bet remains unresolved. In various embodiments, the secondary player's bet is settled for the expected value (EV) of the secondary player's winnings. For example, if, based on the current time, the current winnings of the primary player, and the odds of the game that the primary player has been playing, the expected winnings of the secondary player are $8, then the secondary player may be paid $8 when the primary player terminates his session. The bet may also be settled for various functions of the EV, such as for the EV less a processing fee, 50% of the EV, and so on.
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      • 1.4.6. Bets are returned to the secondary player. In some embodiments, when the primary player terminates a session, a bet made be the secondary player that was dependent on the primary player finishing the session may be returned to the secondary player.
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      • 1.4.7. Options to participate in the games of other primary players are shown to the secondary player. In some embodiments, when the primary player terminates a session, the secondary player may be presented with other primary players on whom or on whose games the secondary player might bet. By selecting one or more of the new primary players, the secondary player may continue participating in games. For the purposes of a bet that required the completion of the session by the original primary player, the new primary player may be treated as if he was continuing where the original primary player left off. For example, the new primary player may be treated as if he has lost $6 during the past half hour, as the original primary player actually did. If the new primary player subsequently wins $10 in the next half hour, a bet made by the secondary player that the original primary player would be ahead after an hour of play would be a winning bet.
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      •  When a selection of new primary players is presented to the secondary player, primary players presented may be chosen by the casino based on similarities to the original primary player. For example, suppose the original primary player was from Texas. When the original primary player terminates his session, new primary players may be presented wherein each is also from Texas. Other characteristics that the original and new primary players may share include: (a) both may play the same type game (e.g., both may play IGT's Wheel of Fortune® slot machines); (b) both may be of the same gender; (c) both may be the same age; (d) both may have the same occupation; (e) both may have the same geographic location of residence or origin; (f) both may have common interests (e.g., in music, food, sports, etc.); and (g) both may share common birthdays.
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      • 1.4.8. The secondary player is given the opportunity to become a primary player. He's told where he can sit down and start playing. In some embodiments, when a primary player terminates his session, the secondary player is offered the chance to become a primary player. For example, the secondary player is shown the location of the slot machine or table game where the primary player had been playing. The secondary player may be offered the opportunity to take the seat and/or take the place of the primary player.
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      • 1.4.9. Historical games of the primary player are found. In some embodiments, when the primary player terminates a session of play, the secondary player may be offered the opportunity to participate in historical games of the primary player. In various embodiments, the historical games may include games in which the secondary player has not already participated. The secondary player may thereby have the opportunity to continue benefiting from the skill, luck, or other value he associates with the primary player.
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      +
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    • 1.5. Maintenance of player privacy. In various embodiments, the identity of a primary player may be shielded from the secondary player. This may prevent a secondary player from finding out sensitive financial information about the primary player, from scolding the primary player for unfavorable outcomes, or for otherwise causing harm or discomfort to the primary player. +
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      • 1.5.1. The secondary player doesn't see who he is betting on. In various embodiments, facial features or any other potentially identifying features of a primary player are hidden from the secondary player. For example, in video footage of the game of the primary player, the face is blurred, covered, or completely omitted from the field of view. Voices may be edited out or masked.
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      • 1.5.2. The secondary player does not know the location of the person he is betting on. In various embodiments, the location of the primary player is disguised or kept hidden. Otherwise, especially for a live game, it would be conceivable that the secondary player could find the primary player by simply going to the location of the primary player. Thus, in various embodiments, video footage of the game of the primary player may omit distinguishing characteristics of the primary player's location. Such characteristics may include identifiable features of a casino, such as pictures, sculptures, fountains, names of restaurants, signs for a bathroom, signs for a poker room or other casino sector, and so on. Distinguishing features of a table game may also be disguised or omitted. For example, a unique design or color of a table may be omitted. In various embodiments, games or locations with readily identifiable and/or unique characteristics may be ineligible for participation by secondary players.
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      • 1.5.3. Limits to how many times a secondary player can bet on one particular person. In various embodiments, there may be a limit as to the number of games of a primary player in which a secondary player may participate. This may lessen the likelihood of the secondary player developing any strong feelings towards the primary player one way or the other. In various embodiments, there is a limit to the amount of time that the secondary player is allowed to spend participating in the games of a given primary player.
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      •  In various embodiments, a secondary player may be switched from participating in the games of a first primary player to participating in the games of a second primary player. The secondary player may be switched without the secondary player knowing that he has been switched. For example, the secondary player may receive data about a game that includes the symbols, indicia, and/or outcomes generated during the game. However, the secondary player may not necessarily receive identifying information about a primary player of the game. Thus, when the secondary player is switched from participating in the games of a first primary player to participating in the games of a second primary player, the secondary player may not be aware of the switch since the secondary player may have no access to identifying information for either the first or second primary players. In various embodiments, the secondary player may be switched form participating in the games of a first primary player to participating in the games of a second primary player after a predetermined number of games. For example, after participating in 25 games of a first primary player, the secondary player may be switched to participating in the games of a second primary player. In various embodiments, a switch may occur at random. For example, after every game played by a first primary player, the casino may randomly generate a number between 1 and 100. If the number is greater than 80, the casino may switch the secondary player from participating in the games of the first primary player to participating in the games of a second primary player. In some embodiments, the switch may occur after a random number of games with an upper boundary. For example, if the secondary player has not been switched after 20 games with a first primary player, the secondary player may be switched automatically. In some embodiments, a secondary player may be switched upon his own request. In various embodiments, when a secondary player is switched between the games of different primary players with reasonable frequency, the chances with which a primary player's privacy becomes compromised may be reduced. In some embodiments, a secondary player may be informed when he has been switched from the games of a first primary player to the games of a second primary player. In some embodiments, the secondary player is not informed of the switch.
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      • 1.5.4. Introduction of a time delay so that the primary player is no longer located where he had been by the time the secondary player begins participation in the games of the primary player. In various embodiments, a secondary player is restricted to betting on games that have occurred a predetermined amount of time in the past, e.g., one day or more in the past. In this way, the secondary player is unlikely to be able to contact the primary player, as the primary player may no longer be in the vicinity. In various embodiments, the secondary player is restricted to betting on games that have been played by a primary player who has already left the location in which the games were originally played.
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    • 1.6. A secondary player or spectator is provided with knowledge about what the next cards will be, or what the primary player's opponent holds. The secondary player may watch the primary player struggle with a decision while the secondary player already knows the correct decision. In various embodiments, a secondary player may be informed of some information about a game that the primary player does not know, or at least did not know at the time the primary player was participating in the game. For example, a primary player may be engaged in a game of video poker. The secondary player may watch the progress of the game from a remote terminal. The secondary player may be informed that the next four cards in the deck are all aces. However, this information is not known to the primary player. Thus, the secondary player may experience the excitement of hoping the primary player will draw four cards. +
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      • 1.6.1. The secondary player knows the next cards, the symbols that will occur on reels, the proper door to open in a bonus game, etc. In various embodiments, a secondary player may be informed of one or more of the following at a point in a game prior to when a primary player finds out (or found out): (a) an outcome of a game (e.g., “cherry-cherry-cherry”); (b) a payment that the primary player will receive based on the game; (c) a game result (e.g., win, lose); (d) a reel position; (e) a symbol that will appear on a reel (e.g., the secondary player may know that the third reel of a slot machine will show a symbol “bar” that will complete a winning outcome of “bar-bar-bar” prior to when the primary player finds out); (f) a card that will be received by the primary player; (g) a card that will be received by a dealer; (h) a card that is at or near the top of the deck being used in a game of cards; (i) a hand of cards that will be achieved by a primary player should the primary player make a particular decision (e.g., a hit decision in blackjack); (j) an order of cards in a deck of cards (k) a payment, result, or outcome that would result from a particular choice in a bonus game of a gaming device (e.g., the primary player would win 200 coins by choosing door number 3 in a bonus game); (l) a card that will be received by the primary player's opponent; (m) a card held by the primary player's opponent (e.g., in a poker hand); (n) a number that will appear on a die in a game (e.g., in craps); (o) a number that will come up in the game of roulette; and so on.
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      • 1.6.2. The secondary player may make a new bet at apparently good odds if the primary player is not likely to make a decision that would win for the secondary player. In various embodiments, a secondary player may be allowed to place a bet on a game being played by the primary player after finding out information about the game. The bet may be made at odds apparently favorable to the primary player. For example, suppose that a primary player holds an initial hand of video poker comprising the Ks, Kc, 10h, 3c and 7d. Unbeknownst to the primary player, but known to the secondary player, the next four cards in the deck are the Ah, Kh, Qh, and Jh. Thus, were the primary player to discard the Ks, Kc, 3c, and 7d, the primary player would achieve a royal flush, the highest paying outcome, in various embodiments. The secondary player may be allowed to bet four coins on the game. The secondary player may win 1 coin for a pair, jacks or better, 2 coins for two-pair, 3 coins for three-of-a-kind, and 800 for a royal flush. Thus, the secondary player may bet 4 coins with an apparent potential to win 800 coins. Indeed, it is possible that the second player will win 800 coins. However, it would be very unlikely for the primary player to discard a pair of kings in order to draw four cards to the 10h. Thus, it is more likely the primary player will keep his pair of kings, draw three cards, and end up with three kings, providing the secondary player with a payout of 3 coins. Thus, in various embodiments, the strategy of a primary player may be predicted, e.g., by the casino server. The predicted strategy may be, e.g., an optimal strategy given lack of any knowledge about future results or outcomes (e.g., future cards in a deck). Based on predictions of the primary player's strategy, the casino server may provide betting opportunities for the secondary player such that the house will maintain an advantage given the predicted strategies. The same betting opportunities provided to the secondary player may have provided the house with a disadvantage if the primary player were to be able to utilize knowledge of future results or outcomes (e.g., future cards in a deck). Accordingly, a secondary player may make certain bets on a game in the hopes that the primary player will deviate from optimal or conventional strategy.
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      • 1.6.3. The secondary player may provide hints. In various embodiments, a secondary player may have the opportunity to convey a hint to the primary player. A hint may take the form of a suggested decision. For example, a hint may indicate that the primary player should discard the first and third cards in his hand of video poker. A hint may take the form of a veto. For example, the primary player may first indicate a particular choice of strategy, such as a particular combination of cards to discard in a game of video poker. The secondary player may provide an indication that such a strategy should not be followed. The secondary player may be allowed only one veto, or may be allowed up to a predetermined number of vetoes. A hint may take the form of information about a symbol, result, or outcome of a game. For example, in the bonus round of a slot machine game, the secondary player may inform the primary player of the number of coins behind door 2. It may happen that there are more coins behind door 3, but the secondary player may only be allowed to give a hint about door 2, in some embodiments.
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      • 1.6.4. The secondary player may watch the primary player for entertainment purposes. The secondary player may watch facial expressions during good outcomes or during near-misses. In various embodiments, the secondary player may derive entertainment or other gratification from watching the experiences of the primary player. The secondary player may, for instance, watch a primary player play a game in which the primary player will win a large payout. The secondary player can watch the expression on the face of the primary player (e.g., from video footage) and see the expression change from neutral to an expression of surprise and elation. The secondary player may choose to participate in games that are likely to have or to have had an emotional impact on the primary player. The secondary player may thus choose games in which a payment above a predetermined amount was won, in which a certain outcome (e.g., a winning outcome) was achieved, in which a jackpot was achieved, in which a bonus round was played, and so on. A secondary player may also choose a game in which the primary player comes close, or apparently comes close to achieving a large payment. For example, the secondary player may choose a game in which the primary player has four cards to a royal flush in video poker, and will draw a fifth card. The secondary player may also choose a game in which two out of three reels of a slot machine line up on jackpot symbols.
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      • 1.6.5. A search is performed to find games that include near misses of high paying outcomes, or any other characteristic. In various embodiments, a secondary player may receive information about various games that will happen, are in progress, or have happened already. Based on the information, the secondary player may choose a game in which to participate, or which to watch. The secondary player may have a preferred game he likes to play, a preferred primary player he likes to bet with (or on), a preferred dealer in whose game he wishes to participate, and so on. The secondary player may also wish to participate in games where he knows something about the outcome, results, or other information about the game. For example, the secondary player may wish to participate in games where the first two reels of a slot machine show the jackpot symbols.
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      •  In various embodiments, the secondary player may indicate a desired criterion, or desired criteria about the game. Various games satisfying the criterion or criteria may then be made available for the secondary player to participate in. The secondary player may then choose one or more of the games to participate in. In various embodiments, once the secondary player has indicated a criterion or criteria, the secondary player may automatically begin participating in a game matching the criterion or criteria. Criteria indicated for a game by a secondary player may include one or more of the following: (a) the game has a particular dealer; (b) the game has a particular number of players; (c) the game is played at a particular gaming device; (d) the game is played at a particular type of gaming device; (e) the game is played by a particular primary player; (f) the game is played by a primary player with a particular characteristic (e.g., age, race, marital status, nationality, area of residence, occupation, etc.); (g) the game has a potential payout above a particular level (e.g., the game has a payout of more than 1000 times the bet); (h) the game has an expected payout above a certain level (e.g., an expected payout of more than 95% of the original bet); (i) the game has a bonus round; (j) the game is played in a certain location; (k) the game is played at a certain time or date; (l) the game is, or will be a winning game (e.g., the game will pay at least three times an initial bet of the primary player); (m) the game will feature an outcome that has almost all the required symbols necessary for a large payout (e.g., a game of video poker has four cards to a royal flush); and so on.
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      • 1.6.6. Preventing collaboration. In various embodiments, measures may be taken to prevent collaboration between the primary player and the secondary player. Particularly if the secondary player knows information about the game, such as hidden cards in a deck, the secondary player would be able to confer an advantage to the primary player and to himself by communicating with the primary player. As discussed previously, the identity of the primary player may be shielded from the secondary player. Similarly, the identity of the secondary player may be shielded from the primary player. One or both of the primary and secondary players may be kept in an enclosure, such as a sound-proof room or Faraday cage, that reduces the possibility of communication. Signal detectors, such as antennas, may be placed near the primary or secondary players to detect possible communications between the two. Cell phones, pagers, Blackberries™ and other communication devices may be temporarily confiscated from either or both of the primary and secondary players. The secondary player may participate in the game only after one or more, including all game decisions have been made in the game.
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    • 1.7. What happens if a machine needs servicing in the middle of a role? What happens if the primary player is taking too long to finish a game? In various embodiments, the completion of a game may be delayed or prevented. For example, a gaming device may break down in the middle of a game. A primary player may get into a discussion with a friend in the middle of a video poker game, and may thus delay a decision in the game for several minutes. A secondary player participating in a delayed game may find the delay frustrating and may wish to complete the game in some other manner. +
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      • 1.7.1. A game is completed automatically. In various embodiments, the game may be completed automatically, e.g., by the casino. The game that is completed automatically may, in fact, be a copy of the original game, so that the primary player can complete the original game on his own. However, the secondary player may receive a payment based on the automatically completed game. The game may be completed using a predetermined strategy, such as optimal strategy. The game may be completed using a random strategy where, for example, one of several possible strategies is selected at random.
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      • 1.7.2. The secondary player makes the decisions in a game. In some embodiments, the secondary player may have the opportunity to complete the game by making his own decisions. For example, if the game is blackjack, the secondary player may indicate decisions such as “hit” or “stand” so as to complete the game. The secondary player may, in various embodiments, complete a copy of the original game, so that the primary player may complete the original game on his own. A copy of the original game may include a second game with one or more similar parameters or aspects to the first game. For example, in the copied version of the game, one or more of the player hand, the dealer's hand, the order of cards in a deck, the prizes available behind certain doors in a bonus game, etc., may be the same as in the original game.
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      • 1.7.3. A bet is returned to the secondary player. In various embodiments, when a game is delayed, the bet placed by the secondary player on the game may be returned to the secondary player.
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      • 1.7.4. The secondary player is provided with an expected value of his winnings at that point in the game. In various embodiments, when a game is delayed, the expected payment or the expected winnings to be paid the secondary player may be provided to the secondary player. In some embodiments, a function of the expected payment is provided, such as the expected payment less a fee.
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    • 1.8. Communication between the secondary player and the primary player. In some embodiments, the primary player and the secondary player may be given the opportunity to communicate. Communication may occur via text, voice, or any other means. Communication may occur through the casino server. Communication may be monitored by the casino, such as by a computer program or a casino representative. Communication may be edited or prevented if there is inappropriate or threatening language and/or if communication somehow provides either the primary player or secondary player with an unfair advantage. +
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      • 1.8.1. The secondary player sends help to the primary player. For example, “you should hit here”. In some embodiments, the secondary player may send help to the primary player. The secondary player may help the primary player with strategy in a game such as blackjack, video poker, or live poker. In video poker, the secondary player may suggest which cards the primary player should discard. In blackjack, the secondary player may suggest whether to hit, stand, double down, split, etc. In a live game of poker, the secondary player may advise the primary player whether to check, bet, raise, fold, or call. The secondary player may also suggest an amount of a bet or raise. The secondary player may provide other suggestions or opinions, such as suggesting that another player is probably bluffing. The secondary player may provide additional information, such as the probabilities of various events occurring given a particular strategy. For example, the secondary player may indicate that the primary player would have roughly 2 to 1 odds against making a flush should he continue in a game of poker.
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      • 1.8.2. The secondary player takes over the game. In various embodiments, a secondary player may take the place of a primary player in making decisions in a game. For example, the secondary player may transmit signals that cause game decisions to be made without additional input by the primary player. For example, the primary player may press a button on a gaming device labeled “defer to secondary player”. The secondary player may then select, e.g., cards to discard from a remote terminal. The remote terminal may, in turn, transmit to the gaming device indications of which cards the secondary player has chosen to discard. The chosen cards may then be removed from the primary player's hand and replaced with new cards. The primary player may win or lose, and may receive payments based on the decisions made by the secondary player.
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      • 1.8.3. Sending a tip to the primary player. In various embodiments, the secondary player may send a tip, other consideration, or other token of gratitude to the primary player. For example, if the primary player has just won a large payment, thereby causing the secondary player also to win a large payment, the secondary player may be grateful and wish to tip the primary player. The secondary player may provide an indication that he wishes to tip the primary player, e.g., by pressing a button on a remote terminal. The casino server may then deduct the amount of the tip from an account associated with the secondary player, and add such amount to an account associated with the primary player. The casino server may also cause the amount of the tip to be paid out at the primary player's gaming device or table, e.g., in the form of a coin or cashless gaming receipt. In some embodiments, the primary player may pay to have something delivered to the primary player. For example, the secondary player may pay for a bottle of wine. A casino representative, such as a waitress, may then deliver the bottle of wine to the primary player at the location of the primary player.
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    • 1.9. Betting interfaces. A secondary player may participate in the game of a primary player using various interfaces. The interfaces may allow the secondary player to select a game in which to participate, including selecting various aspects of a game, such as the machine on which the game is played, the primary player playing the game, the time, and so on. The interface may allow the secondary player to select a bet type. For example, the secondary player can bet for a primary player to win, or for a primary player to lose. The interface may allow the secondary player to select a bet amount. The interface may allow the secondary player to insert cash or other consideration, to identify himself (e.g., for the purposes of receiving comp points), and to cash out winnings or remaining balances. +
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      • 1.9.1. Internet. A secondary player may participate using a network, such as the internet or a casino intranet. The secondary player may employ a computer, such as a personal computer, for this purpose. The secondary player may view a selection of games to participate in, progress of a current game, credit balances, etc., using a computer monitor. The secondary player may input decisions using a mouse, computer keyboard, or any other computer input device. For example, the secondary player may key in a bet amount using a numeric keypad on a computer keyboard. The secondary player may also use a device such as a phone, a cell phone, personal digital assistant, or Blackberry™. The contents of the following United States patent applications, listed with serial numbers, titles, and matter numbers in parenthesis, are incorporated by reference herein for all purposes: (a) Ser. No. 10/835,995 System and Method for Convenience Gaming (075234.0121); (b) Ser. No. 11/063,311 System and Method for Convenience Gaming (075234.0136); (c) Ser. No. 11/199,835 System and Method for Wireless Gaming System with User Profiles (075234.0173); (d) Ser. No. 11/199,831 System for Wireless Gaming System with Alerts (075234.0174); (e) Ser. No. 11/201,812 System and Method for Wireless Gaming with Location Determination (075234.0176); (f) Ser. No. 11/199,964 System and Method for Providing Wireless Gaming as a Service Application (075234.0177); (g) Ser. No. 11/256,568 System and Method for Wireless Lottery (075234.0178); (h) Ser. No. 11/210,482 System and Method for Peer-to-Peer Wireless Gaming (075234.0179); (i) Ser. No. 60/697,861 Enhanced Wireless Gaming System (075234.0183). The device used by the secondary player for participating in games may communicate with a casino server via the network, as is commonly known in the art. Messages may be exchanged back and forth between a device used by the secondary player and the casino, the messages taking the form of streams of bits represented by electronic pulses, optical pulses, or any other practical representation.
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      • 1.9.2. Felt table with live dealer. In various embodiments a secondary player may participate in a game by sitting at a table and interacting with a casino representative. The table at which the secondary player sits may be different from the table the primary player sits at. Thus the game activities of the primary player may occur elsewhere from the location of the secondary player. However, the secondary player may store cash or chips at his table, and may indicate bets by placing chips at certain parts of the table. From this table, the secondary player may watch the action in the game of the primary player, e.g., using closed circuit television. Based on the outcome of the game played by the primary player, the secondary player may receive payments at his table. Thus, for example, the casino representative at the table of the secondary player may collect bets from the secondary player, and may pay winnings to the secondary player if the outcome of the game of the primary player is winning for the primary player. The table of the secondary player may appear similar to that of the primary player. For example, the table may have the same shape and surface markings. The secondary player may even sit at the same position with respect to his table as the primary player sits with respect to the primary player's table. The secondary player may enjoy a similar experience to that of the primary player, only, perhaps, without the cards, dice, or other game apparatus used at the table of the primary player. In various embodiments, the table of the secondary player may serve as a means for the secondary player to make bets, receive winnings, and possibly to view the game of the primary player.
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      •  In some embodiments, the secondary player uses the same table or gaming device as does the primary player. For example, the secondary player may place a bet beside the hand of the primary player. The secondary player may then receive payments based on the outcome of the game of the primary player.
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      • 1.9.3. Machine at the casino. In some embodiments, a secondary player may participate in a game using a machine or terminal configured to allow participation in a separate game. The terminal may include a coin slot, bill validator, credit card reader, and/or other means for accepting consideration. The terminal may include buttons, keys, roller balls, and/or other input devices that may be used by the secondary player for selecting a game in which to participate, for selecting bet amounts, for selecting bet types, and so on. The terminal may be in communication with the device that conducts the actual game. For example, the terminal of the secondary player may be in communication with a gaming device at which the primary player is playing. The terminal may thus receive from the device of the primary player an indication of games played by the primary player, amounts bet, outcomes received, and other pertinent information. The terminal of the secondary player may be in direct communication with the device of the primary player, or may be in communication with the casino server which, in turn, communicates with the device of the primary player. The terminal of the secondary player may also be in communication with sensors, detectors, and/or other monitoring devices at a game played by the primary player, such as at a blackjack game. For example, the terminal of the secondary player may receive feeds from cameras located at a blackjack game being played by the primary player. In various embodiments, a dealer or other casino representative may report information about a game of the primary player. For example, a dealer may input into keypad connected to the casino server that a primary player has been dealt an ace and a ten in a game of blackjack. Such information may subsequently be received at the terminal of the secondary player, and may be used in determining a payment for the secondary player. The terminal of the secondary player may be a mobile device, e.g., a mobile device as set forth in Nevada bill AB471.
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      •  In some embodiments, the terminal of the secondary player may be constructed or configured to look like a gaming device. Betting interfaces at the terminal may be designed to mimic or appear similar to those at the gaming device. Graphics shown on the housing or the screen may also be similar. However, the terminal may simply recreate and redisplay games and outcomes generated by the gaming device. The terminal may not, in various embodiments, generate games or outcomes of its own, e.g., using its own processor or locally stored algorithms. In various embodiments, the terminal may comprise a kiosk.
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      • 1.9.4. Casino desk. In various embodiments, a secondary player may visit a casino desk, casino cage, or other casino venue where bets may be placed in person. The secondary player may there select a game in which to participate. The secondary player may place a bet. The secondary player may receive some record of his bet. The record may be a paper receipt, for example. The record may include the name of the secondary player, the name of the primary player, the type of game, the time of the game, the machine or location at which the game was played, the amount of the bet, the terms of the bet (e.g., what outcomes constitute winning outcomes), and any other pertinent information. Upon resolution of the game, the secondary player may return to the desk and receive payment of any winnings.
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      • 1.9.5. How bets are entered. In various embodiments bet amounts and bet selections may be entered using buttons, keyboards, microphones, computer mice, joysticks, or any other input devices. A secondary player may also place bets and indicate bet amounts according to rules. Rules may include instructions that may be followed by a computer algorithm, the instructions indicating rules or conditions specifying when and how much to bet. By betting according to rules, the secondary player may save himself the effort of repeatedly indicating a desire to place a bet. Rules may include the following: (a) continue betting $1 on each new game until the secondary player provides an indication to stop; (b) continue betting $1 on each new game for the next 20 games; (c) bet $1 on the game following every win, and double the prior bet following every loss; (d) continue betting until a credit balance reaches either 0 or $100; and so on. In some embodiments, rules may be entered explicitly by the secondary player. In some embodiments, different sets of rules may be predefined. A secondary player need then only select one of the predefined sets of rules to have betting done automatically on his behalf according to the selected set of rules. In some embodiments, a set of rules indicates that the prior bet should be repeated. A secondary player may simply need to confirm each new bet before it is made. For example, for a first game, a secondary player may bet 5 coins on each of 7 pay lines of a slot machine game. For a second game, the secondary player may simply press a “repeat prior bet” button in order to once again bet 5 coins on each of 7 pay lines. Without pressing such a button, the process of entering the bet again might be time consuming. Further, the primary player may have continued on with the next game before the secondary player had time to enter the bet a second time. In various embodiments, a secondary player may specify a bet with reference to a prior bet. For example, the secondary player may indicate a desire to bet twice his prior bet, or to make the same bet he made two games ago. +
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        • 1.9.5.1. Layout of the betting screen and the graphical user interface. In various embodiments a secondary player may choose a bet type; choose a bet amount; follow the progress of a game; follow the progress of a primary player; view statistics related to a gaming device, table, dealer, primary player, casino, etc.; all using a betting interface on a display screen. The display screen may also function as a touch screen so that the secondary player may interact with the screen by touching it in certain locations. A first location of the screen may include a selection area. Shown in the selection area may be any number of attributes pertaining to a game. For example, a selection area may list a number of primary players. The secondary player may select one of the primary players to indicate that the secondary player would like to participate in the game of the selected primary player. The selection area may present a selection of: (a) primary players; (b) gaming devices; (c) times; (d) dates; (e) casinos; (f) game types (e.g., video poker, slot, etc); (g) dealers; (h) opponents; (i) game results (e.g., ranges of payouts provided by the game, such as games which paid 0-2 coins, games which paid 3-4 coins, games which paid 5-6 coins, etc); and so on. Possible selections may be presented as a menu, a list, a scroll bar, or any other presentation. The secondary player may go through various layers of selection until he has completely specified a game in which to participate. For example, the secondary player may first select a primary player, then a gaming device, then a time of a game. Each set of choices may be presented as a new menu.
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        •  A second location of the screen may include a betting area. In the betting area, the secondary player may indicate an amount to bet on a game. The secondary player may specify a number of outcomes to bet on, such as a number of pay lines to bet on, or a number of hands of video poker on which to bet. The secondary player may also specify an amount to bet on each pay line or each outcome. If different types of bets may be made (e.g., a main bet and an insurance bet in blackjack, or pass line and hard eight in craps), then the secondary player may specify which of such bets he wishes to make. A secondary player may specify bets to be made on the primary player. For example, the secondary player may specify a bet that the primary player will lose or will win, or may specify a bet that the primary player will win more than a certain amount.
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        •  A third location of the screen may include an area where information about a game is displayed. The area may allow the secondary player to follow the progress of the game. In this area, the secondary may watch as new symbols (e.g., cards in a card game or symbols on slot reels) arise, as new bets are made by the primary player and/or his opponent(s), as decisions are made by the primary player, as decisions are made by the dealer, as hidden symbols are revealed (e.g., as a dealer's down card is turned face up in the game of blackjack), as bets are collected (e.g., from the primary player), and as winnings are paid out (e.g., to the primary player). The third location of the screen may include live video, animations depicting a reenactment of the game, pre-recorded video of the game, pre-recorded video depicting a game similar to the game in which the secondary player is participating, or any other video depiction. The third location may include text descriptions of events in the game. For example, a text description may read, “Joe Smith has just been dealt a pair of kings.”
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        •  A fourth location of the screen may allow a secondary player to view statistics related to a gaming device, table, dealer, primary player, casino, etc. For example, the fourth location may show the number of times a primary player has won or lost in his last 100 games, a graph depicting the bankroll of the primary player over the last two hours, the number of times a particular gaming device has paid more than 20 coins in the last day, and so on. Statistics may be presented in any conceivable form, such as using tables, graphs, bar graphs, line graphs, pie charts, and so on.
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        •  A fifth location of the screen may allow a secondary player to communicate with the primary player, with a casino representative, with other secondary players, or with others. The fifth location may comprise a chat area, for example, where text conversations are tracked, and where different statements are labeled with the name of the originator of the statement.
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        •  A sixth location of the screen may allow the secondary player to follow his own progress. For example, the secondary player may see his account balance and statistics about his own wins or losses.
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        •  A seventh location of the screen may allow the secondary player to cash out a portion of his winnings and/or account balances.
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        •  An eighth location of the screen may allow the secondary player to summon a casino representative, e.g., to order food.
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        •  As will be appreciated, the locations described above may be overlapping. All locations need not have the same function at once, but may alternate. For example, at a first point in time, the screen may be occupied completely with video footage of a game. When the game finishes, the video footage may be replaced with statistics about the player. It will be further appreciated that there may be additional locations on the screen.
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      • 1.9.6. In order to participate in the games of a primary player, a secondary player may provide identifying information about himself. Identifying information may include a name, age, state of residence, nationality, driver's license number, social security number, and/or any other identifying information. The casino may use such identifying information in order to verify that the secondary player is authorized to place bets and/or to participate in games as a secondary player. For example, the casino may use identifying information to verify that a secondary player is over 21 years of age. The casino may only permit the secondary player to participate in games of the primary player if the secondary player is over 21 years of age. In various embodiments, a secondary player may be identified automatically by the casino. For example, the secondary player may seek to participate in a game while situated at a remote terminal or device. The remote terminal or device may be configured to check the identity of the secondary player prior to communicating with the casino. The terminal or device may only communicate with the casino, in some embodiments, if the secondary player is a particular player. Thus, the casino may automatically identify a secondary player by virtue of the terminal or device at which the secondary player is situated. If a terminal or device is configured only to communicate with the casino when a particular secondary player has identified himself to the terminal or device, then the casino can be assured that a particular secondary player is desirous of participating in games. The particular secondary player may be, for example, a particular secondary player that is authorized to participate in games. In some embodiments, a remote device or terminal may constitute a mobile device (e.g., a mobile device as set forth in Nevada bill AB471). The mobile device may be programmed to be used only by a particular secondary player. Therefore, if the secondary player is authorized to make bets, and the mobile device is configured to communicate with the casino only when the particular secondary player is using it, then the casino may assume that it is an authorized secondary player that is placing bets through the mobile device.
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    • 1.10. The secondary player bets on outcomes on which the primary player did not. In various embodiments, a secondary player may place bets on results or outcomes that were not bet on by the primary player. As will be appreciated, for a given game, there can be many possible outcomes, and many types of bets placed on the various outcomes. For example, in craps, many different bets can be placed in the same game, among them pass and don't pass. +
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      • 1.10.1. The secondary player bets on a pay-line that the primary player did not. In various embodiments, the secondary player may bet on a pay-line of a slot machine that was not bet on by the primary player. For example, a slot machine may include three pay-lines, e.g., lines 1, 2, and 3. The primary player may bet on pay-line 1. The secondary player may bet on pay-line 2 and/or pay-line 3. The secondary player may, in various embodiments, bet on pay-line 1 as well. In some embodiments, the secondary player is only allowed to bet on pay-lines that the primary player has not already bet on. Such embodiments may help prevent a secondary player from determining a game in which the primary player has achieved a winning pay-line, and then betting on the same pay-line. In some embodiments, a secondary player may bet on pay-lines that were not available to the primary player when he played. For example, the secondary player may bet on a custom pay-line consisting of the top two symbols on a first reel, and the bottom symbol on a second reel of a slot machine. In some embodiments, the secondary player may bet on a pay-line that was not even visible to the primary player during his play of the game. For example, a slot machine may only show one symbol on each reel in a viewing window. The symbol on each reel that is one position above the viewing window may not be visible. Nevertheless, the secondary player may have the opportunity to bet on a pay-line comprising the row of symbols one position above the viewing window. Similarly, the secondary player may bet on a pay-line comprising the row of symbols one position below the viewing window. In various embodiments, any other pay-line or outcome may be constructed using visible and non-visible symbols. For example, a pay-line may be constructed using some symbols that were visible, and some symbols that were not visible to the primary player.
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      • 1.10.2. In various embodiments, the secondary player may place bets on symbols that were never even shown to the primary player. Such symbols may have occurred, for example, well above the viewing window. In some embodiments, such symbols may be shown to the secondary player.
        • +
      • 1.10.3. Play a card game with unused cards. For example, in video poker, only the top 10 cards may be used during a game. The secondary player could play another game using cards from the bottom of the deck. In various embodiments, a secondary player may play a game using cards, symbols, or other indicia that were not revealed to the primary player. For example, a primary player may participate in a game of video poker. The primary player may use the top nine cards from a shuffled deck during the game (e.g., the primary player receives an initial deal of five cards, and subsequently draws four additional cards). However, in a standard 52-card deck, 43 cards would remain in the deck. The secondary player may play a new game using the 43 remaining cards. The secondary player may thus engage in a game for which no person yet knows the outcome. This may help to avoid situations where a secondary player can choose to participate in a game where he knows the outcome will be favorable to him. In various embodiments, a secondary player may participate in a new game using cards remaining after a game of blackjack, after a game of poker, after a game of casino war, or after any other game. In various embodiments, the secondary player may make his own decisions in the game, e.g., rather than relying upon decisions of the primary player. In various embodiments, a secondary player may use cards remaining in a deck for a game other than the game for which the deck was first used. For example, after a deck is used for a video poker game of the primary player, the secondary player may use the remaining cards in the deck for a game of blackjack.
        • +
      • 1.10.4. The secondary player bets on some function of the data from a game. In some embodiments, a secondary player may bet on some function or transformation of the outcomes, results, or other data used in a game played by a primary player. As used herein, the term “function” may refer to a process or procedure for relating any acceptable input to an output, such that there is only one output per unique input. The output and input may be numerical or non-numerical. As used herein, a “function of” an input may refer to the resultant output when the function is used to relate the input to the output. As used herein, the term “transformation” may refer to a process or procedure for relating any acceptable input to an output. +
          +
        • 1.10.4.1. An outcome is generated using a function of a random number used in generating an outcome in the primary game. Suppose a random number 10232 was used to generate an outcome in a game of a primary player. The random number +1 could be used, such that the number 10233 is used. This could yield a completely different outcome. Various games played at a casino utilize random number generators. For example, a slot machine may utilize a random number generator to choose a random number for each reel of the slot machine. Each random number is then used to determine the symbol that should be revealed by the corresponding reel. In various embodiments, a game played by a secondary player may use a new set of random numbers generated based on some function of the random numbers used in a game played by the primary player. For example, the random numbers used in the game played by the secondary player may consist of the random numbers used in the game played by the primary player with one added to each. Thus, {10245, 31189, 19320} may be transformed to {10246, 31190, 19321}. The new set of random numbers may be used as inputs to an algorithm (e.g., the same algorithm used in the game played by the primary player), to generate the symbols or outcomes of the game played by the secondary player. As will be appreciated, any function of the random numbers in the primary player's game may be used to come up with random numbers in the secondary player's game. For example, one may be subtracted from each random number, the order of the random numbers may be changed (e.g., so each random number now corresponds to different one of the reels), each random number may be multiplied by a factor, and so on.
          • +
        •  In various embodiments, seed numbers may be used in the generation of random numbers. Thus, in some embodiments, a seed number used in a game played by a primary player may be transformed according to some function (e.g., one may be added) in order to generate a seed to be used in the game played by the secondary player.
          • +
        •  In various embodiments, a game played by a primary player may result in a first outcome with a first associated payout. The game may be disguised by changing the first outcome to a second outcome with the same payout. Thus, the primary player may view the first outcome while he plays the game, but the secondary player may view the second outcome when he participates in the game. Monetarily, the primary player and the secondary player may have had the same experiences. In other words, given identical bets, both the primary player and the secondary player will have had the same payouts, in various embodiments. However, the primary player and the secondary player will have seen different representations of the game. For example, suppose a slot machine game includes several possible outcomes. Among the possible outcomes are “bar-bar-bar” with an associated payout of 10 coins, and “cherry-cherry-cherry”, also with an associated payout of 10 coins. The primary player may play the game and achieve the outcome “bar-bar-bar”. The secondary player may also participate in the game. When the game is presented to the secondary player, the secondary player may be shown an outcome of “cherry-cherry-cherry”.
          • +
        •  Thus, in various embodiments, a first outcome of a game may be generated for a primary player. The casino may determine what other outcomes have the same payout as the first outcome. From among the other outcomes, the casino may select one to present to a secondary player who has participated in the game.
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        •  In various embodiments the outcome presented to a secondary player may differ both in terms of the constituent symbols and in terms of the payout from the outcome that was seen by the primary player. However, over the course of two or more games, a secondary player may be presented with outcomes whose associated payouts sum to the same total as do the payouts associated with the outcomes presented to the primary player over the course of the same two or more games. For example, both a primary player and a secondary player may participate in the same two games. In the first game, the primary player may be presented with outcome A and receive an associated payout of 4 coins. For the first game, the secondary player may be presented with outcome C and receive an associated payout of 3 coins. In the second game, the primary player may be presented with outcome B and receive an associated payout of 6 coins. For the second game, the secondary player may be presented with outcome D and receive an associated payout of 7 coins. Thus, neither the primary and secondary players have been presented with different outcomes over the course of the two games. However, after two games, both have received the same total payouts, each having received 10 coins in total. In various embodiments, a secondary player may view what is essentially the same game that the primary player is playing. However, the game may be disguised by replacing symbols from the presentation to the primary player with new symbols for presentation to the secondary player. For example, a “cherry” when viewed by the primary player becomes a “dog” when viewed by the secondary player. In terms of underlying logic, however, the games may remain the same. For example, “cherry” may always map to “dog”, and likewise there may be a consistent function which maps the symbols shown to the primary player to the symbols shown to the secondary player. The pay tables on display for the primary and secondary players may exhibit a similar functional relationship. For example, suppose the primary player's pay table includes a line showing a payout of 15 for “cherry-cherry-cherry”. A corresponding line on the pay table for the secondary player may include a line showing a payout of 15 for “dog-dog-dog”. In various embodiments, other graphics may be altered. For example, a background coloration of the game viewed by the primary player may be blue, whereas the background coloration of the same game viewed by the secondary player may be green.
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        •  In various embodiments, a second game presented to the secondary player may be a different type of game from that presented to the primary player.
          • +
        •  However, an outcome may be chosen for presentation to the secondary player that has the same payout as an outcome that occurred in a game played by the primary player. For example, a primary player may be involved in a game of Casino War. The secondary player may view the outcomes of the games of the primary player, but disguised as the game of craps. For example, if the primary player wins a game of Casino War (e.g., by being dealt a card with a higher rank than the card dealt to the dealer), then the secondary player may be shown an animated sequence of dice rolling a seven during the first roll of the game (i.e., a winning outcome in craps). If, however, the primary player loses the game of Casino War, then the secondary player may be shown an animated sequence of dice rolling a two on the first roll of the game (i.e., a losing outcome in craps).
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        •  The various methods of disguising a game described herein may provide an advantage, in certain embodiments, of making it difficult for the secondary player to determine details about the original game in which he is participating. For example, this may make it difficult for the secondary player to vary his bets based on advanced knowledge about the outcome of the original game. The same random number may be used, but a different reel configuration. In various embodiments, a gaming device may store an internal table or function which maps random numbers to symbols or outcomes. For example, the random number 1293 may map to the symbol of “cherry” on reel 1 of a slot machine. In various embodiments, a game played by a secondary player may utilize the same random numbers used in a game played by a primary player. However, the game of the secondary player may include a different table or matching function between random numbers and symbols. Thus, for example, in the game played by the secondary player, the number 1293 may map to the symbol “bell” instead of “cherry”. Accordingly, using the same random numbers, the game of the secondary player may arrive at different symbols or outcomes than those that occurred in the game of the primary player. In various embodiments, a gaming device may store an internal table or function which maps random numbers to reel positions. For example, the random number 2451 may instruct a gaming device to stop reel 1 with position 12 visible in the viewing window of the gaming device. Each position on a reel may feature a symbol. For example, a reel may have ten positions, each position corresponding roughly to 36 degrees of arc of the circular reel. Thus, by instructing a gaming device to stop a reel at a certain position, a random number will also instruct the reel to display the symbol featured at the certain position. In various embodiments, the game played by the secondary player may utilize the same random numbers utilized by the game played by the primary player. However, the positions and/or ordering of one or more symbols may be changed. Thus, the same reel position in the game of the secondary player may corresponding to a different symbol than it did in the game of the primary player. Thus, using the same set of random numbers, the game of the secondary player may nevertheless result in different symbols or outcomes than does the game of the primary player.
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        • 1.10.4.2. What if all cherries were transformed into bars? A secondary player may bet on real outcomes, but with one aspect altered into another. In some embodiments, one or more symbols obtained in a game played by a primary player may be mapped to other symbols in a game played by a secondary player. For example, any “cherry” symbol in a game of a primary player may be transformed into a “bar” symbol in a game of a secondary player. Thus, if the primary player receives the outcome of “cherry-bell-cherry”, the secondary player will receive the outcome of “bar-bell-bar”. The pay table, between the two games, may remain the same. In embodiments where the pay table remains the same, it is possible for a winning outcome to be mapped to a losing outcome, and for a losing outcome to be mapped to a winning outcome. In some embodiments, a first card in one game is transformed into a second card in another game. For example, the two of hearts becomes the king of diamonds. In some embodiments, an entire outcome in a game of the primary player may be mapped to a different outcome in a game of the secondary player. For example, the outcome of “bell-lemon-plum” may map to “cherry-cherry-cherry”. In various embodiments, when one symbol in a game played by a primary player is mapped to another symbol in a game presented to a secondary player, the same mapping may also occur in the pay table. For example, suppose the symbol “lemon” in a game played by the primary player is mapped to the symbol “tree” in a game presented to the secondary player. If there is a line in the pay table of the primary player indicating a payout of 100 associated with the outcome “lemon-lemon-lemon”, then there may be a corresponding line in the pay table of the secondary player indicating a payout of 100 associated with the outcome “tree-tree-tree”.
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        • 1.10.4.3. A secondary player may bet on original deals of cards, but with 7s now wild. In some embodiments, symbols in a game played by the primary player can take new meaning in the game of the secondary player. For example, in a game of cards, any seven dealt in the game of the primary player may count as a wild card in the game of the secondary player. Thus, for example, the primary player may receive a final poker hand of Qs Qh Jd 3h 7s. The primary player may then be paid based on having a hand with a pair, jacks or better. The secondary player may be paid based on having a hand with three of a kind, since the 7s, as a wild card, may count as a queen.
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        • 1.10.4.4. A secondary player may bet on a blackjack hand occurring with poker, or vice versa. In various embodiments, the secondary player may use the same symbols or outcomes obtained by the primary player, but to play a different game. For example, the primary player may be engaged in a game of blackjack. The secondary player may use the cards received by the primary player to form a poker hand. Thus, if the primary player receives the 2s 7s 3s As and 6s, yielding 19 points in the game of blackjack, the secondary player may receive a flush (all spades) in a game of poker.
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        • 1.10.4.5. A secondary player may bet on shifted data. For instance, an outcome consists of the last two reels from one slot pull, and then the first reel of the next slot pull. Or a hand of poker consists of the last three cards from one hand and the first two cards from the next hand. In various embodiments, data, symbols, or outcomes from two or more games of a primary player may be combined to create a single game for the primary player. For example, three cards used in a first game of the primary player, and two cards used in a second game of the primary player may be combined to form a single hand of cards for a single game of the secondary player. Data used in consecutive games of the primary player may be treated as a stream of data frames, each frame including all the data from one game. For example, each frame may include the three symbols appearing on the pay-line of a slot machine. A new stream of data frames may be created by shifting the frame limits over (e.g., left or right) by some number of data points, e.g., by some number of symbols. Thus, for example, each frame in the new stream of data frames may include symbols from reels two and three followed by a symbol from reel one. In other words, new games have been created by using the last two symbols in a first game of the primary player and the first symbol in a second game of the primary player. Thus, by shifting data frames used in a sequence of games of a primary player, a new sequence of games may be generated for a secondary player.
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        • 1.10.4.6. A secondary player may bet on the same outcome, but with a different pay structure. For example, a secondary player may lose on a royal flush. In some embodiments, a secondary player may receive the same outcomes as does a primary player. However, the pay table that applies to the secondary player may differ from that which applies to the primary player. For example, in a game of video poker, the primary player may win 5 coins with a flush, but the secondary player may only win 2 coins.
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    • 1.11. A secondary player may bet on an aggregate outcome of a primary player. For example, a secondary player may bet that a primary player will be ahead or behind after an hour. In some embodiments, a secondary player may place a bet that depends on multiple games or outcomes of a primary player. For example, the secondary player may bet that the primary player will win the next three games in a row, or that the primary player will win the next game but lose the following game. The secondary player may bet that the winnings or losses of the primary player will satisfy one or more conditions after a designated period of time. The secondary player may bet that the winnings of the primary player will total more than a given amount in the next hour. The secondary player may bet that the losses of the primary player will exceed more than $1000 in the next 6 hours. The secondary player may bet that primary player will either lose more than $100 or will win more than $200 in the next 15 minutes. Winnings and losses may be net of each other (e.g., a $20 win and $10 loss may net to a $10 win) or may count separately (e.g., a winnings total is the sum of all amounts won regardless of bets lost). The secondary player may bet on any statistic pertaining to outcomes received by the primary player. For example, the secondary player may bet that the primary player will receive more than 10 payouts of more than 20 coins each in the next 25 minutes. The secondary player may bet that the primary player will achieve 4 full-houses in the next 50 games. In various embodiments, the secondary player may track the net winnings or net losses of the primary player. Thus, for example, if the primary player has lost $200 after an hour, the secondary player will also have lost $200. If the primary player has won $734, the secondary player will also have won $734. +
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      • 1.11.1. A secondary player may take the upside of a primary player, but not his downside. In some embodiments, the secondary player may make a payment or place a bet that entitles the secondary player to an amount equal to the primary player's winnings, if any, over a period of time, but does not obligate the secondary player for anything if the primary player has net losses. For example, if the primary player achieves winnings over the next hour of $50, the secondary player may also receive $50. However, if the primary player loses in the next hour, the secondary player does not owe anything beyond his initial bet or payment. In various embodiments, the secondary player may receive, or owe monies based on more complicated functions of the primary player's winnings and losses. For example, the secondary player may receive three times the primary player's winnings (if there are any) for the next hour, but may owe 1.5 times the primary player's losses if the there are losses.
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      • 1.11.2. In some embodiments, a secondary player may bet that a primary player will receive five payouts of over 20 coins.
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      +
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    • 1.12. A secondary player may bet the difference between what a primary player bet and what the primary player could have bet. A secondary player may complete a partial bet and thereby win only the extra payouts that resulted from the extra amount bet. In some embodiments, a secondary player may place a bet that a primary player could have made but did not. This includes completing a bet that the primary player made. The secondary player may, in this fashion, win any payments that a primary player would have won, beyond those the primary player actually did win, had the primary player made the bet. +
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      • 1.12.1. For example, many machines require three coins bet to win the jackpot. If a primary player bets only two coins, then a secondary player may bet the 3rd and then win the difference of what someone would win with three coins versus two coins bet. Various gaming devices include pay tables that are based on the number of coins bet. For example, if a player bets one coin and receives the outcome “bell-bell-bell”, then the player wins 100 coins. If, however, the player bets two coins and receives the same outcome, then the player wins 200 coins. Many gaming devices provide better payout odds for each incremental coin bet. Thus, in the prior example, if the player bets three coins and receives the outcome “bell-bell-bell”, then the player wins 400 coins. Thus, the incremental payout odds for the third coin bet are better than those for the second coin bet, at least with respect to “bell-bell-bell”. Accordingly, for example, if a primary player bets only two coins in a game, a secondary player may take advantage of the better incremental payout odds offered for the third coin bet by betting the third coin himself. If the outcome of “bell-bell-bell” occurs, the secondary player may thus receive the difference between the payout for three coins bet and the payout for two coins bet, i.e., the difference between 400 coins and 200 coins, equal to 200 coins.
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      •  In various embodiments, a secondary player may add to or complete a bet on a game made by a primary player so that the total bet of both the primary and secondary player would result in a higher set of payouts. The secondary player may receive any extra payouts associated with his bet. Thus, if the payout associated with the primary player's bet alone is X, and the payout associated with the primary player's bet plus the secondary player's bet is Y, then the primary player may receive X, and the secondary player may receive Y-X.
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      • 1.12.2. In craps, placing bets behind the bets of other people. In various embodiments, a primary player in a game of craps is given additional opportunities to bet during the course of a game. For example, when the primary player establishes a point for a pass line bet, he has the opportunity to place bets behind his pass line bet, called “odds bets”. The odds bets often have no house edge, and therefore are typically more advantageous to a player than almost any other bet in a casino. However, a player at a craps table often does not make an odds bet, or does not make the full amount of an odds bet that he is allowed. In various embodiments, a secondary player is allowed to make an odds bet that a primary player could have made. The secondary player may then be paid for the odds bet if the odds bet wins. Accordingly, the secondary player may enjoy the opportunity to make a bet at true odds, without the requirement of first making a disadvantageous pass line bet.
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      • 1.12.3. In various embodiments, a secondary player may make odds bets or may make partial bets such as betting the third coin at a slot machine, even if the primary player has already made such bets. The secondary player may nevertheless receive the incremental payouts associated with such bets. For example, the secondary player may bet a single coin which counts as the third coin bet at a slot machine. The secondary player may thus be eligible to win the difference in payouts between the payout for three coins bet and the payout for two coins bet.
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      +
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    • 1.13. Primary players might see who or how many people are betting on them. In various embodiments, a primary player may be made aware of a secondary player who is participating in the game of the primary player, or who subsequently participates in the game of the primary player. The primary player may receive a name, an image, and description of various attributes (e.g., age, occupation, area of residence, etc.) of the secondary player. The primary player may also receive an indication of the performance of the secondary player while participating in the games of the primary player. For example, the primary player may see how much the secondary has won or lost, what types of bets he has made, how many games he has participated in, for how long he has been participating in the games of the primary player, and so on. The primary player may derive a measure of satisfaction or gratification from the participation of secondary players. For example, a primary player may feel proud that a large number of secondary players have participated in his games. He may feel proud to have won money for them. In various embodiments, the primary player may have the opportunity to communicate with a secondary player. For example, the casino server may provide the primary player with contact information for a secondary player.
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    •  In various embodiments, a primary player may be compensated based on participation by secondary players in the games of the primary players. The primary player may be compensated per secondary player and per game. For example, the primary player may receive 0.5 cents per secondary player per game. Thus, if three secondary players each participate in two games of the primary player, the primary player may receive 0.5 cents×3 secondary players×2 games=3 cents. Thus, the primary player benefits by having more secondary players and by increasing the number of games in which each secondary player participates. The primary player may be compensated with a percentage of the bets made by secondary players participating in his games. The primary player may be compensated with some percentage of expected winnings to be derived from the bets of secondary players participating in the games of the primary player.
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    •  A primary player may thus be encouraged to convey some value to secondary player so as to attract secondary players to participating in his games. The primary player may convey value by employing good strategy, for example. The primary player may also attempt to provide entertainment, e.g., by telling jokes or by making commentary about his games.
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    •  In various embodiments, the games of a primary player, and/or data from the games of a primary player may be made available for participation and/or for viewing by interested secondary players. Data from the games of a primary player may be made available on an ongoing, continuous, and/or real-time basis. Secondary players may, at their leisure or pleasure, view or participate in the games. As such, data from the games of the primary player may be broadcast or transmitted in an analogous fashion to programs on a television or radio show, or analogously to periodically updated Web pages. Secondary players may tune in or out as desired. Each primary player may constitute a “channel” or “station”. A secondary player may, for example, view a list of primary players just as he would a list of television stations. The secondary player may then decide which primary player or “station” he wants to participate with. When selecting a primary player, the secondary player may also have the opportunity to review data about historical games played by the primary player. For example, the secondary player may be able to review the primary player's wins and losses over the prior 20 games.
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    •  In various embodiments, a casino may select from a subset of available primary players to choose primary players for whose games data will be made available to secondary players. In some embodiments, a casino may serve as a “disc jockey” by choosing which primary players will have their data made available to others. The disc jockeys may be humans (e.g., casino employees), or may be computer algorithms which automatically select certain primary players based, for example, upon a defined set of rules. The disc jockey or jockeys may select primary players based on any number of factors. A primary player may be selected based on: (a) recent results (e.g., recent wins or high payouts); (b) based on long term results (e.g., long term profits); (c) based on skill at playing a game (e.g., based on his use of basic strategy in blackjack); (d) based on his celebrity status (e.g., based on whether his name has been published in any newspaper in the past year); (e) based on a history of being favored by secondary players; and so on. At any given time, a disc jockey may decide to stop making data available from certain primary players, and/or to commence making data available from other primary players. For example, a disc jockey may decide that a primary player has hit a string of losses and therefore would not be of interest to any secondary player. The disc jockey may accordingly stop making data from the primary player available. For example, a disc jockey may decide that a given primary player has just won a large payout and therefore would be of interest to secondary players. Accordingly, the disc jockey may commence making data from the primary player available.
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    •  In various embodiments, the data about the games of a primary player may be made available across one or more casinos. A first casino may broadcast or transmit data from the games of one or more primary players to a second casino. The broadcast may occur via the radio or television spectrums, via mobile wireless frequencies, via microwave frequencies, via metal or optical cables, or via any other means. Secondary players in one or more of the casinos may view the data (e.g., may view games that are reconstructed based on the data). The data may be made available on the Internet, on one or more radio stations, on television, on interactive television, and so on. For example, a secondary player may visit a web page on which are listed names or identifiers for one or more primary players. The secondary player may click on an identifier in order to view data about games of the corresponding primary player. In some embodiments, a secondary player may set the channel on his television to a particular channel whereby identifiers for various primary players are listed on a menu. The secondary player may select an identifier from the menu (e.g., using a remote control) and may thereby call up on the television screen further data pertaining to the games of the primary player.
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    •  In various embodiments, data about the game of a primary player may originate in a first casino. For example, the primary player may play the game in the first casino. Data about the game may be transmitted to a second casino. From the second casino (e.g., from a terminal located in the second casino), a secondary player may participate in the game. The second casino may thereby derive revenue from the secondary player by using data originating from the first casino. In various embodiments, the first casino and the second casino may split revenue, win, profits, theoretical win, or any other financial gain that has been derived from the use of the data at the secondary casino. For example, 50% of the theoretical win from a bet by the secondary player (i.e., the casino advantage on the bet multiplied by the amount bet by the secondary player) may be given to the first casino by the second casino. The financial gain may be split with one percentage going to the first casino and another percentage going to the second casino. In some embodiments, the second casino pays a flat fee to the first casino for the use of the data. The flat fee may cover all possible uses of the data (i.e., uses of the data in as many games as the second casino desires) or may cover a single use of the data (i.e., in one game). In some embodiments, the second casino keeps a fixed financial gain from the use of the data and pays any remaining financial gain to the first casino. For example, the second casino may keep 2 cents of theoretical win per game in which the data is used, and give the remaining portion of the theoretical win to the first casino. As will be appreciate, financial gain may be split between the first and second casinos in many other ways.
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    • 1.14. A secondary player watches games in progress. The secondary player may have various ways of watching or following the game or games in which he is participating. Following a game may include receiving information about the outcome or result of the game, receiving information about symbols or indicia that have arisen in the game (e.g., cards that have been dealt), receiving information about outcomes or results received by a dealer or opposing players, receiving information about decisions that are available or have been made in a game (e.g., decisions by a primary player to hit or stand), receiving information about player mannerisms in a game (e.g., facial expressions of a primary player or his opponents), information about amounts bet on a game (e.g., amounts bet by the primary player or the secondary player), information about amounts won on a game (e.g., amounts won by the primary player or the secondary player); and so on. +
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      • 1.14.1. A split screen allows the secondary player to see all the roulette wheels in the casino at once. In various embodiments, the secondary player may follow the progress of one or more games in which he participates using one or more display screens. Display screens may include cathode ray tubes, flat panel displays, plasma displays, liquid crystal displays, diode displays, light-emitting diode displays, organic light-emitting diode displays, projection displays, rear projection displays, front projection displays, digital light processing (DLP) displays, surface-conduction electron-emitter (SED) displays, electronic ink displays (e.g., E-Ink Corp's display technology), holographic displays, and so on. A secondary player may follow the progress of a game using a device such as a Blackberry®, iPod®, personal digital assistant, mobile phone, laptop computer, camera, personal computer, television, electronic book (eBook) and so on. A single screen may contain information about a single game in which the secondary player participates. A single screen may also contain information about multiple games in which the secondary player participates. The display screen may display information about one game on one part of the screen, and about another game on another part of the screen. For example, the screen may be divided into four quadrants, each quadrant showing information about a different game that the secondary player is participating in. A secondary player participating in two games may view a first of the two games on one display screen, and a second of the two games on another display screen. A secondary player may thus watch or follow the progress of games using multiple displays screens.
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      • 1.14.2. Views come from overhead cameras. In various embodiments, a secondary player may follow the progress of a game in which he participates using video and/or audio feeds from the proximity of the game. For example, a camera may capture the progress of a blackjack game played by a primary player. By watching a video feed, the secondary player may see the cards dealt in the game, the decisions made by the primary player, the decisions made by the dealer, and the result of the game (e.g., win for the primary player, win for the dealer, blackjack for the primary player, tie). In various embodiments, video or audio feeds may be live, delayed, or may be stored and played back at a later time for the secondary player.
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      • 1.14.3. Data is piped electronically from the slot machines. In various embodiments, data may be captured from a gaming device or live table game, encoded into electronic form, and transmitted to a display device, speaker, or other output device used to present the data to the secondary player. The output devices may decode the electronic data and present it in a sensible form for human viewing. The presentation may include a text description of occurrences in the game. For example, text may read, “At 9:02 pm, slot machine number 1423 achieved the outcome of bar-bar-bar. Congratulations, you have won 20 coins.” The presentation may include a reconstruction of the game. For example, the game may be reconstructed using animated renditions of the game. For example, an animated slot machine may show animated reels spinning and stopping to show the outcome achieved by the actual slot machine which generated the game the secondary player participated in. In another example, an animated dealer using animated cards may be used to reconstruct a live table game of blackjack. In various embodiments, a computer synthesized voice may report to the secondary player occurrences in a game in which the secondary player participates.
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      • 1.14.4. Only active machines are shown to the secondary player. For example, the machine currently resolving into an outcome is shown. In various embodiments, a secondary player may participate in several games at once. The games may not necessarily all proceed at the same pace. For example, one game may finish while another is still in progress. In some embodiments, games or aspects of games may be presented to the secondary player only as important or relevant events occur in the game. For example, when a first game finishes, all or part of the game may be presented to the secondary player. For example, when the first game finishes, a depiction or an image of the final outcome (e.g., the final cards in the primary player's hand) may be flashed onto a display screen viewed by the secondary player. The image pertaining to the first game may be removed when a second game finishes. When the second game finishes, a depiction or image of the final outcome in the second game may be flashed onto the display screen. In this way, the secondary player need only view aspects of a game that are most relevant, most important, or most interesting to him. When a game is in an uninteresting stage (e.g., when the reels of a slot machine are spinning), the secondary player may view information about other games. Information that may be deemed worthy of showing to a secondary player may include: information about a decision that is to be made in a game (e.g., the primary player has received an initial hand of blackjack and must now decide to hit or stand); information about a decision that has been made in a game (e.g., the primary player has decided to hit); information about a new card, symbol, or other indicium obtained in a game (e.g., a new reel of the slot machine has stopped, showing a new symbol for the pay-line); information about a final outcome of a game; information about entry into a bonus round or bonus game (e.g., the primary player has just won the opportunity to play a bonus round); information about a symbol, card, or other indicium obtained by a dealer or by an opponent of the primary player; information about an amount bet (e.g., by the primary player or by the secondary player); and information about an amount won (e.g., by the primary player or by the secondary player).
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    • 1.15. The secondary player is alerted when his favorite primary player sits down. In various embodiments, a secondary player may prefer to participate in the games of particular primary players, in the games of particular gaming devices, in games played at particular gaming tables, in games played with particular dealers, and so on. A secondary player may explicitly record his preferences, e.g., by informing the casino. In some embodiments, the secondary player may be assumed to have certain preferences, based, for example, on a history of participating in the games of a particular primary player. For example, if a secondary player has participated in 300 games of a particular primary player, the secondary player may be assumed to prefer or to enjoy participating in the games of the primary player. In some embodiments, the casino may inform a secondary player when a game in which the secondary player may be interested in participating is or will be in progress. For example, suppose that the secondary player has indicated that he likes to participate in games played by primary player Joe Smith. When Joe Smith sits down at a gaming device and begins playing, the casino may detect the presence of Joe Smith (e.g., by means of a player tracking card inserted by Joe Smith) and may then alert the secondary player that Joe Smith has begun playing. The secondary player may then place bets on the games of Joe Smith. The casino may alert the secondary player using any number of communication means. A casino representative may call the secondary player, may send a text or email message to the secondary player, may page the secondary player, may find the secondary player in person, and so on. +
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      • 1.15.1. A secondary player is alerted as to the presence of a primary player who has done well for him. A secondary player may be alerted when a primary player commences play if the secondary player has had favorable results in the past when participating in the games of the primary player. Favorable past results may mean that: the secondary player is ahead in terms of winnings based on all prior participation in the games of the primary player; the secondary player was ahead in the most recent time period during which he participated in the games of the primary player; the secondary player won more than a predetermined amount of money (e.g., more than $500) in a single session while participating in the games of the primary player; the secondary player won a jackpot or other high-paying outcome while participating in the games of the primary player; the secondary player was ahead in the most recent X number of games when participating in the games of the primary player; or any other measure of performance while participating in the games of the primary player.
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      • 1.15.2. A secondary player is alerted as to the presence of a primary player with good statistics. A secondary player may be alerted when a primary player commences play if the primary player has a certain historical record or certain statistics that may be of interest to the secondary player. The historical record may include a record of: having won one or more jackpots or other high-paying outcomes; having won money for other secondary players; having achieved profitable sessions in the most recent gaming session or in any prior gaming session; having achieved a profit during some prior time period (e.g., during the past six months); and so on. A secondary player may also be alerted if a primary player that has some measure of popularity commences play. For example, primary players may be rated, e.g., by one or more secondary players, based on the secondary players' degree of satisfaction with, or other feelings towards the primary player. A primary player may, for example, be rated highly if he has won money for many secondary players in the past. Thus, for example, if a highly rated primary player commences play, a secondary player may be alerted and may be given the opportunity to participate in the games of the primary player.
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      • 1.15.3. A secondary player is alerted when good machine is taken. In various embodiments, a secondary player may be alerted if play commences at a gaming device or table that is or may be of interest to the secondary player. The gaming device may be of interest due to a number of factors, among them: the secondary player has won a jackpot or other high-paying outcome while participating in games of the gaming device; the secondary player has had profitable sessions at the gaming device; the secondary player has had recent profitable sessions at the gaming device; the secondary player has had profitable sessions at another gaming device similar to the gaming device (e.g., at a gaming device of the same type or from the same manufacturer); one or more recent games at the gaming device have resulted in jackpots or high-paying outcomes; recent games at the gaming device have resulted in profits for the player or players at the gaming device; the gaming device is highly rated (e.g., by secondary players); and so on.
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    • 1.16. A secondary player pays a fee to participate in games. In various embodiments, a secondary player may be required to pay in order to participate in the game of a primary player. The amount paid may be based on the status, rating, historical results, or requests of the primary player. For example, if the primary player is a well-known celebrity, the fees required of a secondary player may be higher than if the primary player were a lesser-known celebrity. If the primary player has had highly favorable historical results (e.g., has made large profits in the past), then the fees required of the secondary player may be higher than if the primary player did not have such favorable historical results. In various embodiments, the primary player may also declare a fee required for secondary players to participate in his games. A portion of such fee paid by a secondary player may be paid to the primary player.
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    • 1.17. Rules for using old data in a game with real money on the line. There is opportunity of misconduct since the player and/or the casino may know the data already. The use of historical games, outcomes, and other data related to a game presents an opportunity for an advantage by any party with knowledge of a data. For example, a casino might provide secondary players with the opportunity to participate only in games whose results the casino knows are losing for the player (and therefore winning for the casino). In another example, a secondary player may have already participated in a particular game (e.g., as a primary player) and may therefore know the outcome of the game in advance. The secondary player may thus make a large bet on the game if he knows the game will result in a winning outcome for him, and will make a small bet or no bet on the game if he knows the game will result in a losing outcome for him. +
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      • 1.17.1. Before the original data is generated, it may be tagged for reuse at a particular date and time in the future. That way, the casino may be afforded no discretion as to whether or not to use the data. In various embodiments, before a particular game is played for the first time, a casino designates a time, date, location, and/or any other situation or circumstance under which the game will be made available for participation by others. The situation under which the game will be made available may be chosen randomly, according to some algorithm, or in any other fashion. Once the situation or circumstances for future participation in the game have been established, the game may commence for the first time. In this way, the casino has established future circumstances under which the game may be made available for participation by others (e.g., by secondary players) before the casino is aware of the outcome of the game. The casino cannot, therefore, decide not to allow participation in the game if the game turns out to result in a jackpot for the player. In various embodiments, the establishment of future circumstances under which a game will be available for participation by others is binding upon the casino. Regulators may keep track of when games must be made available for future participation, and may verify that the games have in fact been made available. In various embodiments, players or other parties may not necessarily know the circumstances under which a game must be made available in the future. In this way, players will not be able to selectively choose games to participate in based on advanced knowledge of the outcomes. In various embodiments, a record is stored, the record including information about a game and information about circumstances under which the game is to be made available in the future for participation by others.
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      • 1.17.2. Data may be put in a queue. When it reaches the front of the queue, it must be used. In various embodiments, when a game is played or generated for the first time, data or information about the game is placed in a queue. Games from the queue are then made available for participation by secondary players based on a first-in-first-out model. Thus, a game becomes available for participation based on a relatively straightforward scheduling algorithm, and there is little discretion on the part of the casino as to when the game will become available for participation. In various embodiments, other scheduling algorithms may be used. For example, games are made available according to a last-in-first-out scheduling algorithm. Any other scheduling algorithm may be used, particularly if the casino has little control over the schedule once the outcome of a game is known.
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      • 1.17.3. One set of data may be used after and only after another set of data. In various embodiments, data about a second game may be associated with data about a first game. The association may dictate that the data about the second game may be used to allow participation in the second game by a secondary player when, and only when, the data about the first game has been used. Similarly, data about a third game may be associated with the data about the second game, such that the data about the third game may be used when, and only when, the data about the second game has been used. In this way, through a chain of association, data about different games can be made available in sequence, allowing the secondary player to participate in a sequence of games. Data about different games may be associated in many ways. For example, data about a first game and a second game can be stored in locations with sequential addresses in a semiconductor memory. The casino may access the locations in the memory sequentially by address, and thereby make available data about the first game and data about the second game in sequence. In some embodiments, data about a given game may be associated with an index. The index may be a numerical index using integer numbers, for example. With such an indexing scheme, data about a game associated with index 235, for example, would be made available once data about a game associated with index 234 had already been made available. In some embodiments, the index may be a time. The time may represent a time during which the associated data was originally generated, or a time when the data should be made available again, for example. For instance, when the time associated with a particular set of data actually comes to match the current time, the particular set of data may be made available so that a secondary player might participate in a game generated using the data.
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      • 1.17.4. The time, date, and/or the machine that generated the data may be chosen at random. In various embodiments, a game that is made available for participation by a secondary player is selected at random using one or more randomly chosen variables or parameters. For example, a time and/or date may be chosen at random. Once a time and date have been chosen, for example, a game played at that time and date may be made available for participation by the secondary player. A gaming device, player, dealer, casino, location, and type of game may also constitute parameters that are chosen at random. In various embodiments, several parameters must be chosen at once in order to narrow down the universe of games to one particular game. For example, to determine a unique game, a time, date, and machine number may be required. In various embodiments, the parameters may be chosen by the secondary player, by the casino, or by third parties, such as regulators. Parameters may, in various embodiments, be chosen after the game has been played for the first time.
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      • 1.17.5. The secondary player may choose the time and/or machine. In various embodiments, a secondary player may choose the time, date, machine, or other parameter used to select a game. The choice may not necessarily by random.
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      • 1.17.6. Regulators may choose the time and/or machine. In various embodiments, a third party, such as a gaming regulator, may select a game that will be made available for participation by a secondary player. The third party may, in particular, have no stake in the outcome of the game. Therefore the third party may not be biased towards selecting a game that is winning for the secondary player or winning for the casino. The regulator or other third party may not necessarily select the game directly. Rather the third party may select one or more parameters (e.g., a time, date, machine number) that may be used to select a game that meets the selected parameters.
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      • 1.17.7. A player who had his player tacking card in a gaming device when the data was originally generated may be prevented from playing a game based on that data. In various embodiments, the casino may verify that the secondary player was not present for a game when it was originally played and/or had no knowledge of the result of the game. The casino may verify that the player was not staying at the casino's hotel during the day or time when the game was played. For example, the casino may check records of who had checked into its hotel on the day of the game. The casino may check to see whether the player made any bets at the casino on the day of the game. For example, the casino may check to see whether the player had a player tracking card inserted into a gaming device, or otherwise on record, for the day of the game. It will be understood that the casino may verify the presence of the player not just during a particular day, but during longer or shorter time periods as well. For example, the casino may verify that there is no record of a player's presence during an entire 5 day period surrounding the day of the game. A casino may verify that a player was not in the same city where the game was played at the time the game was played. For example, the casino may verify that there is no record of the player at any other casino affiliated with the casino (e.g., under the same ownership as the casino) during the day of the game. The casino may use any practicable means to verify that the player had no knowledge of the game or the outcome of the game.
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      • 1.17.8. Disallowing variation of bet size. In various embodiments, a secondary player may be prevented from varying the sizes of his bets over the course of a gaming session. In particular, the secondary player may be prevented from varying his bet sizes if he is participating in games that were first played in the past. The secondary player may thereby be prevented from varying his bet sizes based on advanced knowledge of the outcomes of the game. For example, the secondary player may be prevented from making larger bets when he knows the outcome of a game will be favorable, and a small bet when he knows the outcome of a game will be unfavorable.
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      • 1.17.9. Bet limits on game. In various embodiments, limits may be placed on the size of bets placed on games that have already been generated or played. For example, a secondary player may be permitted to bet no more than $1 on a game that has been played in the past. In this way, the casino's losses will be limited even if the secondary player has knowledge of the outcome of the game. In some embodiments, the total amount of bets placed on a game may be limited. For example, bets placed by all secondary players participating in a particular game may be limited to totaling less than $5.
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      • 1.17.10. Limits on winnings. In various embodiments, potential winnings or payouts for a game may be capped. For example, if the payout for an outcome of “bell-bell-bell” in an original game was 2000 coins, the potential payout for the same game may be reduced to 500 coins when a secondary player is participating in the game. This may limit the potential losses to a casino for a secondary player that has knowledge of the outcome of a game.
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      • 1.17.11. Disguising a game. In various embodiments, one or more aspects of a game may be disguised before a secondary player is allowed to participate in the game. Thus a secondary player who had previously participated in the game may still fail to recognize the game and to bet accordingly. A game may be disguised in a number of ways. One or more graphics of the game may be changed to appear differently. For example, a “cherry” symbol may appear in a different shade of red or with three cherries on a stem rather than two. In some embodiments, new symbols are substituted in for old symbols. For example, rather than “cherry” symbols, a game may use “blueberry” symbols. However, outcomes containing blueberries may result in the same winnings as did outcomes with cherry symbols in the original game. In some embodiments, sound effects are changed or disguised. For example the background music in the disguised game may be different from that in the original game. In some embodiments, the animation or video sequences may be altered. For example, reels of a gaming device may appear to spin faster or slower, to appear jerkier or less jerky, etc., than they did in the original game. For live games, features of one or more players may be hidden or disguised. For example the face of a dealer at a live game may be blurred out in footage of the game. In some embodiments, a new face may be super-imposed over the old face of a dealer or player so as to heighten the effect of the disguising. As will be appreciated, there are many other possible ways of disguising a game so that its outcome is not predictable to even a player who has knowledge of the original game. As described elsewhere in this document, a game may be disguised by using a different game skin while maintaining the same underlying events, outcomes, logic, etc. In some embodiments, a game may be generated and presented using at least two steps. In a first step, the results of one or more random events are determined, leading to the determination of a final outcome and a final payout for the game. In the second step, data about the results of the random event(s), the final outcome, and the final payout are used to create a graphical presentation for the player. For example, once it is determined that a player will receive an outcome consisting of three like symbols, with an associated payout of 20 coins, such data may be fed into the second step. In the second step, a graphical rendering of slot machine reels may be created, with such rendering showing the reels spinning and finally landing on an outcome with three like symbols. Further the graphical rendering may include a flashing message that says, “Congratulations, you won 20 coins!” It will be appreciated that the first step may be performed by a first device, processor, algorithm or set of algorithms, and that the second step may be performed by a second device, processor, algorithm, or set of algorithms. Accordingly, the second device, processor, algorithm, or set of algorithms may be removed and replaced with a third device, processor, algorithm, or set of algorithms. This third device, processor, algorithm, or set of algorithms may receive the same set of data from the first step as did the second device, processor, algorithm, or set of algorithms. However, the third device, processor, algorithm, or set of algorithms may perform the second step in a different fashion. The third device, processor, algorithm, or set of algorithms may thereby generated a different set of graphics, graphical renderings, or other presentation formats than did the second device, processor, algorithm, or set of algorithms. Thus, the underlying structure of the game has remained the same, but it has been presented using a different skin.
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    • 1.18. Choosing aspects of a game. In various embodiments, a secondary player may choose a game in which to participate based on one or more attributes of the game or associated with the game. The secondary player may indirectly choose the game by first choosing an attribute, and then having the opportunity to participate in one or more games having the chosen attribute. Various attributes may be especially meaningful to a secondary player and thus a secondary player may prefer to play games having those attributes. In various embodiments, the casino may select for the secondary player a game with an attribute that is anticipated to be meaningful for the secondary player. In various embodiments, the casino may provide the secondary player with the ability to search for a game based on one or more attributes of the game. +
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      • 1.18.1. Choose a special date. In various embodiments, a secondary player may find a particular date to be meaningful. Thus, the secondary player may select a game that was played on the date. If the casino knows a date to be meaningful for the secondary player, then the casino may select for the player a game played on that date. +
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        • 1.18.1.1. Choose the secondary player's birthday. A meaningful date for a secondary player may be a birthday. The birthday may be the birthday of the secondary player, of a relative of the secondary player's, of a pet of the secondary player's, of a friend of the secondary player's and so on. The secondary player may indicate to the casino that such a date is meaningful to the secondary player. The casino may accordingly select a game for the secondary player that was played on the date. The casino may also have a record of the secondary player's birthday based on information already provided to the casino by the secondary player. For example, the secondary player may have provided the casino with his date of birth when signing up for a player tracking card, or when taking a loan from the casino. The casino may then select, without request from the secondary player, a game that was first played on the birthday of the secondary player.
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        • 1.18.1.2. Choose a date on which a big jackpot was won. In various embodiments, a secondary player may wish to play a game that was first played on the date that a large payout, such as a jackpot, was won. This may give the secondary player the opportunity to participate in the game in which the jackpot was won. The secondary player may indicate to the casino a desire to play a game that was first played on the day of a big jackpot. The casino may then allow the secondary player to participate in one or more games played on the day of the jackpot. The secondary player may not himself know the date when a big jackpot was won. Thus, the secondary player may request that he be allowed to participate in games from the same date as the date that the last big jackpot was won.
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        • 1.18.1.3. Choose a date when the progressive was still big. The secondary player may have a shot at the large progressive. In various embodiments, a secondary player may wish to have the opportunity to win a large progressive jackpot. As is well known, the size of a progressive jackpot may vary over time. In general, as time passes without a progressive jackpot being won, the progressive jackpot becomes larger. The current size of a progressive jackpot may not be large enough to satisfy the desires of a secondary player. Therefore, the secondary player may wish to participate in a historical game from a time that the progressive jackpot was larger. Accordingly, the secondary player may request to participate in a game that was first played at a time the progressive jackpot was in excess of a certain threshold. The casino may, accordingly, allow the secondary player to participate in such a game.
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      • 1.18.2. Choose a gaming device. In various embodiments, a secondary player may search for a gaming device having desired attributes or characteristics. Upon finding a gaming device with desired attributes or characteristics, the secondary player may choose to participate in games played at the gaming device. The secondary player may search for a gamine device using a search form. In the search form, the player may select from among various characteristics of a gaming device, some of which are described below. +
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        • 1.18.2.1. A secondary player may search for a gaming device based on the historical results of the gaming device. For example, a secondary player may search for a gaming device with one or more of the following characteristics: (a) the gaming device has paid more than X amount of money in the last Y amount of time; (b) the gaming device has paid more than X amount of money in general; (c) the gaming device has paid X amount of in excess of what it has taken in, in the last Y amount of time; (d) the gaming device has made X amount in excess of what it has taken in, in general; (e) the gaming device has generated winning games for players in X % of its games in the last Y period of time; (f) the gaming device has generated winning games for players in X % of its games out of the last Y games; (g) the gaming device generated winning games for players in X of its most recent games; (h) the gaming device has paid X payouts greater than Y in the last Z games; (i) the gaming device has paid X payouts greater than Y; (j) the gaming device has paid a jackpot in the last X days (or other time period); (k) the gaming device has paid X jackpots in general; (l) the gaming device has entered X number of bonus rounds in his last Y games; (m) the gaming device has entered X number of bonus rounds ever.
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        • 1.18.2.2. A secondary player may search for a gaming device based on the type of game or based on a characteristic of a game played at the gaming device. A secondary player may search for a gaming device with one or more of the following attributes: (a) the gaming device uses mechanical reels; (b) the gaming device uses video reels; (c) the gaming device has three reels; (d) the gaming device has five reels; (e) the gaming device has X number of reels; (f) the gaming device accepts a particular denomination of bets (e.g., penny, nickel, quarter, dollar); (g) the gaming device has X number of pay-lines; (h) the gaming device has 1 pay-line; (i) the gaming device has 3 pay-lines; (j) the gaming device has more than 1 pay-line; (k) the gaming device allows multiple bets per pay-line; (l) the gaming device is made by a particular manufacturer; (m) the gaming device or a game at the gaming device was introduced in the last X years (e.g., the game is a new game); (n) the gaming device has a particular theme (e.g., I Love Lucy, Regis Philbin); (o) the gaming device features a slot game; (p) the gaming device features a video poker game; (q) the gaming device features video blackjack; (r) the gaming device is part of a particular cluster of gaming devices (e.g., a cluster of gaming devices where an outcome at one gaming device may influence an outcome at another gaming device in the cluster); and so on.
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        • 1.18.2.3. A secondary player may search for a gaming device based on one or more payouts that may be provided by the gaming device. Such payouts may be contingent on a primary player of the gaming device obtaining a particular outcome at the gaming device. A secondary player may search for a gaming device that has a top payout of over X times a bet, that has a payout of over X amount, and/or that has at least X payouts over Y amount. A secondary player may search for a gaming device that has more than X outcomes that are winning and/or a gaming device that has more than X outcomes that pay more than Y. A secondary player may search for a gaming device that has a particular or a particular range of payout frequency. For example, a secondary player may search for a gaming device that pays, on average, between once ever five games and once every seven games.
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      • 1.18.3. Choose a primary player. In various embodiments, a secondary player may search for a primary player having desired attributes or characteristics. Upon finding a primary player with desired attributes or characteristics, the secondary player may choose to participate in games of the primary player. The secondary player may search for a primary player using a search form. In the search form, the player may select from among various characteristics of the primary player, some of which are described below. For example, the secondary player may enter an age or age range desired in a primary player. The secondary player may also select a characteristic of a primary player from a menu. For example, the secondary player may select one of fifty states from a menu, the state indicating a desired residence location for a primary player. As will be appreciated, a secondary player may search for a primary player in many other ways. For example, a secondary player may communicate to a casino representative (e.g., via text message) a description of a primary player. The casino representative may then check records of people currently checked into its hotel or currently playing at gaming devices (e.g., with tracking cards inserted), and may attempt to locate a person matching the description provided by the secondary player. In some embodiments, a secondary player may seek a particular and unique individual, i.e., the secondary player may submit a description that can only be satisfied by one person in the world. For example, the secondary player may submit a name. In some embodiments, the secondary player may submit a description that may be satisfied by any one or a plurality of primary players. The secondary player need not have a particular individual in mind. +
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        • 1.18.3.1. A secondary player may search for a primary player based on the historical results of the primary player. For example, a secondary player may search for a primary player with one or more of the following characteristics: (a) the primary player has won more than X amount of money in the last Y amount of time; (b) the primary player has won more than X amount of money in general; (c) the primary player has made X amount of profits in the last Y amount of time; (d) the primary player has made X amount of profits in general; (e) the primary player has won X % of his games in the last Y period of time; (f) the primary player has won X % of his games out of the last Y games; (g) the primary player won X of his most recent games; (h) the primary player has won X payouts greater than Y in the last Z games; (i) the primary player has won X payouts greater than Y; (j) the primary player has won a jackpot in the last X days (or other time period); (k) the primary player has won x jackpots in general; (l) the primary player has used optimal strategy in his last X games; (m) the primary player has used good or expert level strategy in his last X games; (n) the primary player has entered X number of bonus rounds in his last Y games; (o) the primary player has entered X number of bonus rounds ever.
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        • 1.18.3.2. A secondary player may search for a primary player based on a historical relationship between the primary player and the secondary player. The secondary player may search for a primary player in whose game or games the secondary player has previously participated. The secondary player may search for a primary player, where, participating in the games of the primary player: (a) the secondary player has won a jackpot; (b) the secondary player has made a profit; (c) the secondary player has entered X number of bonus rounds; (d) the secondary player has won in X of the last Y games; (e) the secondary player has won X % of the last Y games; (f) the secondary player has won X payouts more than Y amount; and so on. The secondary player may also search for a primary player where the secondary player has participated in more than X number of games with the primary player.
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        • 1.18.3.3. A secondary player may search for a primary player based on demographic characteristics of the primary player. For example, the secondary player may search for a primary player based on one or more of the primary player's: (a) age; (b) race; (c) marital status; (d) number of children; (e) number of grandchildren; (f) religion; (g) place of birth; (h) place of residence; (i) gender; (j) occupation; (k) income; (l) disability status; (m) education level; (n) high school attended; (o) college attended; and so on. For example, the secondary player may wish to participate in games of a primary player who shares one or more demographic characteristics with the secondary player.
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        • 1.18.3.4. A secondary player may search for a primary player based on hobbies enjoyed by the primary player. For example, the secondary player may search for a primary player that enjoys a particular game or sport, or for a primary player that is a fan of a particular sports team.
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        • 1.18.3.5. A secondary player may search for a primary player with whom the secondary player has some prior connection or relationship. The secondary player may search for a primary player in whose games the secondary player has previously participated. The secondary player may search for primary players in whose game the secondary player has previously won money, won a jackpot, won a large payout, or had some other result of interest to the secondary player.
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      • 1.18.4. In various embodiments, a secondary player may search for a particular game based on attributes of the game. The search may be particular to an individual game. For example, a search may distinguish between two games played by the same primary player at the same gaming device. In some embodiments, a secondary player may search for a game in which a certain amount has been bet. For example, a secondary player may search for a game in which three coins have been bet. The bet of three coins may make the primary player of the game eligible to win the jackpot. The secondary player may search for a game in which X number of pay-lines are activated, or a game in which X number of hands of video poker are being played simultaneously. A secondary player may search for a game based on the time or date on which the game was played. +
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        • 1.18.4.1. In some embodiments, a secondary player may search for a game based on events that transpire within the game. For example, the game may have already occurred, or the game may be in process at the time of the secondary player's search. A secondary player may search for a game in which: (a) a particular set of cards have been dealt (e.g., a video poker game where a pair has been dealt in an initial hand, or a blackjack hand where cards totaling 11 have been dealt as a starting hand); (b) a particular symbol or symbols of an outcome have been determined (e.g., two bar symbols have appeared on the reels of a gaming device out of an outcome consisting of three symbols); (c) a bonus round has been reached; and/or (d) a certain level of a bonus round has been reached.
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      • 1.18.5. Providing a game for the secondary player to participate in. At some point, the secondary player may be ready to participate in a game with certain attributes. The attributes may be attributes specified by the secondary player. For example, the secondary player may have searched for a game with the certain attributes, or otherwise provided an indication of a desire to participate in a game with the certain attributes. In some embodiments, the casino may, for other reasons, wish to have the secondary player participate in a game with the certain attributes. +
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        • 1.18.5.1. An actual historical game is provided. Given a set of attributes or characteristics, a casino may retrieve data about a historical game with the given set of attributes or characteristics. The historical game may be a game that was actually played by a real human player. For example, when a secondary player has indicated a desire to play in a game of video poker that was played by a primary player aged 60 years old, the casino may retrieve data about a game that was actually played in the past by a 60 year-old primary player and that was played at a video poker machine. The data retrieved may be used to display information about the game to the secondary player (e.g., to show screen shots of the cards being dealt in the game), to determine what the outcome of the game was, to determine whether the secondary player is a winner based on bets placed on the game by the secondary player, and to determine an amount to pay the secondary player. Data about historical games may be stored in a database or in any other storage means. Data about historical games may be indexed by different attributes, such as the age of the player or the type of game. Games may thus be searched by attributes, and data about games with attributes desired by a secondary player may be retrieved.
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        • 1.18.5.2. A historical simulated game is provided. Given a set of attributes or characteristics, a casino may retrieve data about a historical game that was simulated. The game may not ever have been played by a real human being. In some embodiments, the outcome of the game may have been determined prior to play by a real human being. However, subsequent to the outcome being generated, a person (e.g., a secondary player) may have participated in the game. As with a historical game originally played by a live player, data about a historical game that was simulated may be stored in a database and indexed by attributes. Subsequently, data about historical games may be searched according to desired attributes. The data may then be used to recreate the game for a secondary player, and to determine an outcome and an amount to be paid to a secondary player.
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        • 1.18.5.3. A current actual game is provided. Given a set of attributes or characteristics, a casino may determine a current game in progress with the given set of attributes or characteristics. For example, a 60 year-old primary player from Wisconsin may currently be involved in a game at a video poker machine in which an initial hand with a pair has been dealt. The secondary player may be allowed to participate in the game in progress. For example, the secondary player may be allowed to place a bet on what the final outcome of the game will be. In various embodiments, the secondary player need not have the benefit of the same pay table as does the primary player, since the secondary player is placing a bet in the middle of the game and has more information than the primary player did at the start of the game.
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        • 1.18.5.4. A current simulated game is provided. Given a set of attributes or characteristics, a casino may simulate a game having the given attributes or characteristics. The casino may, for example, use a computer algorithm to determine cards to deal in a card game (e.g., video poker) or to determine symbols to show in a simulated reel slot machine. For example, if a secondary player desires to participate in a game of video poker, the casino may simulate a game of video poker. If the secondary player desires to participate in a video slot machine game, the casino may simulate a video slot machine game. In various embodiments, the casino may use algorithms to simulate table games as well as games typically played on a gaming device. For example, the casino server may simulate craps, blackjack, or poker. If other players would normally be present in a game, the casino may use computer algorithms to simulate the decisions that would have been made by humans. For example, in order to simulate a game of poker, the casino may use algorithms designed to bet, call, fold, raise, or check, according to certain pre-programmed rules. In some embodiments, a secondary player may wish to participate in a game in which certain symbols or outcomes occur. The casino may, in some embodiments, simulate multiple games until the desired symbols or outcomes occur. The secondary player may have the opportunity to participate only in the game, of the multiple games, in which the desired symbols or outcomes occurred. For example, the secondary player may indicate a desire to participate in a game in which three-of-a-kind was dealt on the initial hand in a game of video poker. The casino may deal a number of simulated hands of video poker. Only when the casino finally deals an initial hand with three-of-a-kind, e.g., due to random chance, does the casino allow the secondary player to then place a bet and to receive winnings for the final outcome of the game. In some embodiments, the casino may accept a bet from the secondary player first, simulate multiple games until a game with desired characteristics is simulated, and then pay the player based upon the outcome of the game with the desired characteristics. In some embodiments, the simulation may begin with a game of the desired attributes. For example, if a secondary player desires to play in a game of video poker with three-of-a-kind dealt on the starting hand, then the simulation may begin by immediately dealing three-of-a-kind. The simulation may randomize the remaining cards (e.g., shuffle the cards remaining after the three cards of the same rank have been dealt, the remaining cards completing a standard deck of 52 cards). The game may continue with two additional cards dealt from the randomized deck to complete the initial hand, followed by the discarding of one or two cards, followed by the replacing of the discarded cards with new cards from the randomized deck. In various embodiments, the secondary player may or may not have the opportunity to make decisions in a simulated game. For example, in some embodiments, the secondary player may choose which cards to discard in a game of video poker. In some embodiments, the cards that are discarded may be chosen automatically, e.g., by a computer algorithm employing optimal poker strategy.
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        • 1.18.5.5. An alert is provided for when a game with desired characteristics will be played. Given a set of attributes or characteristics, a casino may determine when such a game will be played or will be likely to be played. For example, a secondary player may wish to participate in a game played by a primary player at a 3-reel slot machine, the primary player having three kids and a birthday in April. The casino may determine that a primary player with three kids and a birthday in April is indeed seated at a 3-reel slot machine. The primary player may have been playing for 20 minutes already, and presumably will continue to play. Therefore, a secondary player may be permitted to participate in games of the primary player from that point forward. The casino may alert the secondary player that a primary player with desired characteristics has been found and that the secondary player may begin placing bets in the games of the primary player. Further, the casino may begin transmitting information about the games of the primary player to the secondary player.
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    • 1.19. A secondary player participates in a game where a progressive jackpot is won. In various embodiments, a secondary player may participate in a game for which the primary player is eligible to win a progressive jackpot. However, in various embodiments, a progressive jackpot constitutes a single pool of money, and therefore cannot be paid in its entirety to multiple different players. +
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      • 1.19.1. The secondary player gets a fixed substitute. In various embodiments, when a primary player wins a progressive jackpot, a secondary player participating in the same game receives a fixed payment. The fixed payment may be some predetermined amount, such as $10,000.
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      • 1.19.2. The secondary player gets a fixed percentage. In various embodiments, when a primary player wins a progressive jackpot, a secondary player participating in the same game receives percentage of the progressive jackpot. +
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        • 1.19.2.1. The primary player gets the full amount, or less so the secondary player can be paid. In various embodiments, when a secondary player receives a percentage of a progressive jackpot won by a primary player, the amount received by the primary player from the jackpot may be correspondingly reduced. For example, if the secondary player receives X % of a progressive jackpot, the primary player may receive 100%-X % of the progressive jackpot. In various embodiments, for each bet placed on a game with a progressive jackpot, a portion of the bet is contributed towards increasing the size of the progressive jackpot. Thus, when a primary player and a secondary player each place a separate bet on a game, a portion of the primary player's bet may add to the size of the progressive jackpot, and a portion of the secondary player's bet may contribute to the size of the progressive jackpot. For each game, a fixed contribution to the progressive jackpot may be required. Thus, if both a primary player and a secondary player participate in a game, the contribution from the primary player towards the progressive jackpot may be less for that game than if only the primary player were participating in the game. In various embodiments, the primary player may receive the full amount of the progressive jackpot. The amount received by the secondary player may be over and above the amount paid out to the primary player. Even so, the secondary player may receive an amount equal to a predetermined percentage of the progressive jackpot, such as 10% of the progressive jackpot.
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      • 1.19.3. Part of progressive amount is set aside for secondary players before it is paid out. In various embodiments, a progressive jackpot is divided into two or more portions. A first portion is available to be won by primary players. A second portion is available to be won by secondary players. If a progressive jackpot is won in a game, a primary player participating in the game would win the portion of the progressive jackpot available to primary players, and a secondary player participating in the game would win the portion of the progressive jackpot available to secondary players. If there is no secondary player for the game, then the portion of the progressive jackpot available for secondary players may remain unclaimed.
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      • 1.19.4. There is a progressive just for secondary players. In various embodiments, a progressive jackpot (other similar terms used herein may include “progressive prize”, “progressive prize pool”, “progressive pool”, “progressive payout”) may grow from the contributions of only secondary players. The progressive jackpot may be available to be won only by secondary players. For example, for each bet a secondary player puts on a particular type of game, a portion of the bet may be set aside and added to a progressive jackpot. If a secondary player participating in the particular type of game later wins the progressive jackpot, the jackpot may go to the secondary player. The size of the progressive prize pool may then go down to zero. In some embodiments, once a progressive prize pool has been claimed, the next pool may be seeded with some money by a casino, e.g., with $10,000, so as to garner interest from secondary players. In various embodiments, a display visible by a secondary player may track the size of a progressive. For example, a secondary player may participate in games using a mobile device (e.g., a mobile device as set forth in Nevada bill AB471). The mobile device may maintain on its display screen a running tally of the size of the progressive pool. In various embodiments, two or more separate progressive jackpots may be available for secondary players. In various embodiments, a secondary player may be eligible to win a progressive prize based on the location or geographic region from which the secondary player participates in games. For example, a secondary player participating while seated in Casino A may be eligible for a first progressive prize pool of $10,000. Another secondary player participating while seated in Casino B may be eligible for a second progressive prize pool of $20,000. A progressive prize pool may be available to be won by a particular secondary player based on one or more characteristics or circumstances of the secondary player, such characteristics or circumstances including: (a) a demographic of the secondary player, such as an age, birthday, birthplace, marital status, educational status, and so on (e.g., there may be a first progressive pool for secondary players aged 60 or over and a second progressive pool for secondary players aged 59 or under); (b) the particular type of game the secondary player is participating in (e.g., there may be separate progressive prizes for slot machine games and video poker games); (c) the location or geographic region from which the secondary player is participating (e.g., there may be different progressive pools for different casinos, different cities, different states, etc.); (d) the time or date during which the secondary player is participating (e.g., there may be a different progressive prize offered during each six-hour period in a day); (e) the identity of the primary player (e.g., there may be a first progressive prize pool associated with the games of a first set of primary players, and a second progressive prize pool associated with a second set of primary players); (f) a characteristic or circumstance of the primary player (e.g., demographic, location, etc. of the primary player); (g) a bet being made by the secondary player (e.g., a secondary player may be eligible for a first progressive prize if his bet is more than $3, and a second progressive prize if his bet is less than $4); and so on. In various embodiments, a progressive prize pool may be associated with a given period of time. For example, a progressive prize pool may be associated with a particular day. The progressive prize pool may be associated with a guarantee that it will be won on its associated day (or its associated period of time). According to the guarantee, the progressive prize may be claimed by the first secondary player to achieve outcome A, the first secondary player to achieve outcome B if no secondary player achieves outcome A, the first secondary player to achieve outcome C if no secondary player achieves outcomes A or B, and so on. In various embodiments, a progressive prize pool may have its probability of occurrence set so that it is likely the pool will be won during an associated time period. For example, if it is anticipated that secondary players will play 10,000 games during a given time period in which they have a chance of winning a progressive, the probability of winning for each game may be set at 1/5000. The probability that the progressive will be won during the time period may then be approximately 86%. In some embodiments, as the casino may be aware in advance of the outcomes of games to be played by a secondary player, the casino may intentionally offer for play at least one game that will result in a progressive prize being won. One such game may be offered during every period in which a progressive prize is guaranteed to be won. In various embodiments, two or more progressive prize pools may be simultaneously available to be won by a secondary player. One progressive pool may be associated with a relatively shorter period of time, while another progressive pool may be associated with a relatively longer period of time. For example, a first progressive prize pool may be won, on average, once a year. In fact, the first progressive prize pool may be guaranteed to have a winner every year. A second progressive prize pool may be won, on average, once a day. A secondary player may be eligible to win either of the progressive prize pools in the same game. In some embodiments, a secondary player may win only the first progressive prize pool while participating in a first game. In some embodiments, a secondary player may be eligible to win only the second progressive prize pool while participating in a second game.
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      • 1.19.5. A secondary player cannot play games with progressives. In various embodiments, secondary players may not be allowed to participate in games with progressive payouts.
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      • 1.19.6. A secondary player wins the full amount of the progressive. In various embodiments, when a progressive payout is won in a game, the secondary player may receive the full amount of the progressive. For example, suppose a primary player wins a progressive jackpot in a game for which the progressive jackpot is $100,000. The primary player may receive $100,000. The secondary player may also receive $100,000.
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      • 1.19.7. Making up extra funds to pay secondary players. In various embodiments, a progressive payout (e.g., a progressive jackpot) may consist of funds held in reserve for a time when the jackpot must be paid out. If a progressive jackpot is won in a game where a secondary player is participating, the progressive jackpot may go to the primary player and additional funds must be obtained by the casino to pay the secondary player. In various embodiments, the casino may pay the secondary player out of a separate pool of funds, such as an account used by the casino for general business expenses. In some embodiments, the secondary player may receive a promise of payment. The secondary player may receive a portion of contributions towards future progressive payouts. For example, the secondary player may receive 50% of all portions of bets withheld for a subsequent progressive jackpot until such time as the subsequent progressive jackpot is won.
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    • 1.20. Anti-vulture provisions. A secondary player may be prevented from playing in games with a positive expected value. Various situations may arise with respect to a gaming device or with respect to a live table game where betting circumstances are favorable to a player. Favorable circumstances may include circumstances where a player might expect to receive, on average, more than 100% of his bet from winnings in a game. For example, if a progressive jackpot or other payout at a slot machine reaches a certain level, the slot machine may return, on average, more than 100% of an amount bet. In some slot machines, certain symbols, tokens, or other objects may be accumulated from game to game. For example, Double Diamond Mine® slots, made by IGT, allow a player to accumulate diamond symbols from game to game. Once 10 diamond symbols from a particular reel have been accumulated, the player wins a payout. A slot machine in which a number of such objects have been accumulated may return, on average, more than 100% of an amount bet. In games of blackjack, such as in live table games of blackjack, a game may return more than 100% of an amount bet if the cards remaining in a deck have a predominance of one type of card (e.g., of high cards).
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    •  In various embodiments, a secondary player may be allowed to search for historical games in which the expected payout is more than 100% of the bet. For example, the secondary player may search for games at a Double Diamond Mine® slot machine where nine diamond symbols for each reel have already been accumulated. In another example, the secondary player may be allowed to search for gaming devices in which a progressive jackpot has exceeded a certain threshold. The secondary player may be allowed to participate in such games. However, in some embodiments, the secondary player may be prevented from participating in games in which an expected payout is more than 100% of the bet. In some embodiments, a secondary player may only be allowed to participate in games returning more than 100% of an amount bet if such games arise during a longer sequence or session of play. For example, a secondary player may be allowed to participate in a Double Diamond Mine® slot game for which nine diamond symbols have accumulated for each reel only if the secondary player has already participated in immediately prior games that had occurred at the same slot machine.
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    •  Tracking of game data usage. In some embodiments, a game that was originally played at a first casino or other establishment may subsequently be recreated at a second casino or establishment. For example, a secondary player at a second casino may participate in a game that was originally played at a first casino. The second casino may derive revenue, profit, or other financial gain from the recreation of the game at the second casino. For example, when a secondary player places a bet on the game at the secondary casino, the secondary casino may expect to win some portion of the bet, on average. In some embodiments, the second casino may compensate the first casino for the privilege of using or recreating the game that was first generated or played at the first casino. In various embodiments, the use of games for participation by secondary players may be tracked. The tracking of such use may allow a first casino (e.g., the casino that originally generated a game) to track how much it is owed, and a second establishment (e.g., the casino that recreated the game for play by the secondary player) to track how much it owes. The use of a game at a casino may be tracked in a number of ways. Data related to the game, e.g., a game identifier, may be stored in a database. A time during which the game was recreated may be stored. Other items stored may include: (a) an identity of a secondary player who played the game; (b) an amount bet on the game; (c) an amount won or lost by the casino recreating the game; (d) a type of bet placed on the game; (e) a number of secondary players who participated in the game; (f) a location of a secondary player who bet on the game; (g) an amount owed to the casino that originally generated the games; and so on. Data about individual games may not be stored, in some embodiments. Rather, data about blocks or groups of games may be stored. For example, a casino may store a record indicating that a group of 1000 games was recreated during the afternoon of Aug. 17, 2010, and that a total of $40,000 was bet on the games.
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    •  In various embodiments, a casino that used or recreated one or more games may send a report about the use of the games to the casino that originally generated the games. For example, the casino that recreated the games may send a printed report with each line on the report detailing, e.g., a particular game, a particular time the game was recreated, an amount bet, and an amount owed to the casino that originally generated the games. The report may be a paper or electronic report. The report may be sent by postal mail, email, fax, via download from the Internet, or via any other means. A report may cover a single game or a group of games. A report may be sent in real time (e.g., a report about the use of a game may be sent to the casino that originated the game as the game is used or immediately after the game has been used), periodically (e.g., every hour), or once (e.g., at the end of a period for which the casino using the games is authorized to use the games by the casino that first generated the games).
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    •  Data stored by a casino relating to the use or re-creation of games within the casino may be obtained from devices used for play by secondary players. For example, a terminal at which a secondary player participates in a game may store and/or transmit various data to the casino server, such as amounts bet by the secondary player, which games the secondary player played, and so on.
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    •  In various embodiments, a casino that uses data about games originally generated at another casino may track or record the use of various images associated with the game. Based on the use of images, royalties may be paid to copyright holders of the image. Also, the casino that originally generated the game may track the use of images from the game.
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    • 1.21. Bucket shop paradigm. Under this paradigm an establishment hopes to invest the least amount possible in casino infrastructure, including games, and even licenses to be a casino operator. Instead, the establishment plans to just reuse data from a real casino, set up a nice façade, and open up for business. In various embodiments, an operator may set up a gaming facility which uses solely or predominantly games or outcomes that have already been generated. The operator may thereby save various costs, possibly including the costs of purchasing gaming equipment, costs of obtaining accounting software and other infrastructure, and costs associated with meeting various regulations. For example, by reusing outcomes that have already been generated, an operator need not buy expensive gaming machines to generate original outcomes. Further, the operator need not submit such gaming machines for regulatory approval or inspection. In some embodiments, an operator of a facility that only reuses games and outcomes already generated may not be required to obtain the same types of regulatory approval as does a facility that generates original games and outcomes. The operator of the facility that reuses games and outcomes need not, in some embodiments, submit devices used by secondary players to the same process of regulatory approval that ordinary gaming devices (e.g., slot machines) are subject to. Rather the regulatory approval process may be simpler for the devices used solely by secondary players. In some embodiments, an entire facility that only reuses games or outcomes may not be subject to the same regulatory processes as is a facility that generates original outcomes. Rather, the regulatory processes may be simpler for facilities that solely reuse games or outcomes.
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    •  In some embodiments, by using outcomes already generated, an operator may use accounting data that has already been generated to account for amounts received, won, and lost based on the outcomes. Thus, the operator may save on accounting software and other accounting infrastructure, such as networks or intranets for conveying accounting related information. +
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      • 1.21.1. Use of shell machines that simply display outcomes from other machines. In various embodiments, an operator may install machines or devices with simplified functionality. The machines may include currency acceptors, credit card acceptors, or other acceptors for consideration to be used for betting purposes. The machines may include output devices, such as microphones for audio output and display screens for video or graphical output. The machines may further include dispensers for cash, coins, currency, tokens, chips, cashless gaming receipts, or other consideration. Consideration may be paid to a player based on amounts won while participating in games, or based on amounts remaining from an initial deposit made by a player. The machines may further include media players and/or media storage devices. For example, the machines may include DVD players or VHS players. The machines may include VHS tapes, DVDs, CDs, flash memory, or other media storage devices. The machines may further include buttons, handles, and touch screens for use by a player to input information, such as amounts to bet. The machines may further include network interfaces for sending and receiving information via a network, such as an intranet or internet. Network interfaces may include wireless network interfaces, such as antennae. Operationally machines according to various embodiments may receive a record of historical games, stored on a media device, such as a DVD. The machines may receive currency from a player. The machines may then receive an indication of an amount to bet. The machines may then receive an initiation signal for a game from the player. The player may convey the initiation signal, for example, by pressing a button labeled “spin” on the machine. The machine may then play for the player a video or other depiction of a stored game from the DVD. For example, the machine may play a 10-second video clip from the DVD, the video clip depicting a historical game that occurred at an actual slot machine. The machine may determine an outcome of the game. For example, the DVD may store, in association with each game, information about a payout or payout ratio associated with the game. Based on the information about the payout, the machine may pay the player. The player may be paid by, e.g., dispensing currency through a dispenser of the machine, or by adding to a balance of player credits stored on the machine. In various embodiments, the machine does not itself generate any outcomes or games. The machine merely replays games that have been previously generated. In various embodiments, the machine may recreate games based on a limited amount of information about the games. For example, the machine may receive information about the outcome of a game. The machine may then display an animated sequence depicting slot reels spinning and stopping to show the outcome. In some embodiments, the machine need not store information about prior games locally on the machine. Rather, the machine may receive information about historical games via the network. As information about historical games is received, the machine may recreate the historical games for the benefit of a secondary player at the machine.
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      • 1.21.2. Simplified regulatory license. An operator is just reusing data that's already been certified. There is no need to recertify data. In various embodiments, an operator using historical outcomes may operate without one or more licenses required of a typical gaming operator. A special license may be granted for operators who use only historical outcomes. A special license may be granted for operators who use only historical outcomes which have come from licensed gaming establishments.
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      • 1.21.3. Reuse of accounting data. There is no need for an operator to generate his own accounting data. In various embodiments, a casino operator may generate a number of original games or outcomes. Based on the outcomes, the casino may generate a record of amounts won, amounts lost, amounts collected, amounts owed in taxes, and so on. Such data may constitute accounting data. The casino operator may subsequently share such accounting data with a second operator who reuses the outcomes generated by the first casino operator. Since the outcomes used are the same, the accounting data required may be the same or similar. Therefore, in some embodiments, the second operator may receive the accounting data from the first casino operator, and reuse the accounting data for its own records.
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      • 1.21.4. Pre-inspection of the data is not allowed, as then the bucket shop could be accused of knowing the outcomes in advance. In various embodiments, an operator using historical games or outcomes is forbidden by law, regulation, convention, or other policy from obtaining knowledge about the games or outcomes prior to the participation in the games by a secondary player. In this way, the operator may be discouraged from selectively making available games or outcomes that are unfavorable to the operator.
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    • 1.22. Multi-Tiered Poker Game. In various embodiments, a poker game occurs. The poker game may include a number of live players at a table at a casino. The poker game itself may be referred to as a first tier game. Based upon the first tier game, a second tier game may be played. The second tier game may involve a different set of players. In some embodiments, the second tier game includes one player for each player in the first tier game. Each person in the second tier game may be associated or matched with a person in the first tier game. In various embodiments, a person in the second tier game may bet on what his associated player will do in the first tier game. For example, the player in the second tier game may bet that his associated player in the first tier game will check, bet, raise, call or fold. Further, the person in the second tier game may place a bet on the amount that the associated person in the first tier game will bet. For example, if Joe in the second tier game is associated with Sue in the first tier game, then Joe may bet that Sue will raise by at least 30 chips. In various embodiments, a person in the second tier game cannot communicate with his associated person in the first tier game. In various embodiments, no one in the second tier game can communicate with anyone in the first tier game, and vice versa. In various embodiments, a person in the second tier game knows the cards of the associated person in the first tier game, but does not know the cards of any other player in the first tier game.
      • +
    •  In various embodiments, a person in the second tier game may also check, bet, raise, fold, or call against other people in the second tier game. He may bluff and hope other people in the second tier game will fold. Should two or more players remain in a second tier game once the first tier game has reached its conclusion, a pot in the second tier game may be awarded to a person in the second tier based on the results of the first tier game. Namely, if a person in a second tier game is associated with the person in the first tier game who won the first tier game, then the person in the second tier game will also win in the second tier game. In some embodiments, the result or outcome of the second tier game is decided as if each person in the second tier game held the cards of his associated person in the first tier game. In various embodiments, if a player in the first tier game folds, the associated player in the second tier game folds automatically, and thus loses in the second tier game.
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    •  In various embodiments, there may be higher tiers. For example a third tier may include the same number of players as are in the second tier (or, equivalently, the first tier). Each player in the third tier may be associated with a player in the second tier. Thus, the player in the third tier may automatically be associated with the person in the first tier to whom is associated the player in the second tier that is associated with the player in the third tier. In other words, one player in each tier may be associated with a particular hand of cards, and all such players may be associated with one another. Players in the third tier may place bets on what bets will be made by associated players in the second or first tiers, and on how much will be bet by such players. Further players in the third tier may make bets against one another to be decided by results of lower tiers. A player in the third tier may win a pot if he has not folded, his associated player in the second tier has not folded, his associated player in the first tier has not folded, and his associated player in the first tier has the best poker hand at the conclusion of the first tier game. However, if an associated player in the first or second tier folds, a player in the third tier is automatically folded. Note, however, that a player in the second tier is not automatically folded if an associated player in the third tier has folded. It will be appreciated that there may be any number of tiers, with fourth, fifth, sixth, etc., tiers operating in an analogous fashion to what has been described with respect to the first three tiers. In some embodiments, a person in a tier greater than the first tier may see the cards of all players in the first tier. +
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      • 1.22.1. There may be time limits on people in higher tiers so they can't stall to see what happens in the actual game. In some embodiments, a player in tier two or above may have a time limit for making bets or other game decisions. The time limit may force a player in tier two or higher to take action before the game proceeds in tier one, and thus before the player in tier two or above discovers important information from watching the first tier players that might aid him in his game decision.
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      • 1.22.2. A higher tier game may not occur in a live environment. Thus higher tier players may bet after the fact. In various embodiments, tier two, tier three, and higher tier games may occur after the tier one game has occurred. Accordingly, a playback of the action in the tier one game may be halted until all appropriate actions have been taken in the higher tier games.
        • +
      • 1.22.3. Tiers could form among people at the pool, using handheld devices. In various embodiments, a second tier, third tier, or higher tier game may form amongst players that are remote from a poker table. For example, players located poolside at a casino may engage in a second tier game using handheld devices, such as personal digital assistants. Thus, the second tier players may benefit from the work of a dealer and from the use of physical cards, but without having to be physically present at a poker table.
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    • 1.23. In various embodiments, a first secondary player may receive an alert regarding the activities of a primary player and/or of a second secondary player. An activity that may trigger an alert may include: (a) the primary player inserts a tracking card into a gaming device; (b) the primary player inserts currency or other consideration into a gaming device; (c) the primary player presents a tracking card or other identification at a table game (e.g., at a blackjack game); (d) the primary player buys chips at a table game; (e) the primary player places a bet in a slot machine game; (f) the primary player places a bet in a game; (g) the primary player participates in a game; (h) the primary player receives a payout in a game; (i) the primary player checks into a hotel; (j) the primary player pays for a meal at a restaurant (thereby identifying himself with a credit card, for example); and so on. Similar activities by the second secondary player may trigger an alert for the first secondary player. An alert may be sent to the secondary player if the primary player was or is flagged for any reason, such as being of interest to the first secondary player. For example, the first secondary player may have indicated that the primary player is the favorite player of the secondary player. Thus, the first secondary player may wish to be alerted any time the primary player is playing or will begin playing so that the first secondary player may have the opportunity to participate in the games of the first primary player. An alert may be transmitted to a device of the second secondary player, including a cell phone, personal digital assistant, Blackberry®, laptop, personal computer, television, and so on.
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    •  An alert may also be transmitted to the first second secondary player under other triggering conditions. An alert may be sent to the first secondary player if a primary player of interest: (a) is playing a particular game (e.g., a favored game of the second secondary player); (b) has had a streak, such as a winning streak or losing streak (e.g., the primary player has won 10 games in a row; e.g., the primary player has lost games in a row); (c) the primary player has won a certain amount (e.g., the primary player has won more than $100); and so on. An alert may be sent to the first secondary player based on similar triggering conditions involving the second secondary player.
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    • 1.24. Embodiments disclosed herein need not apply only to casino gaming. Rather, where applicable, disclosed embodiments may apply to a wide variety of games, contests, sporting events, random events, unknowns, and so on. Where applicable, disclosed embodiments may apply to anything that may be the subject of a bet. Disclosed embodiments may apply to table games, video games, boxing matches, sporting events, the price movements of equities, the price movement of bonds, the movements of other market securities, the results of elections, the weather, the temperature, the average test scores of a body of students, and so on. For example, a secondary player may place a bet on whether a stock price will go up or down in the next ten minutes. Note that, in various embodiments, a primary player need not be explicitly present. For example, a secondary player may bet on the temperature a day in the future even though there is no primary player per se who effects the temperature.
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    • 1.25. Embodiments described herein need not apply only to complete games. Where applicable, embodiments described herein may apply to events within games. For example, a secondary player may bet on the next card that a primary player will receive in a game. A secondary player may bet on the next roll of the dice, on how many times a player will hit in a game of blackjack, on the point total of the dealer's hand in a game of blackjack, on the contents of a flop in a poker game of Texas Hold'em, and so on. A secondary player may be alerted when certain sequences of events have occurred. For example, a secondary player may be alerted when the last ten cards dealt in a game were red cards (i.e., hearts or diamonds). A secondary player may view historical data about events within a game or games. For example, the secondary player may examine historical data about the number of times the number 12 has been rolled in craps in the last 10 minutes.
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    • 1.26. A secondary player just watches a primary player. In various embodiments, a secondary player may wish to watch the play of a primary player, watch the games of a primary player, watch the facial expressions of the primary player, follow the strategies of the primary player, examine the historical results of the primary player, or otherwise track the primary player. The secondary player may wish to track the primary player without betting or risking any money on the games of the primary player. For example, a secondary player may wish to watch the games of a primary player who is a celebrity. Simply watching the celebrity player may provide entertainment for the secondary player.
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    •  A secondary player may search for a primary player based on any number of criteria, such as those mentioned above. A secondary player may search for a primary player based on a name (e.g., Ben Affleck); based on a demographic; based on a celebrity status (e.g., a name that generates more than 1000 hits in a Google search); based on a typical amount bet (e.g., a secondary player may search for any player who bets more than $100 per game); based on a history of wins or losses; based on strategies employed; based on facial expressions (e.g., a computer algorithm may score the expressiveness of a primary player's face and allow the secondary player to search for the most expressive faces); and/or based on any other criteria.
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    •  In various embodiments, a secondary player may pay a fee for watching the games of primary players. A fee paid by the secondary player may allow the casino to profit from the secondary player even if the secondary player does not place any bets. The secondary player may pay a fee per game watched, per time period during which he watches, or based on any other metrics. In various embodiments, the primary player may receive a portion of the fee paid by the secondary player.
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    •  In various embodiments, the primary player's permission must be obtained before a secondary player may track the play of the primary player.
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  • 2. Bet on a smaller aspect of someone else's game. For example, bet on what the next card will be, what the next roll of the dice will be, etc. In various embodiments, a person who does not directly participate in a game at a casino may nevertheless place bets on various events in the game. An event may include the rolling of a die, the drawing of a card, the spinning of a roulette wheel, the spinning of a reel of a slot machine, and so on. An event may come to a resolution in the form of a number revealed on the top face of a die, in the form of a rank or suit of a card drawn, in the form of a number achieved at a roulette wheel, in the form of a symbol appearing on a reel at a pay-line, and so on. An event may also include a decision or action made by a player who is directly involved in the game. For example, an event may include a player making a decision to hit or stand in blackjack, a player making a decision to bet or fold in poker, a player making a decision of which prize door to choose in a bonus round of a slot machine game, and so on. Such an event may come to a resolution in the form of an actual decision made. For example, a resolution may include an actual decision made by a player, such as “hit”, “draw”, or “fold”. An event may include a dealer making a decision in a game. For example, in a game of Pai Gow poker an event may include an arranging of the dealer's seven cards into a two-card hand and a five-card hand. The resolution of the event may take the form of an actual five-card hand and an actual two-card hand that the dealer has arranged.
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  •  As used herein, the term “payout odds” may refer to a statement of an amount a player will receive, in the event of a win, per amount bet. For example, 3:2 payout odds means that a player will receive 3 units per 2 units bet (in addition to keeping his original bet), provided the player wins the bet. It will be understood that a payout ratio may be readily determined from payout odds and vice versa via mathematical operations. Therefore, it will be understood that embodiments described herein using payout ratios could readily be performed with payout odds, and vice versa.
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  •  For a given event, an appropriate set of payout ratios may be determined. For example, if a secondary player is betting on a two as the resolution of a roll of a six-sided die, the secondary player may stand to win five times his initial wager (a payout ratio of 5) if the two is in fact rolled. Note that the player is assumed to give up his bet initially, so his net profit would be 4 times his initial wager if a two occurs. A set of payout ratios may be determined based on the inherent probabilities of various possible resolutions of the event. In the above example, the inherent probability of a two being rolled is 1/6. Thus, a payout ratio of five seeks to provide the player with a payout commensurate with the inverse of the probability of the resolution that would be winning for the player, while still allowing for a casino profit, on average.
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  •  Once the event has resolved, it may be determined whether the secondary player has won. For example, suppose a secondary player has bet that the next card dealt in a game of poker will be the ace of spades. Once the next card has been dealt, it may be determined whether the card is in fact the ace of spades, and therefore whether the secondary player has won. If the secondary player has won, the secondary player may be paid according to the payout odds.
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  •  In various embodiments, an event on which a secondary player bets does not constitute a complete game for the primary player of the game. For example, a secondary player may bet on what the next card will be in a game of video poker. However, the outcome of the game of video poker is not solely based on the next card, but rather is based on at least four other cards making up a complete hand of poker. Thus, a primary player may place a bet and may be paid based on his bet and based on the resolutions of a first and a second event in a game. A secondary player may place a bet on the same game and may be paid based on his bet and based on only the resolution of the second event in the game.
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  •  In various embodiments, the secondary player may be remote from the game. For example, the primary player may participate in the game while physically present at a slot machine, video poker machine, table game, or other game location. However, the secondary player may be remote from the primary player, such as 50 feet away, such as in a different room, such as in a different building, such as in different city, and so on. In various embodiments, the secondary player may bet on an event in a game after the game has been completed. For example, the secondary player may bet on an event in a game completed the prior week. The events of the game may be unknown to the secondary player, since the secondary player may not have been observing or participating in the game when it was originally played. +
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    • 2.1. Betting interface. In various embodiments, a secondary player may use a betting interface to make bets on events within a game. The betting interface may be a graphical user interface, and may include interactive features such as buttons, microphones, touch areas, mice, keyboards, and any other features for receiving designations of a secondary player's bet. An exemplary betting interface is shown in FIG. 9. The betting interface depicted in FIG. 9 includes an area where the names of available primary players are listed. The secondary player may elect to bet on events for the games played by these primary players. Next to each primary player is listed an indication of the last event resolution. For example, next to primary player Robert Clemens is listed the Jcustom character, or the jack of spades. This indicates that in the most recent event of Robert Clemens' game, the event being the dealing of a card, the resolution to the event was that a jack of spades was dealt. Next to Sue Baker is listed a “bar”. This indicates that in the most recent event of Sue Baker's game, the event being the random determination of a symbol to show in a viewing window of a slot machine game, the resolution to the event was that a bar occurred. In the case of TeeBone, the most recent card dealt was the two of hearts. The betting interface depicted in FIG. 9 includes two game windows in which a secondary player may bet on events within a game. In the game of TeeBone, the secondary player has just bet $5 that the next card dealt in the game will be a club. In the game of Sue Baker, two symbols have already appeared in the viewing window of the slot machine game in which Sue Baker is involved. The status of the game is such that the secondary player may bet on the third symbol that is yet to come in the same game of Sue Baker. The secondary player may use the “Bet Menu” area of the screen to select a symbol to bet on. At present, a “cherry” symbol appears in the Bet Menu area. The secondary player may, however, scroll through additional symbols in the menu and select (e.g., by touching three times in rapid succession) a symbol on which to bet.
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    • 2.2. Determining pay tables. In various embodiments, payout ratios may be determined for an event within a game. Payout ratios may be based on the probability that a bet on the event becomes a winning bet. Payout ratios may also be determined based on a number of other factors. Payout ratios may be displayed or otherwise presented for a secondary player. In some embodiments, payout ratios are displayed in the form of a pay table. The pay table may include a first column depicting various possible resolutions of an event, and a second column depicting the amount to be paid per amount wagered on each of the possible resolutions. +
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      • 2.2.1. Determining appropriate odds. In various embodiments, payout ratios may be determined based on a desired average amount to be won by a casino per bet received by the casino (e.g., based on a desired house advantage), on a house advantage of the game within which the event is occurring, and/or based on jurisdictional rules pertaining to allowable house advantages. +
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        • 2.2.1.1. A desired house advantage. In various embodiments, a casino may determine a desired house advantage for a bet on an event in a game. It will be appreciated that the casino may determine any number of equivalent desired metrics, where such equivalent metrics may be determined through deterministic mathematical transformations of a house advantage. For example, a casino may equivalently determine a desired average amount that a player will win per unit wagered. Exemplary house advantages may be 15%, 10%, and 5%. The desired house advantage may be determined based on any number of factors, including perceptions as to what house advantages would be attractive to players while still providing the casino with adequate profits.
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        • 2.2.1.2. Same as the gaming device. In various embodiments, a house advantage for an event within a game is determined based on the house advantage for the game itself. For example, the house advantage for a bet on an event in a game may be the same as for the house advantage for a bet on the game. In various embodiments, the house advantage for an event within a game may be close, but not identical to the house advantage of the game. For example, the house advantage of the event may differ by 2 percentage points from the house advantage of the game. Achieving identical house advantages may not be practical due, for example, to a requirement for integer payouts or to a limited number of possible resolutions of an event (e.g., there are only 6 resolutions to the roll of a die).
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        • 2.2.1.3. Amount wagered. In various embodiments, the house advantage for an event within a game may be determined based on the amount bet on the event. In some embodiment, the greater the amount bet, the less the house advantage. This provides the player with an incentive to bet more.
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        • 2.2.1.4. Jurisdiction minimum. In various embodiments, laws, rules, policies, or other conventions may dictate a maximum allowable house advantage for a gaming device. Accordingly, a house advantage for an event may be determined which is less than or equal to the maximum allowable house advantage.
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      • 2.2.2. Player preferences affecting the pay table. In various embodiments, an event in a game may have more than two possible resolutions. For example, the rolling of a die may have six possible resolutions, while the drawing of a card from a deck may have 52 possible resolutions. Payout ratios may be associated with each of the possible resolutions. Thus, a pay table may be formed for the event, where the pay table details payout ratios for one or more of the possible resolutions. In various embodiments, it may be possible to form many different pay tables for the same event. Further, many different pay tables may result in the same or similar house advantages. For example, a first pay table for a roll of a die may provide a payout ratio of 5 for a roll of a 6, and a payout ratio of 0 for any other roll. A second pay table for a roll of a die may provide a payout ratio of 3 for a roll of 6, a payout ratio of 2 for a roll of 5, and a payout ratio of 0 for any other roll. With the first pay table, the player may expect to win 5 times his wager with probability 1/6, yielding an expected payout of 5/6 times his wager, which yields a house advantage of (1−5/6)/1=16.67%. With the second pay table, the player may expect to win 3 times his wager with probability 1/6, or two times his wager with probability 1/6, yielding an expected payout of 3/6+2/6=5/6. Thus, the second pay table has the same house advantage of 16.67%. +
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        • 2.2.2.1. Player selects pay tables from range of pay tables. In various embodiments, a secondary player may select among various possible pay tables to use for an event. For example, when betting on the draw of a card, a secondary player may choose a pay table which pays 48 times an initial wager only if an ace of spades is drawn, or the secondary player may choose a pay table which pays 12 times an initial wager if any ace is drawn. In one embodiment, a secondary player may choose between a pay table which provides a relatively high payout with a relatively low probability and a pay table which pays a lower payout or payouts, but with greater probability. Over a set of repeated games, the former pay table would tend to provide less frequent but greater rewards, while the latter pay table would tend to provide more frequent but smaller rewards. A secondary player might therefore decide on his preferred method of receiving rewards. A secondary player may be given the opportunity to select among a range or continuum of possible pay tables, each with approximately the same house advantage, but each having different maximum payouts and/or different frequencies for providing payouts. A player may select a pay table by selecting a maximum payout. Typically, though not necessarily always, a pay table with a relatively higher maximum payout ratio will tend to pay less frequently than does a pay table with a relatively lower maximum payout ratio. A player may also select a pay table based explicitly on a payout frequency associated with a pay table. In some embodiments, the player may adjust a dial, where one limit on the dial is associated with a pay table with one or more relatively high payouts and a relatively low frequency of payout, and an opposite limit of the dial is associated with a pay table with one or more relatively low payouts and a relatively higher frequency of payout.
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      • 2.2.3. Determining odds of a particular symbol in a slot machine on a reel. In some embodiments, a player may bet on the occurrence of a particular symbol or indicium during a game. In some embodiments, the probability of occurrence of a symbol may be determined. In some embodiments, the probability of occurrence of a symbol at a particular position may be determined. For example, the probability of occurrence of a particular symbol in the first position across a pay-line of a slot machine may be determined. The determination of a probability of occurrence of a symbol or of a symbol at a particular location may allow the determination of a payout ratio that is commensurate with the probability. For instance, if the probability is determined to be lower, then the payout ratio may be set relatively higher, and vice versa. +
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        • 2.2.3.1. Monte Carlo. In some embodiments, the probability of occurrence of a particular symbol may be determined through a large number of trials, where each trial may include the playing of a game, or a simulated game. The game may be played at an actual gaming device, at a table game, or on a computer executing game software. The game may be played or run with actual money at risk (e.g., in the form of bets) or with no money at risk. For example, a game at a slot machine may be played ten thousand times. A program may track statistics of interest from the game, such as how often a “cherry” symbol occurred in the first position of the pay-line, how often a “bar” symbol occurred in general, and so on. The probability that a symbol occurs at a particular location on a pay-line may then be determined as the number of trials in which the symbol occurred at the particular location divided by the number of trials. Analogously, the probability of any an event coming to a particular resolution can be determined or estimated through a large number of trials in which the event occurs, and measuring the proportion of the trials in which the particular resolution occurred.
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        • 2.2.3.2. Going through virtual pay table. In some embodiments, the probability of occurrence of a particular symbol at a particular location on a pay-line may be deduced with reference to an internal algorithm used by a gaming device for generating game outcomes. In some embodiments, the algorithm used may employ one or more “virtual reels”. A virtual reel may comprise a table with one column of outcomes (e.g., a set of symbols), and with one column of ranges of numbers, each range of numbers corresponding to an outcome. A random number generator may generate a random number. The random number may then be matched to an outcome from the virtual reels based on the range of numbers in which the random number falls. Each outcome may thus be assumed to have a probability of occurrence that is proportional to the size of the corresponding range of numbers. For example, an outcome with a corresponding range of numbers of 100-299 is twice as likely to occur as an outcome with a corresponding range of numbers of 300-399, since the first range includes 200 numbers that may be generated by the random number generator, and the second range includes only 100 numbers that may be generated by the random number generator. With reference to the virtual reel, the probability of occurrence of each possible outcome may be determined. Then, the probabilities of all outcomes which include a particular symbol may be added up, thus yielding the probability of the occurrence of that symbol in a game. The probabilities of all outcomes which include a symbol in a particular location may similarly be added to determine the probability of occurrence of that symbol at that particular location. For example, to determine the probability that a “bell” symbol occurs at position 3 in an outcome, the probabilities of occurrence of all outcomes containing the “bell” symbol at position 3 may be added.
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      • 2.2.4. Odds of a particular card. In various embodiments, the probability that a particular card will constitute the resolution of a particular event may be determined as follows. First, the number of unknown or unrevealed cards may be determined. Unknown cards may include cards that have not already been shown face-up in a game. Provided the card of interest has not already been shown, the probability may be determined to be equal to one divided by the number of unknown cards.
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    • 2.3. Distinguishing between two dice. In various embodiments, a secondary player may wish to place a bet that would have an ambiguous resolution during conventional play of a game. For example, a secondary player may wish to bet that a particular die in a game of craps will show a six. However, the way craps is often played conventionally, it may be difficult or impossible to distinguish between the two dice used in a game. Thus, once the two dice land following a roll, it might conventionally be ambiguous as to which was the die that the player bet on. +
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      • 2.3.1. Distinguishing two otherwise similar objects. In various embodiments, two or more similar objects used in the play of a game may be made to appear distinct. In a game of craps, two dice may be colored differently. For example, one die may be colored green, while the other is colored red. In this way, a secondary player would be able to bet on either the red die or the green die without worry of an ambiguous result. In a game with three dice, such as in Sic Bo, there may be three dice of different colors. In a game of roulette involving the use of two balls at once, the two balls may include different patterned markings. A player may thereby bet on, e.g., the striped ball or the spotted ball. In some embodiments, two or more similar objects may be made detectably distinct, even if the distinction cannot be made visually. For instance, radio frequency identification (RFID) tags may be placed in or on objects. Two dice with different RFID tags inside them would be distinguishable by an RFID tag reader from the differing signals coming from the tags.
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      • 2.3.2. Bet that the lower die will be above two. In some embodiments, a secondary player may place a bet on a resolution of one of several events, in which the one event becomes distinguishable only after all of the events have been resolved. For example, a secondary player bets that the higher of two dice rolled in a game of craps will show a 6. In this example, two events may be deemed to occur, each event constituting the rolling of a die. However, the actual die a player is betting on becomes clear only after both events have resolved. In other words, only after both dice have been rolled and have come to rest can it be determined which is the higher die. A secondary player may, in some embodiments, bet on the lower of two dice, on the middle die (e.g., in a game with three dice), on the roulette ball showing the highest number, and so on. In various embodiments, a secondary player's bet may comprise at least two parts. The first part may be a method to distinguish between two or more events to determine which of the two or more events the secondary player is betting on. The second part may be an indication of what will constitute a winning or losing resolution for the secondary player. For example, suppose that a secondary player bets that the higher of two dice will show a five. The first part of the bet is a way to distinguish the rolling of one die from the rolling of the other die, and indicating which of the now distinct events the secondary player has bet on. The second part of the bet indicates that a winning resolution will be for the die that the player has bet on to show a five.
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      • 2.3.3. Specify a position of a card. For example, the third card drawn is the Ace of spades. In some embodiments, in order to clarify the specific event that a secondary player is betting on, a position, location, sequence number, or other clarification may be specified. For example, rather than betting that “a” card will be an ace of spades, a secondary player may bet that “the third card dealt” will be an ace of spades. In a game of video poker, a secondary player may bet that a card in a specified position in a video poker hand (e.g., the fourth card in the final hand), will be of a certain rank and suit. In a game of a blackjack, a secondary player may bet, for example, on the first card dealt to a player, the second card dealt to a player, the third card dealt to a player, etc. The secondary player may also bet, for example, on the first card dealt to the dealer, the second card dealt to the dealer, etc. The player may also specify an event by means of an orientation. For example, in a game of blackjack, the secondary player may bet on the dealer card that is face down, or on the dealer card that is face up.
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    • 2.4. Receive aids in your prediction. In various embodiments, a secondary player may be provided with data, hints, or other aids in making bets on an event in a game. Data may include historical data relevant to the game at hand. For example, if a secondary player is to bet on the decision that will be made by a primary player, data about the decision of the primary player in prior games might aid the secondary player in his bet. +
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      • 2.4.1. The sequence of what occurred in the past. In various embodiments, a secondary player may be shown or otherwise provided with data from games or events within games that were played prior to the game that includes the event on which the secondary player is betting. The data may help the secondary player to choose a resolution of the event which will constitute a winning resolution. A secondary player who is to bet on a particular event in a particular game played by a particular primary player may be shown data about other events that have occurred. Other events may include events that have occurred: (a) in games played by the same particular primary player; (b) in games under similar circumstances to those which are present in the particular game (e.g., the same initial two cards occurred in a prior game of blackjack as have in the particular game, and the particular event of interest is the dealing of the third card in the particular game); (c) in games played at the same gaming device that the particular game is or was played at; (d) in the recent past (e.g., events that have occurred in the five minutes prior to the time that the secondary player bets on the particular event); (e) just prior to when the particular event originally occurred (e.g., events occurring in games that had been played in the five minutes prior to the particular game); (f) in games played at the same gaming device that the particular game is or was played at, where such games constitute a sequence of games that immediately preceded the particular game (e.g., such games were the five games played before the particular game); and (g) in games played by the same particular primary player, where such games constitute a sequence of games that the primary player played immediately preceding the particular game.
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      • 2.4.2. What would perfect strategy be here? In various embodiments, a secondary player may be provided with an indication of a decision that would be made according to some strategy. For example, if a secondary player is betting on the decision that will be made by a primary player in a game of blackjack, the secondary player may be shown what decision would be made using Basic Strategy (i.e., the strategy used to maximize expected winnings without any special knowledge of what cards have already been dealt). For example, the secondary player may be told that the proper decision according to Basic Strategy is for the primary player to hit. As another example, if a secondary player is betting on what cards will be discarded by a primary player in a game of video poker, the secondary player may be told which combination of discards would maximize the expected winnings for the primary player. In various embodiments, the secondary player may be told what decision would be made according to a strategy that is not a perfect or optimal strategy. For example, a secondary player might be told which decision would be made according to a strategy that aims for the highest payout in a game.
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      • 2.4.3. What has this player done in similar situations? In various embodiments, a secondary player may be provided with an indication of what decisions a primary player has made in situations which are similar to the situation of the game in which the secondary player is participating. Games in which a primary player was in a similar situation may include games in which the primary player: (a) had the same cards; (b) had the same point total (e.g., in a game of blackjack); (c) had the same hand ranking (e.g., in a game of poker); (d) had the same sequence of initial events (e.g., in a game of craps, the primary player had the same three initial rolls as he does in the game situation under consideration); (e) was in the same seat position (e.g., the primary player was just to the left of the dealer); (f) faced the same opponent or opponents; (g) was at the same gaming device; (h) faced the same bet or bets from opponents (e.g., in a game of poker, the primary player may have faced the same bets that he does at present); and so on. Games in which the primary player was in a similar situation may include games in which the dealer had a similar hand (e.g., in a game of blackjack, the dealer had the same card showing), or games in which an opponent of the primary player had a similar card to what the primary player's opponent has in the game under consideration. In some embodiments, the secondary player may be provided with an indication of what the primary player did in games with similar external contexts, such as games played at the same time of day, games played at the same table, games played at the same casino, games played just after a big loss for the primary player, and so on.
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      • 2.4.4. What cards have been dealt already? In various embodiments, a secondary player may be provided with an indication of what cards have already been dealt in a game. For example, in a game of blackjack, the secondary player may be told what cards have been dealt from a deck in prior games where the deck was used. If, for example, the secondary player thinks the primary player has been counting cards, the secondary player may use information about prior cards dealt in order to predict the reaction by the primary player to the card count. In a game of poker, the secondary player may have the opportunity to view cards that have been dealt, e.g., as part of an initial hand. Looking at the cards of the initial hand may then help the secondary player to better predict a primary player's decision.
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      • 2.4.5. The secondary player is provided with a probability. In various embodiments, a secondary player may be provided with the probability of a particular resolution to an event. For example, if the secondary player is betting on the roll of a die, the secondary player may be told that the probability of a six being rolled is 1/6.
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      • 2.4.6. Regulatory requirements for hints. In various embodiments, regulations may dictate whether or not a hint must be provided. In some embodiments, regulations may dictate that the probability of a resolution be provided. In some embodiment, regulations may require that a secondary player be given a probability that an event comes to a particular resolution if there would be no way for the secondary player to know such a probability. For example, while it is possible for a secondary player to know the probability that a 6-sided die will land in a certain way, a secondary player may have no way of knowing that a reel of a slot machine will display a certain symbol since the reel may be controlled by a secret algorithm. In some embodiments, regulations may dictate that a hint not mislead a secondary player. For example, in game of video poker, a hint inform a secondary player of a decision that would be made by a primary player using a particular strategy. However, the strategy may not be a strategy that would typically be employed by any player, and thus the hint would not likely give the secondary player the proper direction. In some embodiments, regulations may dictate the form in which a hint must be provided. Regulations may require that a hint be given in multiple languages. Regulations might require that a player have the option of which language will be used to view the hint.
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      • 2.4.7. Form of hints (for example, secondary players are simply not allowed to make certain bets). In some embodiments, a hint may take the form of preventing a secondary player from making certain bets. Such bets may be disadvantageous for the secondary player or for the casino. For example, a graphical user interface may display options for what resolutions the secondary player can bet on. In a game of blackjack, such options may include a “hit” option for betting that a primary player will hit, a “stand” option for betting that a primary player will stand, and a “double down” option for betting that a primary player will double down. If the primary player has been dealt an initial hand with a point total of 10, then the “stand” option may be grayed out such that the secondary player cannot bet that the primary player will stand. This is because it would make no sense for the primary player to stand when the primary player can hit, increase his point total, and have no risk of busting.
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    • 2.5. Setting the odds on an event. In some embodiments, the casino may set the payout odds on an event by reference to historical data. Historical data may be used to arrive at a probability of a resolution of an event. For example, historical data may be used to determine the probability with which a primary player will make a particular decision in a game. This probability may be used, in turn, to provide payout odds to a secondary player who wants to bet that the primary player will make the particular decision. +
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      • 2.5.1. Data not including the current game. In some embodiments, the casino may use data from historical games of primary players in order to determine a probability that a primary player will make a particular decision. For example, the casino may examine a set of historical games in which various primary players had hands with 16 points against a dealer's 10 points showing. The casino may determine the number of primary players who hit and the number of primary players who stood in order to arrive an estimated probability for what a primary player will do in a particular game under consideration. For example, the casino may look at 100 historical games and may find that 45 times the primary player hit, and 55 times the primary player stood. Thus, the casino may determine that there is a 45% chance that a primary player will hit and a 55% chance that a primary player will stand under a similar situation. Once the casino has an estimate of the probabilities of various outcomes, the casino may set payout odds in order to create a positive house advantage. For example, in the aforementioned example, the casino may set payout odds of 1:1 if the secondary player bets on “hit”, and 3:4 odds if the secondary player bets on stand. In various embodiments, historical data may include data about historical games of the primary player who is involved in the particular game in question. For example, to determine the probability that a particular primary player will make a decision, the casino may look at historical data for that primary player.
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      • 2.5.2. Data including the current game. In some embodiments, payout odds may be set for a game based on a set of games which include that game. For example, the casino may use a set of games that include X (e.g., 1000) games in which a player had a pair of nines and the dealer showed an 8 in a game of blackjack. The casino may determine how many times the player with the nines split, and how many times the player just stood. The casino may thus know, with certainty, the probability that the nines would be split and the probability that the primary player would stand for a game randomly selected from the set of X games. Accordingly, the casino could then set payout odds for a bet on standing and a bet on splitting. The casino could set such payout odds in order to create a positive house advantage. The casino may then allow a secondary player to bet on a decision of a primary player in a game from the set of 1000 games, such as from a randomly selected game of the set of 1000 games.
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    • 2.6. Bet on a random action in the game. In various embodiments, a secondary player may bet on the resolution of any desired event. For example, in a table game of craps, the secondary player may bet that one die will bounce off the table. In a game of poker, the secondary player may bet that one of the primary players will throw his cards, that a primary player will get ejected from the game, that a primary player will bet out of order, or that any other resolution to an event will occur. In some embodiments, a secondary player may bet on any resolution that is external to the normal play of a game. For example, the secondary player may bet that a player will spill a drink at a gaming table.
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    • 2.7. Bet on a particular sub-outcome. There are many events on which a secondary player may bet. For each event, there may be one or more resolutions on which the secondary player may bet. +
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      • 2.7.1. blackjack. In a game of blackjack a secondary player may bet on: (a) the rank or suit of a particular card, such as the first, second, third, etc. player card or the first, second, third, etc. dealer card; (b) a decision that will be made by a primary player (e.g., hit, stand); (c) a decision that will be made by a dealer; (d) whether a primary player will bust; (e) whether a dealer will bust; (f) whether the primary player will receive two identical cards; (g) whether the primary player will receive two or more cards of the same suit; (h) whether two primary players in a game receive the same cards; (i) a starting point total for a primary player; (j) a starting point total for a dealer; (k) whether a primary player's ending point total will fall within a particular range; and so on.
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      • 2.7.2. Roulette. In a game of roulette, a secondary player may bet on (a) red; (b) black; (c) a particular number; (d) a particular range of numbers; (e) the occurrence of a number in a particular sector of a wheel; (f) an amount that a primary player will bet; (g) a number that a primary player will bet on; (h) green; and so on.
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      • 2.7.3. Slot machines. In a slot machine game a secondary player may bet on: (a) the occurrence of a symbol on a reel; (b) the occurrence of a set of symbols on a set of reels (e.g., the secondary player bets that the first reel will show a “bar” and the second reel will show a “lemon”); (c) whether a bonus round will be reached; (d) the level of a bonus round that will be reached; (d) a decision that a primary player will make in a bonus round; (e) a resolution of a bonus round (e.g., how much money the primary player will win from the bonus round); (f) the amount that the primary player will bet; (g) the number of pay-lines that the primary player will bet; (h) the number of pay-lines that will win, and so on.
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      • 2.7.4. Card Games. In a card game, such as a game of poker, a secondary player may bet on: (a) the occurrence of a particular card in a hand of cards; (b) the occurrence of a particular combination of cards in a hand of cards (e.g., the occurrence of a pair); (c) an order in which cards are dealt (e.g., the secondary player may bet that each card dealt will have a higher rank than the last card dealt); (d) a position in which a card will be dealt (e.g., an ace will be dealt as the first card in a player's hand; and so on. +
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        • 2.7.4.1. Poker. In a game of poker, a secondary player may bet on what bets will be made by primary players in the game. A secondary player may bet on whether a bet will be a check, call, bet, raise, or fold; on how much a primary player will bet; on how many callers there will be for a bet or raise; on how many times a pot will be raised; on how many rounds of betting there will be; on how many players will be all-in; and so on. In some embodiments, a secondary player may bet on the total size of a pot. In some embodiments, a secondary player may bet on whether there will be a tie. In some embodiments, a secondary player may bet on the size of a side-pot.
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      • 2.7.5. Dice Games. In a game of dice, a secondary player may bet on one roll of the dice. For example, the secondary player may bet that two dice rolled will total to 12. In a game of Sic Bo, a player may bet that one of the three dice rolled will show a 4.
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    • 2.8. Bet on length of the game. In various embodiments, a secondary player may bet on the length of a game. +
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      • 2.8.1. Time. A secondary player may bet on the time that a game will last. A game may be counted to start when a primary player makes a bet, when a first random event occurs in a game, when a first card is dealt, when a first roll of the dice is made, when a first player decision is made, and so on. A game may be counted to end when a payout is made, when a player's bet is collected, when a last random outcome is generated, when objects used in a game are collected (e.g., when cards are collected), when a payout is announced), or when a subsequent game starts.
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      • 2.8.2. Number of cards required. In some embodiments, a secondary player may bet on the number of cards that will be dealt in a game. A secondary player may bet on the number of cards that will be dealt to a particular hand (e.g., to a player hand in blackjack; e.g., to a dealer hand in blackjack); or to a particular combination of hands (e.g., to the hands of both the player and the dealer; e.g., to three players in a game of blackjack). A secondary player may bet on the number of cards that will be dealt as common cards. For example, regarding a game of Texas Hold'em, the secondary player may bet that all five common cards will be dealt. In other words the secondary player may bet that at least two people will remain in the game until the fifth common card is dealt.
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      • 2.8.3. Number of rolls of dice required. In various embodiments, a secondary player may bet on the number of rolls of dice that will occur in a game. For example, a secondary player may bet that there will be seven rolls of dice in a game of craps. In other words, the secondary player may bet that the primary player will set a point and then take six additional rolls to either roll the point number again or achieve a seven.
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      • 2.8.4. Number of bonus round levels reached. In various embodiments, a secondary player may bet on the number of levels that a primary player will reach in a bonus round, e.g., in a bonus round of a slot machine game. A bonus round may have a plurality of separate levels. If a primary player does well in earlier levels, e.g., by correctly choosing the location of hidden treasures, the primary player may make it to later levels. However, if the primary player does poorly in earlier levels, the primary player may not reach later levels. Thus, the number of levels reached in a bonus round may be effectively random. In some embodiments, a secondary player may bet on the number of spaces a character will advance on a game board in a bonus round. For example, regarding a bonus round in a game of Monopoly®, a secondary player may bet on the number of spaces that a game character will traverse on the game board. In some embodiments, a secondary player may bet on the space or spaces on which a game character will land in a game. For example, a secondary player may bet that a game character will land on Boardwalk in a game of Monopoly®.
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    • 2.9. Bet on a different game within the game. E.g., bet on poker within blackjack. In some embodiments, a secondary player may bet on the occurrence of an outcome from a first game, but in the context of a second game. For example, a secondary player may bet that a primary player who is involved in a game of blackjack will receive cards that create a poker hand which is three-of-a-kind. In a game of Sic-bo, a secondary player may bet that two of three dice used will form a winning roll in a game of craps.
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    • 2.10. Bet on the order in which people will remain in the game. Various games include multiple primary players. In some multi-player games, players may be eliminated or may drop out of the games. For example, in a game of poker, players may drop out of the game as they fold. In various embodiments, a secondary player may bet on the manner in which primary players are eliminated. +
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      • 2.10.1. Who will be the first one out? In various embodiments, a secondary player may bet on which primary player will be the first primary player eliminated. A secondary player may bet on who will be the second primary player eliminated, the third primary player eliminated, or who will be the primary player eliminated in any other spot.
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      • 2.10.2. Who will be the last two standing? In various embodiments, the secondary player may bet on which primary player will be the last one remaining. The secondary player may bet on who will be the second to last primary player remaining, who will be the third to last remaining, and so on. The secondary player may bet on who will be the last two primary players remaining. In various embodiments, the secondary player may bet on any combination of primary players and on any combination of places (e.g., last, second to last) in which primary players are eliminated. The secondary player may win the bet if the designated combination of primary players was eliminated in the designated combination of places. A secondary player may bet that a particular three primary players will be the last three remaining, regardless of the order in which they are eliminated after the final three. In some embodiments, the secondary player may bet not only that a particular group of primary players will be the last three remaining, but also on the order in which the last three will be eliminated (e.g., players A, B, and C will be the last three, player A will be the last, and player B will be the second to last remaining).
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      • 2.10.3. Who will be the three in after the flop? In various embodiments, a secondary player may bet on the number of primary players that will be remaining in a game at a certain point in the game. For example, a secondary player may bet on the number of primary players that will be remaining by the flop in a game of Texas Hold'em poker, or by fifth street in a game of seven-card stud poker. A secondary player may bet on how many primary players will be remaining in a game after X number of cards have been dealt in the game, regardless of whom the cards have been dealt to. A secondary player may bet that a particular primary player will remain in a game at a certain point in the game. For example, a secondary player may bet that primary player Joe Smith will be remaining in the game after the flop.
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      • 2.10.4. Which three people won't bust? In various embodiments, a secondary player may bet on a combination of people who will bust in a game of blackjack. For example, a secondary player may bet that, of a particular group of three primary players in a game of blackjack, all will bust. A secondary player may bet that one player will not bust. A secondary player may bet that of a group of primary players, none will bust during a game.
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    • 2.11. Bet on what the primary player himself will do. In some embodiments, a secondary player may bet on a decision that will be made by a primary player in a game. +
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      • 2.11.1. The primary player will hit here. In some embodiments, a secondary player may bet on a decision that a primary player will make in a game of blackjack. A secondary player may bet that a primary player will do one or more of the following: (a) hit; (b) stand; (c) surrender; (d) split; (e) double down; (f) take insurance.
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      • 2.11.2. The primary player will draw to the flush. In some embodiments, a secondary player may bet on a strategy that a primary player will employ in a game of video poker. The strategy may be specified with a specification of which cards a primary player will discard. For example, the secondary player may specify that the primary player will discard the first, third, and fourth cards from a starting hand. In some embodiments, the secondary player may specify one or more cards that will be discarded while not excluding the possibility that additional cards might be discarded. For example, the secondary player may specify that the primary player will discard the second card in his hand. The secondary player may then win his bet if the primary player discards the second card, regardless of other cards that the primary player might discard. A secondary player may specify the strategy of a primary player in terms of a goal attributable to the strategy. For example, the secondary player might specify that the primary player will “draw to a flush” or “draw to a straight”.
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      • 2.11.3. How much will the primary player bet? In some embodiments, a secondary player may bet on the amount that a primary player will bet. For example, the secondary player may bet that a primary player will bet $5 in a slot machine game. For example, the secondary player may bet that the primary player will raise by $25 in a game of poker.
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      • 2.11.4. What bet will the primary player make? In various embodiments, a secondary player may bet on a particular bet that a primary player will make in a game. For example, in a game of craps, there are many possible bets that a primary player can make, including a pass bet a don't pass bet, an “any seven” bet, an “any eleven” bet, a “horn bet”, and so on. The secondary player may bet on which of these, or other possible bets, the primary player will make.
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      • 2.11.5. Which pay-lines will the primary player activate? In various embodiments, a secondary player may bet on whether or not a primary player will bet on a particular pay-line at a gaming device. For example, a gaming device may have three pay-lines. A secondary player may bet that the primary player will bet on the third pay line.
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      • 2.11.6. Bet on primary players' heart rate, breathing, and other bio signatures. In various embodiments, a secondary player may bet on a vital sign of a primary player. The secondary player may bet on the heart rate, breathing rate, blood pressure, skin conductivity, body temperature, pupil dilation, muscle tension, or any other indicator tied to the primary player. For example, the secondary player may bet that the peak heart rate of a primary player will be 120 during a game of poker. For example, a secondary player may bet that a primary player will take 5 breaths in the next minute. The secondary player, by betting on the vital signs of a primary player, may indirectly bet on the stress level of a game and/or the primary player's response to stressful stimuli.
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      • 2.11.7. When will the primary player stop playing? Now? After five games? In various embodiments, a secondary player may bet on the length of a playing session of a primary player. The length may be measured in terms of time, the number of games played, the number of bets made, the number of cards dealt during a session, the number of times dice are rolled, or in terms of any other metric. For example, a secondary player may bet that a primary player will play five more games before quitting. For example, a secondary player may bet that a primary player will play for 40 more minutes before quitting. A session may be defined as having ended after: (a) a primary player has stopped playing for X amount of time; (b) a primary player has left the location of a game; (c) a primary player has cashed out; (d) a primary player has exchanged chips for money; (e) a primary player has run out of money; and so on.
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      • 2.11.8. What drink will the primary player order? In various embodiments, a secondary player may bet on a service that the primary player will receive. A secondary player may bet on a drink a primary player will order, on the type of food the primary player will order, on the price of a primary player's food or drink, on the amount that a primary player will tip a casino representative, and so on.
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      • 2.11.9. How many pulls will the primary player complete in an hour? In various embodiments, a secondary player may bet on the speed with which a primary player plays. A secondary player may bet on: (a) the number of handle pulls that a primary player makes in an hour or in any period of time; (b) the time between two handle pulls; (c) the time between the start of two games of blackjack; (d) the time between the placing of a bet in a game and the time of the provision of a payout; and so on.
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      • 2.11.10. Any combination of what primary players will do. For example, five primary players split. In various embodiments, a secondary player may bet on any combination of decisions that will be made by primary players in a game. For example, a secondary player may bet that at least 3 primary players will split in a game of blackjack; a secondary player may bet that a particular group of three primary players will split in a game of blackjack; a secondary player may bet that exactly three primary players in a game of blackjack will hit and that exactly one will split; and so on. Regarding a game of poker, a secondary player may bet that exactly two primary player will call a particular bet. In various embodiments, a secondary player may bet that certain decisions will or will not be made without regard to who makes the decisions. For example, regarding a game of poker, a secondary player may bet that one primary player will bet and that three primary players will call, without specifying which primary players will be the ones to bet and call. The secondary player may win his bet if any primary player bets and if any three primary players call.
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    • 2.12. Bet only on the third pay-line. Unlike the primary player, the secondary player does not have to bet on pay-lines 1 and 2 before betting on pay-line 3. In various embodiments, a secondary player may bet on an event in isolation on which the primary player was not allowed to bet in isolation. For example, the secondary player may bet on only the third pay-line of a slot machine. However, the primary player may have been required to bet on the first and second pay-lines at the slot machine before he could bet on the third pay-line. In a game of craps, a secondary player may be allowed to make an odds bet even without making a pass-line bet. Often, a primary player must first make a pass-line bet before making an odds bet.
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    • 2.13. Bet on what ad shows on the gaming device. In various embodiments, a secondary player may bet on an advertisement that will be displayed on a gaming device. In various embodiments, a gaming device may display an advertisement. In various embodiments, a gaming device may display an advertisement occasionally or periodically. An advertisement may be displayed at random or according to a schedule that is unknown to the secondary player. Accordingly, the secondary player may bet on what advertisement will be shown at a gaming device. For example, a secondary player may bet that an advertisement for vitamin water will be displayed on a gaming device. An advertisement may take the form of text, a still image, a video, or any other output that serves to promote a product or service, either directly or indirectly. A secondary player may specify a bet on an advertisement by specifying the product that will be promoted. For example, a secondary player may specify that Triscuit crackers will be advertised. A secondary player may specify a bet in terms of a general product category, such as crackers or snack foods. A secondary player may specify a bet on an advertisement by specifying a brand for a product or a name of a manufacturer for a product. In some embodiments, a secondary player may specify a bet on an advertisement through a multiple choice selection, where the secondary player may specify from among multiple possible different products to bet on. In some embodiments, a secondary player may bet on the time until the next advertisement. In some embodiments, a secondary player may bet on when the next advertisement for a particular product will be.
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    • 2.14. Combine sub-outcomes from several games to form larger outcomes. In some embodiments, a secondary player may bet on the outcome of a game which is created synthetically using events from more than one game. For example, synthetic game may be created for the secondary player using a first set of cards that was dealt in a first game for a primary player, and a second set of cards that was dealt in a second game for the primary player. As another example, a synthetic game may be created using a first roll of two dice from a first craps game, and a second roll of two dice from a second craps game. As another example, a synthetic slot machine game may be created using the symbol appearing on reel 1 in a first game, the symbol appearing on reel 2 in a second game, and the symbol appearing on reel 3 in a third game. If, for example, all three symbols are “cherry”, then the secondary player may be paid as if all three cherries had occurred on the same spin on adjacent reels.
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    • 2.15. Bet on a machine malfunction, or coin refill. In various embodiments, a secondary player may bet on the occurrence of a machine malfunction. For example, a secondary player may bet that a machine will malfunction within the next hour. In various embodiments, a secondary player may bet that a gaming device will need a coin refill. For example, the secondary player may bet that a gaming device will need a coin refill within the next 10 minutes.
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    •  Embodiments described herein with respect to complete games or outcomes may similarly apply to events within a game. For example, just as a secondary player may search for games having particular characteristics, a secondary player may search for events within a game having particular characteristics, or a secondary player may search for games with particular characteristics so as to bet on events within such games. A secondary player may search for particular primary players and bet on events within the games of such primary players.
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    •  In some embodiments, a secondary player may seek to view historical or current games. The secondary player may desire to participate in the games. The secondary player may, in some embodiments, perform a search for games which satisfy a first set of criteria. For example a secondary player may search for games which were played by a particular primary player. The search may yield a plurality of games. The games may then be sorted using a second set of criteria. The plurality of games may be sorted according to: (a) the time at which the games were played (e.g., the games may be sorted from the most recently played to the one played the furthest in the past); (b) the amounts won in the games (e.g., the games may be sorted from the game with the highest payout to the game with the lowest payout); (c) the amounts bet on the games; (d) the rankings of hands dealt in the games (e.g., games of poker may be sorted according to the poker ranking of the initial hand; e.g., games of blackjack may be sorted according to the point total of the final hand); (e) the results of the games (e.g., the primary player won; e.g., the dealer won); (f) the initial number rolled on a die in each game of the games; (g) the location in which the games were played (e.g., games may be sorted according to the floor in the casino where the games were played); (h) the name of the gaming devices on which the games were played (e.g., games may be sorted such that the gaming devices on which the games were played are in alphabetical order); (i) the name of the primary players who initially played the games; (j) the number of secondary players who participated in each of the games; and so on.
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    •  Any physical game described herein may be implemented electronically in various embodiments. For example, embodiments pertaining to the play of blackjack at a physical card table may pertain as well to a game of blackjack played over an electronic network. For example, a primary player may play blackjack using a video blackjack device. As another example, a primary player may play blackjack over the Internet. A secondary player may bet on the outcomes of the game of the primary player and/or on events within the game of the primary player.
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    •  In various embodiments, a secondary player may participate in the game of a primary player, but take the game in a different direction from the direction in which the primary player took the game. For example, the primary player may be involved in a game which requires a decision on the part of the primary player. The primary player may make a first decision in the game. The secondary player, meanwhile, may be participating in the game, but may prefer a different decision from the decision made by the primary player. Thus, the secondary player may have the opportunity to complete the game in a different fashion than does the primary player. For example, the outcome based on which the secondary player is paid may be different from the outcome based on which the primary player is paid. Note that the secondary player may participate in a game after the primary player has participated in the game. Thus, the secondary player may participate in a historical game. The secondary player may, nevertheless, seek to take a different direction in the game than what happened in the original game.
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    •  The following is an example of some embodiments. A primary player begins play of a game of blackjack. The primary player is dealt a nine and a three as his initial hand. The dealer shows a two face up. The primary player decides to hit. The primary player is dealt a ten and therefore busts because his point total is now 22. The secondary player, prior to seeing the ten which was dealt to the primary player, decides he would rather stand than hit. At this point, the casino server determines what would have happened had the primary player stood. The casino server may then play the dealer's hand, or at least a simulated version of the dealer's hand. The casino server may reveal the dealer's down card to be a 10, providing the dealer with an initial point total of 12. The casino server may then make a hit decision on behalf of the dealer. The casino server may then deal a 10 to the dealer (the same 10 that had gone to the primary player before). The dealer then busts, and the secondary player wins. Thus, both the primary player and the secondary player have started from the same game. However, the primary player and the secondary player have taken the game in different directions by making different decisions at a juncture in the game. As a result, the primary player has lost but the secondary player has won.
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  • 3. In various embodiments, a secondary player may replay and/or redo some aspect of a game of a primary player. +
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    • 3.1. A secondary player may redo a game knowing different information from what the primary player knew. When facing a decision in a game, a primary player may have a given amount of information available to him. For example, in a game of blackjack, a primary player facing a decision to “hit”, “stand”, “double down”, “split” or “surrender”, may know his own two cards and one of the dealer cards. However, the primary player may not know other potentially valuable information, such as the dealer's face-down card, or the next card to be dealt at the top of the deck. In various embodiments, a secondary player participating in the game of a primary player may have access to additional information that the primary player does not or did not have at the time the primary player originally plays or played the game. +
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      • 3.1.1. Know the cards yet to come. In various embodiments, a secondary player participating in the game of a primary player may be presented with information about a card that was unknown to the primary player at the same juncture in the game. For example, a secondary player participating in a game of video poker may be presented with information about the next card to be dealt in the deck. In various embodiments, a secondary player may be presented with information about a card: (a) in the dealer's hand; (b) in an opponent's hand (e.g., in the hand of an opponent in a game of Texas Hold'em); (c) in another primary player's hand (e.g., in the hand of another primary player in a game of blackjack in embodiments where primary player hands are not dealt completely face up); (d) that was burned; (e) that will not be dealt (e.g., a card at the bottom of a deck of cards may have no chance of being dealt in a game); (f) that is unlikely to be dealt (e.g., a card that is in the middle of a deck may be unlikely to be dealt in a game); and so on. Information about a card may include information about a suit of the card, and information about a rank of a card. For example, a secondary player may be told that a card is a heart, or that a card is not a spade. For example, a secondary player may be told that a card is a 10-point value card (e.g., in a game of blackjack). For example, a secondary player may be told that a card's rank is between two and six, or that a card is not a seven. In various embodiments, a secondary player may be told the exact rank and suit of a card, such as a queen of diamonds.
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      • 3.1.2. Know the primary player made a losing decision. In various embodiments, a secondary player may be given information about the consequences of a primary player's decision in a game. For example, the secondary player may be told that the primary player's decision resulted in the primary player losing a game. For example, if a primary player in a game of blackjack decided to hit and busted, a secondary player may be told that the primary player's decision led to the primary player busting. A secondary player may be told that a primary player's decision did not achieve the best possible outcome of a game. Even if a primary player's decision led to a winning outcome, the secondary player may still be told that the primary player's decision did not lead to the best possible outcome. For example, in a game of video poker, if a primary player drew three cards and made a three-of-a-kind, the primary player may have had the potential to draw three cards in a different way and to make a straight-flush. Thus, the primary player may not have obtained the best outcome that he could of. Of course, the primary player may have made the correct decision from his point of view since he did not know that he would have been able to successfully draw to the straight-flush. In various embodiments, a secondary player may be informed of the relative merits of the primary player's decision or strategy in relation to other possible decisions or strategies. For example, regarding a game of video poker, a secondary player may be told that the primary player made the second best possible decision in terms of what outcomes the primary player could have achieved. In various embodiments, the secondary player may be told the merits of a primary player's decision or strategy assuming the primary player had perfect information about what the results of the various decisions or strategies would be. In some embodiments, the primary player will not have or have had perfect information about the consequences of his decisions, so that pronouncements on the merits of the primary player's decisions would not necessarily indicate that the primary player made a bad or wrong decision. In some embodiments, a secondary player may be provided with an indication of the merits of a strategy or decision, whether or not the primary player chose such a decision or strategy. For example, in some embodiments, a secondary player may be told that a particular strategy is a good strategy but not the best possible strategy. For example, a secondary player may be told that a particular strategy is a losing strategy. In various embodiments, the casino may have knowledge about cards that would be unknown to the secondary player in a game. Thus, the casino may be able to inform the secondary player based on such knowledge and thereby provide useful strategy recommendations to the secondary player without explicitly sharing the knowledge.
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    • 3.2. A secondary player may redo a game with the same ordering of a deck of cards, or with a different ordering. In various embodiments, the consequences of all possible primary player decisions are determined in advance, e.g., at the beginning of a game or prior to a decision of a primary player. For example, in a game of video poker, the shuffling and ordering of a deck of cards before a game serves to determine the consequences of any decision the primary player may make in a game. For example, the shuffling leads to a particular order of the deck such that any new cards that the primary player may decide to draw can be determined deterministically by dealing cards from the top of the deck. In various embodiments, the consequences of all combinations of primary player decisions in a game may be determined in advance. For example, in a game of blackjack, the shuffling of a deck before a game may place the cards to be dealt to primary players in a deterministic order. Thus, for a given set of primary player decisions (and given rules dictating what decisions must be made by the dealer), an outcome of the game for each set of primary player decisions may be determined deterministically from the ordering of cards in the deck. In various embodiments, the symbols that will be revealed on each reel of slot machine are determined in advance and prior to the revelation of even a single symbol. For example, the symbol that will be revealed on the third reel of a slot machine may be determined even before the symbol on the first reel of the slot machine is revealed. In various embodiments, the advanced determination of all possible consequences of a primary player's decision may or may not also apply to a possible alternate decision by a secondary player. In various embodiments, the advanced determination of one or more symbols in a game may or may not apply to the secondary player prior to the revelation of the symbols to the primary player or to the secondary player. +
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      • 3.2.1. Same ordering. In various embodiments, the advanced determination of all possible consequences of a primary player's decision may apply in the same way to the possible consequences of a secondary player's decision. In other words, suppose the primary player is or has played a game, and the secondary player is participating in the game. At a given juncture in the game, a particular decision by the secondary player (e.g., “hit”) will have the same consequences for the secondary player as the same particular decision made by the primary player would have for the primary player. For example, a decision by the secondary player to “hit” would result in the secondary player being dealt a four of diamonds. Likewise, a decision by the primary player to hit would result in the primary player being dealt the four of diamonds. It should be noted that for the primary player and the secondary player to experience the same consequence given the same decision may mean that the primary and secondary players will experience the same outcomes or will receive the same symbols or indicia. The actual payouts received by the primary player and the secondary player may differ, in some embodiments, due to differing bets by the primary and secondary players.
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      •  In various embodiments, a secondary player may decide to continue a game that has already been started. The secondary player may decide to join a game, for example, after an event within the game has been resolved. For example, a secondary player may decide to join a game after a first symbol on reel of a slot machine has been revealed, but before symbols on a second reel or on a third reel have been revealed. Once the secondary player decides to join the game, the game may proceed exactly as it had for the primary player who originally played the game (or exactly as it will for the primary player currently involved in the game). In other words, once the secondary player joins the game, the secondary player may receive the same outcome of the game that the primary player does or has. This may occur by virtue of the outcome of the game having been determined in advance, even before the revelation of the first symbol, for example.
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      • 3.2.2. Different ordering. In some embodiments a secondary player may participate in the game of a primary player, make all the same decisions as does the primary player, yet achieve a different result. The consequences of secondary player decisions may not be the same as the consequences of primary player decisions. In some embodiments, the consequences of a secondary player's decisions are determined after the start of a game. For example, the consequences of a secondary player's decisions are determined at the juncture in a game where a secondary player makes a decision, just prior to when a secondary player makes a decision, or even after a secondary player makes a decision. The consequences of possible decisions to be made by a secondary player may be determined by shuffling a remaining portion of a deck of cards from which cards will be dealt in the game in which the secondary player is participating. For example, suppose a primary player has been involved in a game of blackjack and has received an initial two-card hand. The primary player may decide to hit, and may thereby receive a king of clubs dealt from the top of the deck. A secondary player may participate in the same game. The secondary player may also decide to hit after the initial two-card hand has been dealt. However, prior to the second player receiving a new card in his hand, the remaining portion of the deck of cards may be reshuffled. Thus, the secondary player may receive a different card than did the primary player, e.g., the secondary player may receive the five of hearts. Thus, the consequences of the secondary player's decision to hit will have been determined only after the secondary player has made his decision, the determination being made through the reshuffling of the deck of cards.
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      •  In embodiments where the secondary player does not make the same decision as does the primary player, the consequences of the secondary player's decision may not necessarily be determined at the beginning of the game. For example, in a game of video poker, a primary player may decide to discard the fourth and fifth cards from a starting hand. The secondary player, who is participating in the same game as the primary player and therefore has the same starting hand, may instead decide to discard the first and second cards from the starting hand. The primary player may be dealt a ten of diamonds and a queen of clubs. The secondary player may be dealt a jack of hearts and a nine of hearts. The secondary player may receive different cards than does the primary player because the cards to be dealt to the secondary player after the initial hand may be determined using a separate randomization process from that used to determine the cards dealt to the primary player after the initial hand. For example, after the initial cards in a game of video poker have been dealt, the remaining cards in the deck may be reshuffled from the order they had in the deck used in the game of the primary player. In some embodiments, the remaining cards in the deck may be reshuffled in both the game of the primary player and in the game of the secondary player. The two reshufflings may be different from one another, however, so that the order of the remaining cards in the deck for the primary player is different from the order of the remaining cards in the deck for the secondary player.
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      •  In various embodiments, a copy of a game, a deck, or of other game elements may be used in completing a game of a secondary player. For example, when a primary player begins a game, the deck of cards used in the game of the primary player may be copied. The deck may be copied so that the order of the cards within the deck is copied as well. The primary and the secondary player may then play out the remainder of the game from the two separate copies of the deck, without interfering with one another. In one embodiment, both the primary player and the secondary player start out using the same deck to generate, e.g., an initial hand. Thereafter, the remaining portion of the deck (e.g., the part of the deck that hasn't been dealt yet), is copied. This part of the deck may then be reshuffled, or it may not be reshuffled. The secondary player may then play out the remainder of the game using the copied portion of the deck. Thus, the secondary player may play out the remaining portion of the game separately from the primary player without interfering with the game of the primary player.
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      •  In various embodiments, a secondary player may participate in slot machine game. A first symbol from the slot machine game may be revealed. The secondary player may wish to continue the game from the point after the first symbol has been revealed. However, the secondary player may wish to continue the game in a different fashion from that in which the primary player has continued the game. In other words, the secondary player may want the remaining symbols of his outcome to be generated randomly using a different random process than that used to generate the remaining symbols for the primary player. Thus, in some embodiments, the casino (or the gaming device working on behalf of the casino) may randomly determine additional symbols to generate and display for the secondary player, where such symbols need not necessarily be the same as those generated and displayed for the primary player. In various embodiments, a casino may randomly determine a way to generate additional symbols as follows. A casino may determine all outcomes containing the one or more symbols that have already been generated. Such outcomes may be probability weighted so that, for example, it is understood that some are more likely to occur than others. The casino may then select from among the probability weighted outcomes randomly and in proportion to their weightings. Thus, for example, an outcome with twice the probability weighting of another outcome would be twice as likely to be selected.
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    • 3.3. A secondary player may redo the game after the fact. In various embodiments, a secondary player may replay a game from a certain juncture after the game has already been completed. For example, one hour after a game of video poker has been completed, a secondary player may replay the game starting after the initial hand has been dealt but before any decision has been made as to which cards to discard. As described above, a secondary player may replay a game with different outcomes or consequences than those experienced by the primary player, even if the secondary player and the primary player made the same decisions in the game. This is because the replayed game may be replayed with a different randomization process used than was used for the original game. +
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      • 3.3.1. Replay a live game. In various embodiments, a secondary player may replay a game that was originally played with multiple primary players. For example, the secondary player may replay a game of Texas Hold'em poker in which there were originally 9 primary players. The secondary player may wish to play the hand of one of the 9 players. +
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        • 3.3.1.1. The casino uses AI. In various embodiments, in order for the secondary player to have the opportunity to replay a multi-player game, other entities may take the positions of primary players other than the player who the secondary player has replaced. Thus, in some embodiments, the casino may use computer algorithms to take the place of the other primary players. The computer algorithms may be programmed to make decisions in a game, such as in a game of poker. For example, the computer algorithms may include a set of rules detailing what actions to take for any given game situation. When replaying the game, the secondary player may thus play against one or more computer algorithms. In some embodiments, the casino may disclose to the secondary player one or more attributes of a computer algorithm used in a multi-player game. The casino may disclose the rules used by the computer algorithm. The casino may disclose a personality of the algorithm, such as “aggressive” or “tight”. In various embodiments, the casino may be required to disclose one or more attributes of a computer algorithm. The requirements may come from casino regulators, for example.
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        • 3.3.1.2. Secondary player plays against other secondary players. In various embodiments, if a first secondary player replays a game involving multiple primary players, the positions of other primary player may be filled with other secondary players. Thus, in some embodiments, the first secondary player may replay a game against other secondary players. In some embodiments, a first secondary player may replay a game against one or more other secondary players and against one or more computer algorithms.
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        • 3.3.1.3. Other players are not opponents. In some embodiments, a secondary player may replay a game that included multiple primary players. However, the primary players may not have been opponents of one another. For example, a secondary player may replay a game of blackjack from a live table game which originally included 6 primary players. The primary players were not opponents, but rather were competing against the casino. When the secondary player replays the game, the secondary player may wish for positions of the other primary players at the game to be filled as well. Thus, in some embodiments, computer algorithms may fill the places of other primary players. In some embodiments, other secondary players may fill the places of other primary players.
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    • 3.4. A secondary player may make a different decision in real time and diverge into a different game. In various embodiments, a secondary player may participate in a game that is currently being played by a primary player. Thus, the secondary player may participate in a game of a primary player in real time. However, at a particular point in a game, the secondary player may wish to diverge from the course of the primary player. For example, the secondary player may wish to make a different decision in the game than does the primary player. In some embodiments, the secondary player may not know which decision the primary player will make. However, the secondary player may wish to make his own decision anyway, even if it turns out that the decision of the secondary player will be the same as the decision of the primary player. Once the games of both the primary player and the secondary player have finished, the secondary player may rejoin the primary player for the next game. In other words, the secondary player and the primary player in the next game may receive the same symbols, indicia, or other event resolutions. If the primary player finishes his game before the secondary player does, the primary player may be delayed by the casino until the secondary player has an opportunity to bet on the next game.
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    • 3.5. Searching for games with certain characteristics. In various embodiments, a secondary player may search for games with particular characteristics. As described elsewhere herein, a secondary player may search for the games of a particular primary player, for games played at a particular gaming device, for games played at a particular time of day, for games played at a particular casino, for games played right before a big win, and so on. However, the secondary player may also search for games which would give the secondary player an opportunity to proceed from a certain starting point in a beneficial fashion. Once the secondary player finds a game in a search, the secondary player may have the opportunity to play out the game from a certain point in the game, such as from a decision point in the game. +
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      • 3.5.1. The wrong decision was made. In some embodiments, a secondary player may search for a game in which a primary player made a decision that met or failed to meet one or more criteria. A secondary player may search for a game in which the primary player: (a) did not make a decision which generated the highest expected winnings for the primary player; (b) did not make a decision which made the primary player eligible for the highest paying outcome that the primary player could have been eligible for; (c) did not make a decision that followed a generally recommended strategy (e.g., the primary player did not make a decision in blackjack that followed basic strategy); (d) did not make a decision that followed a strategy of interest to the secondary player; and so on. For example, a secondary player may search for a game of blackjack in which the primary player has a point total of 13 with no aces, in which the dealer shows a 3 up-card, and in which the primary player chose to stand. The secondary player may choose to search for such games because, under various rules, the basic strategy recommendation would be to hit. Thus the secondary player will have searched for a game in which the primary player has not made the correct decision according to the recommendations of basic strategy.
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      • 3.5.2. There is a certain starting hand. In various embodiments, a secondary player may search for a game of a primary player in which there was a particular starting hand or in which there was a particular category of starting hand. For example, a secondary player may search for a game of a primary player which was a game of video poker and which included an initial hand with exactly four hearts in it. A secondary player may search for a video poker game in which the primary player has an initial hand with a pair of jacks. A secondary player may search for a video poker game in which the primary player has an initial hand which includes the ace of spades, king of spades, queen of spades, jack of spades, and the four of hearts. A secondary player may search for a game of blackjack in which the primary player had a particular point total, such as 11. A secondary player may search for a game of blackjack in which the primary player had a first point total or a first combination of cards, and in which the dealer showed a second card. For example, the primary player had a point total of 14 and the dealer showed a 4. A secondary player may search for a game of blackjack in which the primary player had already hit twice and still had a point total of less than 14. In various embodiments, a secondary player may search for a game in which one or more symbols occurred at a slot machine. In replaying the game, the secondary player may have the opportunity to obtain additional symbols where such symbols differ from the ones obtained by the primary player in the same game.
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      • 3.5.3. A primary player had a near miss. In various embodiments, the secondary player may search for games in which the primary player had a near miss. The secondary player may search for games in which: (a) an outcome obtained by the primary player differed by X or fewer symbols from a high-paying outcome (e.g., there was only one symbol different between the outcome achieved by the primary player and a jackpot outcome); (b) a primary player had four cards to a royal flush in video poker but did not obtain the fifth card; (c) an outcome obtained by a primary player differed by one symbol from a jackpot outcome, and the symbol necessary for the jackpot outcome was just one position removed on a reel from the pay-line; and so on. A secondary player may keep the symbols of an outcome from a game of a primary player that would contribute to a high-paying outcome, and may have any additional symbols regenerated in an attempt to obtain all the symbols necessary for obtaining the high-paying outcome.
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    • 3.6. Adjust the odds of a game based on what situation the secondary player is starting from. In various embodiments, a secondary player who begins play from the middle of a game, or who begins play in a game after finding out any information about a possible final outcome of the game, may have different probabilities of achieving a given final outcome from what any player would have had at the start of a game. For example, if a secondary player starts a game of video poker at the midpoint after an initial hand with four cards to the royal flush has been dealt, the secondary player will have a greater chance of achieving the royal flush than if the secondary player were starting the game from the beginning. As described herein, a house advantage may be derived from the products of payout ratios and probabilities corresponding to outcomes. Thus, in some embodiments, if the probabilities of paying outcomes go up, then the payout ratios associated with such outcomes must go down in order to maintain a constant house advantage, or in order to maintain any house advantage at all. Thus, in some embodiments, the payout ratios associated with an outcome may change when a secondary player begins a game after some information has been revealed in the game. For example, a payout ratio for a royal flush may be 500 for a game of video poker in which a player starts from the beginning. However, if a player starts the game with an initial hand that contains the ace of spades, king of spades, queen of spades, jack of spades, and 3 of hearts, then the payout ratio for the royal flush may be set to 25 rather than 500. In various embodiments, payout ratios for outcomes may be adjusted for a game started in the middle so that the house advantage for the game started in the middle is the same (or nearly the same) as for the same game started from the beginning. For example, suppose the house edge on a game of video poker is 2% with perfect play. If a secondary player is allowed to start in the middle of a game (e.g., after an initial hand of poker is dealt), then payout ratios for one or more outcomes may be adjusted so that the house advantage over the secondary player is still approximately 2% (e.g., between 1% and 3%). As will be appreciated, the payout ratio for a game may be adjusted in several ways, any of which are contemplated in various embodiments. In various embodiments, a payout ratio may be changed by changing a required bet from a secondary player while maintaining constant payouts on outcomes. In various embodiments, a payout ratio may be changed by changing the payouts for one or more outcomes while maintaining the same required bet amount. In various embodiments, a payout ratio may be changed by changing both the payouts for one or more outcomes, and the amount of a required bet. +
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      • 3.6.1. Odds adjustments in a game of Hold'em. In various embodiments, a secondary player may wish to participate in a game that involves multiple primary players. The secondary player may wish to take the place of a first primary player in the game and to make one or more decisions in the game going forward from a particular point. However, probabilities for possible outcomes of a multi-player game may not be readily quantifiable since the outcomes may depend on the actions of human beings, each with their own independent wills. As such, it may be difficult for the casino to set a payout ratio for a secondary player who is joining in the middle of a multi-player game. Further, the secondary player will not necessarily be interacting with the other primary players in the game (e.g., the primary players in the game other than the primary player whose place the secondary player has taken), since the game may have been played in the past, or since the primary player whose place the secondary player will be filling may still be in the real game. Thus, the secondary player may complete the remainder of the game against computer algorithms which fill in for other primary players. The secondary player may complete the remainder of the game against other secondary players who fill in for other primary players. +
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        • 3.6.1.1. Assume all players will stay in and then decide? In some embodiments, a probability that a secondary player wins a game may be derived or estimated based on an assumption that all other players in a game (e.g., all algorithms filling in for primary players; e.g., all secondary players filling in for primary players) remain in the game. In other words, there may be an assumption that no player folds after the point at which the secondary player has joined the game. Based on an assumption that no further player will fold in a game, the probability that a secondary player will win can be derived in a straightforward fashion. In one embodiment, all possible combinations of additional cards to be dealt can be tested. For example, in a game of Texas Hold'em in which the flop has been dealt already, all possible combinations of turn and river cards may be tested. The proportion of the combinations that lead to a win for the secondary player may then be used to determine the probability that the secondary player will win. In some embodiments, a large number of deals of additional cards in the game may be simulated in order to determine the proportion of such simulations which the secondary player wins. Such a proportion may be used to estimate the probability that the secondary player will win. It will be appreciated that a probability that the secondary player will tie may be determined in a similar fashion to the way a probability of winning may be determined. For example, all possible combinations of additional cards to be dealt may be tested, and the proportion of such combinations which lead to a tie may be used to estimate the probability that the secondary player will tie.
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        • 3.6.1.2. Do a simulation with good AI players? In some embodiments, a probability that a secondary player will win in a multi-player game may be determined using a simulation in which computer algorithms fill in for each of the primary players in the original game. For example, 1000 simulated games may be run using computer algorithms filling in for each of the primary players. The proportion of the time that the computer algorithm wins while filling in at the position desired to be played by the secondary player may be used to determine the probability that the secondary player will win. In some embodiments, the average amount won or lost by the computer algorithm filling in at the position desired to be played by the secondary player may be used to estimate an expected amount that will be won or lost by the secondary player in the game. In various embodiments, once a probability that a secondary player will win and/or tie in a game is determined, a payout ratio for the game may be determined. In various embodiments, once an expected amount that a secondary player will win or lose is determined, a required bet amount for the secondary player may be determined. A payout ratio or required bet amount may be determined for any manner in which a secondary player completes a game from the point or juncture at which the secondary player joins. For example, a payout ratio or required bet amount may be determined whether a secondary player completes a game against other secondary players, whether a secondary player completes a game against computer algorithms, or whether the secondary player completes a game against any combination of the two.
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    • 3.7. If a secondary player does diverge in time, then there may be some catch-up, or the secondary player may skip to the current outcome. For example, the secondary player may be busy on a bonus round while the primary player goes off playing more games. In various embodiments, a secondary player may complete a game in a different manner from the way in which a primary player completes the game. For example, a secondary player may be participating in real time in a game of a primary player. At some point in the game, the primary player may make a first decision and the secondary player may make a second decision. As a result of the different decisions, or for any other reason, the game of the secondary player may last longer than does the game of the primary player. For example, in a game of blackjack, a decision to “hit” by a primary player may lead to the primary player busting, and thereby to an immediate end to the game of the primary player. On the other hand, a decision to “stand” by the secondary player may cause the dealer in the game of the secondary player to make one or more decisions, thereby prolonging the game of the secondary player. If the game of a secondary player lasts longer than the game of a primary player in whose games the secondary player has been participating, then the primary player may on occasion begin a new game before the secondary player has completed an old game. +
        +
      • 3.7.1. The secondary player sits out the next game and joins a future game. In some embodiments, if a primary player begins a new game before a secondary player has completed a prior game he started with the primary player, then the secondary player may sit out the new game. The secondary player may sit out any number of new games until the old game of the secondary player has finished. The secondary player may then join in the next game to be started by the primary player.
        • +
      • 3.7.2. The secondary player gets involved in two games simultaneously. In some embodiments, even if a secondary player has not completed a prior game, the secondary player may still participate in a new game of a primary player. For example, the secondary player may follow the progress of his old and new games using a split-screen view on his terminal. As will be appreciated, the secondary player may be involved in more than one old game even as a new game is started. The secondary player may potentially view the progress of one or more old games along with the new game.
        • +
      • 3.7.3. The old game is finished quickly. In various embodiments, once when a primary player finishes a first game and/or begins a second game, the older game of the secondary player (e.g., the offshoot from the first game of the primary player) may be sped up. For example, the casino may cause outcomes to be generated or displayed more rapidly or instantaneously. For example, rather than showing renditions of cards being dealt, the house may show cards appearing instantly in the hand of the secondary player. In various embodiments, the house may make decisions for the secondary player automatically. For example, the house may make decisions for the secondary player according to one or more strategies, such as according to optimal strategy or according to basic strategy.
        • +
      • 3.7.4. The games of the primary player are stored and the secondary player can participate in the games later on. In various embodiments, a secondary player who is still involved in an older game may not immediately participate in a new game of a primary player. However, data about the new game may be stored by the casino. The secondary player may then, at a later time, choose to participate in the game. The casino may store a record of which games of the primary player the secondary player missed and may then give the secondary player the option of participating in such games.
        • +
      • 3.7.5. The secondary player gets the EV of a game. In various embodiments, a secondary player may not complete a game in the standard fashion, but may rather receive a settlement payment. The settlement payment may be based on an average amount that the secondary player might have expected to win had he completed the game. In various embodiments, a secondary player may be involved in a bonus round (e.g., the bonus round of a slot machine game). The secondary player, rather than playing out the bonus round, may receive a settlement amount for the bonus round. The secondary player may thereby save the time of playing through the entire bonus round, and may therefore be able to participate in a new game that the primary player would otherwise have started without the secondary player's participation.
        • +
      +
      • +
    • 3.8. The secondary player may bet different pay-lines. In various embodiments, a secondary player may choose to bet on different pay-lines from those on which the primary player bet or bets. For example, the primary player may bet a first pay-line and a second pay-line at a slot machine while a secondary player bets only the first pay-line. For example, a primary player may bet a first pay-line at a slot machine while a secondary player bets a first pay-line and a second pay-line. For example, a primary player may bet a first and second pay-line while a secondary player bets a second and third pay-line. For example, a primary player may bet a first pay-line while a secondary player bets a second pay-line at a slot machine.
      • +
    • 3.9. The secondary player may bet different amounts than did the primary player. For example, the secondary player may bet the full three coins rather than just one. In various embodiments, a secondary player may bet a different amount than does a primary player. For example, in a game of poker, such as in a multiplayer game of Texas Hold'em, a secondary player may decide he would rather raise by $20 instead of the $10 raise made by a primary player. Accordingly, the secondary player may play out the remainder of the game, taking the position of the primary player, and playing against computer algorithms taking the place of other primary players. In various embodiments, a primary player may bet a first amount at the start of the game, while the secondary player may bet a second amount on the same game.
      • +
    •  Embodiments described herein, where applicable may be performed based on games played electronically as well as based on games played using physical tokens, devices, instruments, tables, etc. In various embodiments, a primary player may play a game using physical tokens (e.g., physical cards and chips), while a secondary player may participate in the game and view an electronic version of the game. In some embodiments, a primary player may play an electronic version of a game and a secondary player may participate in the game via an electronic version of the game. In some embodiments, primary player may play a physical version of a game and a secondary player may participate in the game using physical tokens. For example, when a secondary player makes a decision in a game that is different from the decision made by the primary player, the a deck of cards used in the primary player's game may be duplicated by taking another physical deck of cards and putting the cards in the same order as are the cards in the deck used in the game of the primary player.
      • +
    +
    • +
+

+ + +The invention claimed is: + + +1. A method comprising: +receiving an indication of a first bet from a first player; +receiving an indication of a second bet from a second player; +determining an ordering of at least one deck of cards; +providing an indication of a hand of a first set of cards from the deck, thereby yielding the hand of the first set of used cards and a first set of unused cards remaining in the deck; +determining, for at least one outcome, a first payout ratio for the first player; +determining, for the at least one outcome, a second payout ratio for the second player, in which the first payout ratio is different from the second payout ratio; +determining, by a processor, a second set of unused cards that includes the cards of the first set of unused cards; +receiving from the first player a first indication of which cards from the hand of the first set of used cards to discard, the quantity of such cards indicated being equal to a first number; +providing an indication of the first number of cards from the first set of unused cards, thereby yielding a first set of replacement cards; +receiving from the second player a second indication of which cards from the hand of the first set of used cards to discard, the quantity of such cards indicated being equal to a second number; +providing an indication of the second number of cards from the second set of unused cards, thereby yielding a second set of replacement cards; +determining a first payment based on the first bet, the hand of the first set of used cards less the cards described by the first indication, and the first set of replacement cards; +determining a second payment based on the second bet, the hand of the first set of used cards less the cards described by the second indication, and the second set of replacement cards; +providing an indication of the first payment to the first player; and +providing an indication of the second payment to the second player. + + + +2. The method of claim 1 in which the cards described by the first indication are different from the cards described by the second indication. + + +3. The method of claim 1 further comprising: +prior to providing the indication of the second number of cards, determining an ordering of the second set unused cards that is different from the ordering of the first set of unused cards. + + + +4. The method of claim 1 in which the first number is different from the second number. + + +5. The method of claim 1, in which determining the first payment includes determining the first payment based on the first payout ratio, and in which determining the second payment includes determining the second payment based on the second payout ratio. + + +6. The method of claim 1, in which the outcome includes hand of the first set of used cards less the cards described by the first indication, and the first set of replacement cards and the hand of the first set of used cards less the cards described by the second indication, and the second set of replacement cards. + + +7. The method of claim 1, further comprising presenting an indication of the second payout ratio to the second player by transmitting an indication from the processor to a mobile device. + + +8. The method of claim 1, further comprising presenting an indication of the first payout ratio to the first player prior to receiving the first bet. + + +9. The method of claim 1, further comprising presenting an indication of the second payout ratio to the second prior to receiving the second bet. + + +10. The method of claim 1, in which providing the indication of the second number of cards includes causing a mobile device to display the second number of cards. + + +11. The method of claim 1, further comprising: +presenting an indication of the first payout ratio to the first player; and +presenting an indication of the second payout ratio to the second player. + + + +12. The method of claim 1 further comprising: +presenting to the second player an indication of the hand of the first set of used cards prior to receiving the second bet. + + + +13. The method of claim 1, further comprising maintaining the same ordering of the second set of unused cards as the first set of unused cards. + + +14. A method comprising: +receiving an indication of a first bet from a first player; +receiving an indication of a second bet from a second player; +determining an ordering of at least one deck of cards; +providing an indication of a hand of a first set of cards from the deck, thereby yielding the hand of the first set of used cards and a first set of unused cards remaining in the deck; +determining, for at least one outcome, a first payout ratio for the first player; +determining, for the at least one outcome, a second payout ratio for the second player, in which the first payout ratio is different from the second payout ratio; +determining, by a processor, a second set of unused cards that includes the cards of the first set of unused cards; +receiving from the first player an indication of a first decision to receive at least one first additional card; +providing an indication of the at least one first additional card from the first set of unused cards, thereby yielding the at least one first additional card and a third set of unused cards; +receiving from the second player an indication of a second decision to receive at least one second additional card; +providing an indication of the at least one second additional card from the second set of unused cards, thereby yielding the at least one second additional card and a fourth set of unused cards; +determining a first payment based on the first bet, the hand of the first set of used cards, and the at least one first additional card; +determining a second payment based on the second bet, the hand of the first set of used cards, and the at least one second additional card; +providing an indication of the first payment to the first player; and +providing an indication of the second payment to the second player. + + + +15. The method of claim 14 further comprising: +prior to providing the indication of the at least one second additional card, determining an ordering of the second set unused cards that is different from the ordering of the first set of unused cards. + + + +16. The method of claim 14 in which a first number of additional cards of the at least one first additional card is different from a second number of additional cards of the at least one second additional card. + + +17. The method of claim 14, in which determining the first payment includes determining the first payment based on the first payout ratio, and in which determining the second payment includes determining the second payment based on the second payout ratio. + + +18. The method of claim 14, in which the outcome includes the hand of the first set of used cards and the first additional card, and the hand of the first set of used cards and the second additional card. + + +19. The method of claim 14, further comprising: +presenting an indication of the first payout ratio to the first player; and +presenting an indication of the second payout ratio to the second player. + + + +20. The method of claim 14 further comprising: +presenting to the second player an indication of the hand of the first set of used cards prior to receiving the second bet. + + + +21. The method of claim 14, further comprising maintaining the same ordering of the second set of unused cards as the first set of unused cards. + + +22. The method of claim 14, further comprising: receiving from the first player a third decision to receive at least one third additional card; providing an indication of the at least one third additional card from the third set of unused cards, thereby yielding the at least one third additional card and a fourth set of unused cards; and in which determining the first payment includes determining the first payment based on the first bet, the hand of the first set of used cards, the at least one first additional card, and the at least one second additional card. + + +23. An apparatus comprising: +a machine readable medium having stored thereon a plurality of instructions that when executed by a computing device cause the computing device to perform a method comprising: +receiving an indication of a first bet from a first player; +receiving an indication of a second bet from a second player; +providing an indication of at least one first set of symbols in a game involving a number of symbols being chosen that is greater than the number of the first set of symbols; +determining, for at least one outcome of the game, a first payout ratio for the first player; +determining, for the at least one outcome of the game, a second payout ratio for the second player, in which the first payout ratio is different from the second payout ratio; +providing an indication of at least one second set of symbols that in combination with the at least one first set of symbols yields the number of symbols; +providing an indication of at least one third set of symbols that in combination with the at least one first set of symbols yields the number of symbols; +determining a first payment based on the combination of the first set of symbols and the second set of symbols; +determining a second payment based on the combination of the first set of symbols and the third set of symbols; +providing an indication of the first payment to the first player; and +providing an indication of the second payment to the second player. + + + +24. The apparatus of claim 23, in which determining the first payment includes determining the first payment based on the first payout ratio, and in which determining the second payment includes determining the second payment based on the second payout ratio. + + +25. The apparatus of claim 23, in which the outcome includes the combination of the first set of symbols and the second set of symbols, and the combination of the first set of symbols and the third set of symbols. + + +26. The apparatus of claim 23, in which the method further comprises: +presenting an indication of the first payout ratio to the first player; and +presenting an indication of the second payout ratio to the second player. + + + +27. The apparatus of claim 23, in which the method further comprises: +presenting to the second player an indication of the first set of symbols prior to receiving the second bet. + + + +28. The apparatus of claim 23, further comprising the computing device. + + + \ No newline at end of file diff --git a/tests/data/uspto/ipg08672134.xml b/tests/data/uspto/ipg08672134.xml new file mode 100644 index 00000000..85dd3eb4 --- /dev/null +++ b/tests/data/uspto/ipg08672134.xml @@ -0,0 +1,783 @@ + + + + + + +US +08672134 +B2 +20140318 + + + + +US +12936568 +20090331 + + +12 + + +EP +08007030 +20080409 + + + +476 + + + +20060101 +A +
B
+65 +D +83 +04 +F +I +20140318 +US +B +H + + +20060101 +A +
B
+65 +D +85 +42 +L +I +20140318 +US +B +H + + + +US +206531 +206 15 +220 2391 + +Child-resistant medication container + + + + +US +6460693 +B1 +Harrold +20021000 + + +cited by applicant + + + + +US +6848577 +B2 +Kawamura et al. +20050200 + + +cited by examiner +US206449 + + + + +US +7549541 +B2 +Brozell et al. +20090600 + + +cited by examiner +US206531 + + + + +US +2004/0045858 +A1 +Harrold +20040300 + + +cited by applicant + + + + +US +2004/0256277 +A1 +Gedanke +20041200 + + +cited by examiner +US206538 + + + + +US +2007/0045150 +A1 +Huffer et al. +20070300 + + +cited by examiner +US206538 + + + + +US +2007/0284277 +A1 +Gnepper +20071200 + + +cited by applicant + + + + +US +2008/0023475 +A1 +Escobar et al. +20080100 + + +cited by examiner +US220 2391 + + + + +US +2009/0178948 +A1 +Reilley et al. +20090700 + + +cited by examiner +US206531 + + + + +US +2009/0184022 +A1 +Coe et al. +20090700 + + +cited by examiner +US206531 + + + + +US +2009/0255842 +A1 +Brozell et al. +20091000 + + +cited by examiner +US206531 + + + + +CA +2428862 +A1 +20041100 + + +cited by applicant + + + + +WO +2004037657 +A2 +20040500 + + +cited by applicant + + + + +WO +2005030606 +A1 +20050400 + + +cited by applicant + + + + +WO +2007030067 +A1 +20070300 + + +cited by applicant + + + +International Search Report, dated May 28, 2009, from corresponding PCT application. + +cited by applicant + + +43 +1 + + +US +206531 + + +US +206 15 + + +US +206223 + + +US +206539 + + +US +206538 + + +US + 53492 + + +US + 53169 + + +US +220 2391 + + + +9 +19 + + + + +US +20110067363 +A1 +20110324 + + + + + + + +Sprada +Peter John +
+London +GB +
+ + +GB + + + + +Prasser +Robert +
+Guttaring +AT +
+ + +AT + + + + + + +Sprada +Peter John +
+London +GB +
+ + + + +Prasser +Robert +
+Guttaring +AT +
+ + + + + + +Young & Thompson +
+unknown +
+ + + + + + + +Merck Serono SA +03 +
+Coinsins +CH +
+ + + + + +Yu +Mickey +3728 + + +Ortiz +Rafael + + + + +WO +PCT/IB2009/005131 +00 +20090331 + + +20101203 + + + + +WO +WO2009/125267 +A +20091015 + + + + +

The child-resistant medication container includes: +

    +
  • +
      +
    • a housing having an open end,
      • +
    • a support slidably mounted in the housing for supporting medication,
      • +
    • first locking element for locking the support in the housing and for unlocking the support so that the support may be slid to the outside of the housing through the open end, the first locking element including a first locking member coupled to the housing and a second locking member coupled to the support, the first and second locking members being engageable with each other, and
      • +
    • at least one button operable to act on the first locking element, the at least one button including a first button operable to disengage the first and second locking members,
      • +
    • second locking element for maintaining engagement between the first and second locking members, and
      • +
    • a second button operable to act on the second locking element to permit disengaging the first and second locking members by operating the first button.
      • +
    +
    • +
+

+ + +
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+
+embedded image +
+ + + +

The present invention pertains to a container for the delivery of medication, more particularly to a child-resistant medication container.

+

Solid medications, in the form of tablets, pills, capsules or the like, are often stored in a blister card, which consists of a sheet, generally of plastic material, defining chambers (blisters) and on the back side of which a sealant film such as an aluminium or a paper foil is fixed. A medication dose contained in a blister may be released by pressing on the blister to collapse the latter and puncture the sealant foil.

+

To protect children and others from unsupervised access to medication, child-resistant medication containers have been proposed which comprise a housing containing medication and which require, for their being opened, a sequence of operations which a child normally cannot perform or would not think to perform.

+

In particular, the International patent applications WO 2004/037657 and WO 2005/030606 describe child-resistant medication containers comprising a housing and a blister card slidably mounted in the housing but locked therein. The blister card may be unlocked and slid out of the housing through an open end thereof by pressing one button provided at a top wall of the housing and by pulling the blister card while the button is pressed.

+

The American patent application US 2007/0284277 describes a child-resistant medication container comprising a housing and a tray slidably mounted in the housing but locked therein. The tray contains tablets. The tray may be unlocked and slid out of the housing through an open end thereof by simultaneously pressing and then sliding two lateral slide buttons.

+

The American patent application US 2004/0045858 describes a child-resistant medication container comprising a housing and a blister card slidably mounted in the housing but locked therein. The blister card may be unlocked and slid out of the housing through an open end thereof by simultaneously pressing two lateral push buttons and then actuating an optional lever to push the blister card or holding the housing downward to allow the blister card to drop out.

+

The containers described in the above-mentioned patent applications do not have a very high child resistance because only two successive actions are required to open the container.

+

The American patent application US 2004/0256277 describes a child-resistant medication container comprising a housing and a blister card slidably mounted in the housing but locked therein. The blister card may be unlocked and slid out of the housing through an open end thereof by pressing two lateral push buttons and then pulling the blister card while the lateral push buttons are pressed. To enable its being pulled, the blister card defines a tab which projects out of the housing through the open end and which may be seized by the user. This container does not have a very high child resistance because simultaneously pressing two lateral buttons is rather intuitive and only two successive actions are required to open it. Moreover, in this container, the blister card is permanently exposed, leaving the possibility for an unauthorised person to open the blisters with a tool such as a knife and access the medication.

+

The International patent application WO 2007/030067 describes a child-resistant medication container comprising a housing and a blister card. The housing is open in its top portion so as to permanently expose the blister card and has a bottom wall with holes. The blister card is slidably mounted in the housing between a locked position in which the blisters are offset relative to the holes and an unlocked position in which the blisters are aligned with the holes to enable the release of the medication through the holes. An operating member having two finger receiving regions locks the blister card when in a first position and unlocks the blister card when in a second position. The passage from the first position to the second position of the operating member is achieved by successively pushing the two finger receiving regions in two different directions. The operating member, irrespective of its position, retains the blister card in the housing. Since the blister card is permanently exposed, access to the medication using a tool is possible and the security of this container is therefore not very high.

+

The U.S. Pat. No. 6,460,693 describes a child-resistant medication container comprising a housing and a tray slidably mounted in the housing but locked therein. The tray contains a blister card. The tray may be unlocked by being pushed inward into the housing and then by pressing one button provided at the top wall of the housing. A drawback of this container is that it requires a bulky locking/unlocking mechanism at its rear part. This mechanism notably takes up a substantial portion of the length of the container.

+

The present invention aims at providing a medication container which may have a high child resistance without increasing to a large extent the size of the container.

+

To this end, the present invention proposes a container for the delivery of medication, comprising: +

    +
  • +
      +
    • a housing having an open end,
      • +
    • a support for supporting medication, said support being slidably mounted in the housing,
      • +
    • first locking means for locking the support in the housing and for unlocking the support so that the support may be slid to the outside of the housing through the open end, said first locking means comprising a first locking member coupled to the housing and a second locking member coupled to the support, said first and second locking members being engageable with each other, and
      • +
    • at least one button operable to act on the first locking means, said at least one button comprising a first button operable to disengage the first and second locking members,
      • +
    +
    • +
+

+

characterised by further comprising: +

    +
  • +
      +
    • second locking means for maintaining engagement between the first and second locking members, and
      • +
    • a second button operable to act on the second locking means to permit disengaging the first and second locking members by operating the first button.
      • +
    +
    • +
+

+

Typically, the first button is operable to act on the first locking member to disengage the first and second locking members.

+

The second locking means may be arranged to block the first locking member when an attempt is made to operate the first button while the second button is in a rest position.

+

Advantageously, the first and second buttons are operable in respective non-parallel directions.

+

The first and second buttons are preferably operable independently of the support, i.e. without causing a movement of the support.

+

The first and second buttons are preferably part of respective distinct pieces that are movable relative to each other.

+

Typically, the first button is a push button and the second button is a slide button.

+

In an embodiment, the second locking means comprise a surface coupled to the second button and a stop projection coupled to the first locking member, said surface is arranged to block said stop projection when an attempt is made to operate the first button while the second button is in a rest position, and said surface comprises a hole into which the stop projection enters when the second button is in an operated position and the first button is moved to its operated position.

+

Said surface may further comprise a stop projection which is blocked by the stop projection coupled to the first locking member when the first button is in an intermediate position where the stop projection coupled to the first locking member is blocked by said surface, to prevent the second button from being operated.

+

In another embodiment, the second locking means comprise first teeth coupled to the second button and second teeth coupled to the first button, the second teeth are out of engagement with the first teeth when the first and second buttons are in a rest position but engage the first teeth when an attempt is made to operate the first button while the second button is in a rest position, to block the first button in an intermediate position where the first locking member still engages the second locking member while locking the second button, and the first teeth are not on the path of the second teeth when the second button is in an operated position thus permitting the first button to be moved from its rest position to an operated position where the first locking member is disengaged from the second locking member.

+

Advantageously, the first button is provided at a side wall of the housing, said at least one button further comprises a third button provided at another, opposite side wall of the housing, the first locking means further comprise a third locking member coupled to the housing and a fourth locking member coupled to the support, said third and fourth locking members being engageable with each other, and the third button is operable to disengage the third and fourth locking members.

+

The third button may be operable to act on the third locking member to disengage the third and fourth locking members.

+

Preferably, the first and third buttons are arranged to unlock the support only when simultaneously in an operated position.

+

The container may further comprise third locking means for maintaining engagement between the third and fourth locking members and a fourth button operable to act on the third locking means to permit disengaging the third and fourth locking members by operating the third button.

+

The third button may be operable to act on the third locking member to disengage the third and fourth locking members and the third locking means may be arranged to block the third locking member when an attempt is made to operate the third button while the fourth button is in a rest position.

+

Typically, the first and third buttons are push buttons and the second and fourth buttons are slide buttons.

+

The second and fourth buttons may be provided at a top wall of the housing.

+

In an embodiment, the second locking means comprise a first surface coupled to the second button and a first stop projection coupled to the first locking member, the first surface is arranged to block the first stop projection when an attempt is made to operate the first button while the second button is in a rest position, the first surface comprises a hole into which the first stop projection enters when the second button is in an operated position and the first button is moved to its operated position, the third locking means comprise a second surface coupled to the fourth button and a second stop projection coupled to the third locking member, the second surface is arranged to block the second stop projection when an attempt is made to operate the third button while the fourth button is in a rest position, and the second surface comprises a hole into which the second stop projection enters when the fourth button is in an operated position and the third button is moved to its operated position.

+

The first surface may further comprise a third stop projection which is blocked by the first stop projection when the first button is in an intermediate position where the first stop projection is blocked by the first surface, to prevent the second button from being operated, and the second surface may further comprise a fourth stop projection which is blocked by the second stop projection when the third button is in an intermediate position where the second stop projection is blocked by the second surface, to prevent the fourth button from being operated.

+

In another embodiment, the second locking means comprise first teeth coupled to the second button and second teeth coupled to the first button, the second teeth are out of engagement with the first teeth when the first and second buttons are in a rest position but engage the first teeth when an attempt is made to operate the first button while the second button is in a rest position, to block the first button in an intermediate position where the first locking member still engages the second locking member while locking the second button, the first teeth are not on the path of the second teeth when the second button is in an operated position thus permitting the first button to be moved from its rest position to an operated position where the first locking member is disengaged from the second locking member, the third locking means comprise third teeth coupled to the fourth button and fourth teeth coupled to the third button, the fourth teeth are out of engagement with the third teeth when the third and fourth buttons are in a rest position but engage the third teeth when an attempt is made to operate the third button while the fourth button is in a rest position, to block the third button in an intermediate position where the third locking member still engages the fourth locking member while locking the fourth button, and the third teeth are not on the path of the fourth teeth when the fourth button is in an operated position thus permitting the third button to be moved from its rest position to an operated position where the third locking member is disengaged from the fourth locking member.

+

In another embodiment, the second and fourth buttons are one and a same button.

+

According to still another embodiment, the container comprises, besides the first and second locking means and the first and second buttons as defined in the beginning, third locking means for locking the second locking means and a third button operable to act on the third locking means to unlock the second locking means and permit acting on the second locking means by operating the second button.

+

The third locking means may comprise a third locking member coupled to the second locking means and a fourth locking member coupled to the third button, these third and fourth locking members being engaged with each other when the second and third buttons are in a rest position and being disengageable from each other by operating the third button.

+

Typically, the third and fourth locking members each comprise teeth.

+

The first and third buttons may be provided at side walls of the housing and the second button may be provided at a top wall of the housing.

+

The first and third buttons may be push buttons and the second button may be a slide button.

+

The first locking means may further comprise a fifth locking member coupled to the housing and a sixth locking member coupled to the support and the third button may be arranged to also disengage the fifth and sixth locking members when operated.

+

The third button may be arranged to act on the fifth locking member when operated, to disengage the fifth and sixth locking members.

+

In all embodiments above, the various buttons may each be subject to the action of elastic return means. Moreover, said buttons may each be operable independently of the support and may be part of respective distinct pieces that are movable relative to each other.

+

The container may further comprise a cap coupled to the support and which closes the open end of the housing when the support is in its locked position.

+

Typically, the support supports at least one blister card containing the medication, for example several separate blister cards containing the medication and placed side-by-side. The blisters of said at least one blister card are preferably fully encased in the housing when the support is in its locked position.

+

The medication may be in the form of capsules or tablets.

+

Advantageously, the container contains an even number of tablets.

+

The container may contain 2 to 14 tablets, preferably 6 to 10 tablets, most preferably 10 tablets.

+

The container according to the invention is particularly suitable for containing drug for the treatment of cancer, drug having an immediate toxic effect or drug having an effect on the immune system.

+

According to a particular embodiment, the medication comprises Cladribine or derivatives thereof.

+

The container according to the invention typically has a wallet size, preferably a length between 119 and 222 mm, a width between 52 and 98 mm and a thickness between 10 and 21 mm.

+

The present invention further provides a kit comprising separately a container as defined above and medication. Preferably, the kit comprises a description, for example on a separate sheet, containing information on how to handle the container and on the administration and dosing of the medication.

+

The present invention further provides a method of opening a container as defined above comprising first and third buttons and a second button for blocking/unblocking the first and third buttons, the method being characterised by comprising the following steps: +

    +
  • +
      +
    • holding the housing,
      • +
    • operating the second button,
      • +
    • operating the first and third buttons while the second button is in its operated position, and
      • +
    • pulling the support while the first and third buttons are in their operated position.
      • +
    +
    • +
+

+

The present invention further provides a method of opening a container as defined above comprising a first button, a second button for blocking/unblocking the first button and a third button for blocking/unblocking the second button, the method being characterised by comprising the following steps: +

    +
  • +
      +
    • holding the housing,
      • +
    • operating successively the third button, the second button and the first button, and
      • +
    • pulling the support while the first and third buttons are in their operated position.
      • +
    +
    • +
+

+ + + +

Other features and advantages of the present invention will be apparent upon reading the following detailed description of preferred embodiments made with reference to the appended drawings in which:

+

FIG. 1 is a perspective view of a child-resistant medication container according to a first embodiment of the invention, in an open position;

+

FIG. 2 is a top view of the child-resistant medication container according to the first embodiment of the invention, in a closed position;

+

FIGS. 3 and 4 show in top view a sequence of operations required to open the child-resistant medication container according to the first embodiment of the invention;

+

FIG. 5 is a diagrammatic top view of the internal mechanism for opening/closing the child-resistant medication container according to the first embodiment of the invention;

+

FIGS. 6 to 8 diagrammatically show in top view the successive configurations of the internal mechanism of FIG. 5 during the said sequence of operations;

+

FIG. 9 is a bottom view of a child-resistant medication container according to a second embodiment of the invention, in a closed position;

+

FIG. 10 is a partial sectional view showing in an enlarged manner a detail of FIG. 9, namely a locking member located on a housing of the container and engaged with a locking notch located on a tray of the container;

+

FIG. 11 is a partial sectional view showing the locking member and locking notch of FIG. 10 in a position where they are disengaged from one another;

+

FIG. 12 is a bottom view of the internal mechanism for opening/closing the child-resistant medication container according to the second embodiment of the invention, said mechanism being shown in a rest position;

+

FIG. 13 is a bottom view of the internal mechanism for opening/closing the child-resistant medication container according to the second embodiment of the invention, said mechanism being shown in a position corresponding to a wrong opening action by the user;

+

FIGS. 14 and 15 are bottom views of the internal mechanism for opening/closing the child-resistant medication container according to the second embodiment of the invention, said mechanism being shown respectively during right successive actions performed by the user to open the container;

+

FIG. 16 is a top view of a child-resistant medication container according to a variant of the first and second embodiments;

+

FIG. 17 is a bottom view of the internal mechanism for opening/closing a child-resistant medication container according to a third embodiment of the invention, said mechanism being shown in a rest position; and

+

FIGS. 18 and 19 are bottom views of the internal mechanism for opening/closing the child-resistant medication container according to the third embodiment of the invention, said mechanism being shown respectively during successive actions performed by the user to open the container.

+ + + +

With reference to FIGS. 1 and 2, a child-resistant medication container according to a first embodiment of the invention comprises a housing 1 made of a top part and a bottom part assembled together. The housing 1 is of a generally parallelepipedic shape and comprises a top wall 2 and a base wall 3 opposite to one another, a closed end 4 and an open end 5 opposite to one another, and two opposite side walls 6. A tray 7 supporting blisters 8 is slidably guided in the housing 1 along a longitudinal axis A of the container. The tray 7 may take a locked position, corresponding to a closed position of the container, in which the tray 7 is locked inside the housing 1, preventing access to the blisters 8 (FIG. 2). The tray 7 may also be unlocked and then slid toward the outside of the housing 1 through the open end 5 to permit access to the blisters 8 (open position of the container; FIG. 1). A cap 9 is coupled to the front end of the tray 7. The cap 9 closes the open end 5 when the tray 7 is in its locked position. The cap 9 may be of one-piece construction with the tray 7.

+

Each blister 8 contains a dose of solid medication. The tray 7 comprises holes (not shown) under the blisters 8 through which the doses of solid medication may be expelled when the container is in its open position, by applying a pressure on the blisters 8. In the example shown, the blisters 8 are arranged in pairs, each pair being defined by a separate blister card 10 fixed, e.g. snapped, on the tray 7. The blister pairs or cards 10 are aligned side by side so as to form two blister rows as shown in FIG. 1. Such an arrangement of the blisters 8, comprising several separate blister cards 10, facilitates the management of the quantities of medication and permits reducing medication wastage. In a variant, however, a single blister card could be provided on the tray 7, as is conventional.

+

The housing 1 includes opposite openings 11 in the side walls 6 and an opening 12 in the top wall 2. Push buttons 13 are provided in the openings 11, respectively, and a slide button 14 is provided in the opening 12. In the context of the invention, the term “button” is to be understood in a broad sense, as covering any part on which a finger can rest to transmit a force. The lateral push buttons 13 are operable by being moved substantially perpendicularly to the longitudinal axis A toward the inside of the housing 1. The slide button 14 is operable by being moved along the longitudinal axis A. To open the container, the user must perform the following sequence of operations: +

    +
  • +
      +
    • operate the slide button 14 as shown by arrow 15 in FIG. 3,
      • +
    • then operate the lateral push buttons 13 as shown by arrows 16 in FIG. 4 while maintaining the slide button 14 in its operated position,
      • +
    • and then pull the tray 7 as shown by arrow 17 while maintaining the lateral push buttons 13 in their operated position. +
      +Once the lateral push buttons 13 are operated, the user may release the slide button 14. Maintaining the lateral push buttons 13 in their operated position is required only at the beginning of pulling the tray 7, to unlock the latter. Then the tray 7 may be freely moved toward the outside of the housing 1 without maintaining pressure on the push buttons 13. Typically, the container is held in one hand with the thumb and another finger of the hand acting on the lateral push buttons 13 and a finger of the other hand acting on the top slide button 14, the said other hand being used to pull the tray 7 after releasing the top slide button 14. Recesses 18 are provided in the top and base walls 2, 3 at the open end 5 to expose surface portions 19 of the cap 9 when the tray 7 is in its locked position and to thereby facilitate seizing the tray 7. +
      • +
    +
    • +
+

+

It will thus be appreciated that three successive actions have to be performed by the user, in a determined order, to unlock and move the tray 7. As will be explained below, operating the lateral push buttons 13 while the slide button 14 is not in its operated position is not possible because the slide button 14, in its rest position, blocks the lateral push buttons 13 and prevents them from moving beyond an intermediate pressed position in which the tray 7 is still locked. Operating the slide button 14 while a pressure is applied on one or two of the lateral push buttons 13 is not possible either, because the lateral push buttons 13, in their intermediate pressed position, block the slide button 14. Merely operating the slide button 14 frees the lateral push buttons 13 but does not free the tray 7. Simultaneous pressure holding on the operated lateral push buttons 13 and pulling action on the tray 7 are required to initiate the movement of the tray 7. A friction is preferably provided between the tray 7 and the housing 1 so that the tray 7 cannot be moved merely by inclining the container downward while the lateral push buttons 13 are in their operated position.

+

A child will generally not have the manual dexterity nor the cognitive knowledge to perform the above-described sequence of operations required to unlock and move the tray 7. Moreover, the housing 1 may be made sufficiently wide for the lateral buttons 13 to be separated by a large distance, thereby making it impossible for a child to hold the container in one hand and to press the lateral buttons 13 while holding the slide button 14 in its operated position or to pull the tray 7 while pressing the lateral buttons 13. It should also be noted that in the closed position of the container the blisters 8 are fully encased in the housing 1 and thus cannot be accessed.

+

The internal mechanism allowing the above-described sequence of operations is diagrammatically shown in FIGS. 5 to 8. The slide button 14 projects from and is rigidly connected to a plate 20 that is slidably guided in the housing 1 above the blisters 8 along the longitudinal axis A of the container. A return spring 21 is provided between the front end of the plate 20 and a bearing part 22 rigidly connected to the inner face of the top wall 2 of the housing 1. The return spring 21 may be a leaf spring made of one-piece construction with the plate 20 and the button 14, as shown. Alternatively, it could be a conventional metal leaf or helical spring disposed between the front end of the plate 20 and the bearing part 22. The two side surfaces 23 of the plate 20 along the longitudinal axis A of the container include respective opposite holes 24 and, between the holes 24 and the front end of the plate 20, respective stop projections 25.

+

Each lateral push button 13 is part of a piece 26 comprising, inside the housing 1, a locking part 27 and a return U-bent leaf spring 28 extending between a corresponding side surface 23 of the plate 20 and the button 13. The piece 26 is held by a part 29 rigidly connected to the housing 1. The locking part 27 comprises a stop projection 30 extending toward the inside of the housing 1 perpendicularly to the longitudinal axis A and a locking member 31 extending toward the outside of the housing 1 perpendicularly to the longitudinal axis A. The locking member 31 engages a corresponding locking member 32 of the cap 9 to lock the tray 7, as is shown in FIG. 5. The locking member 32 extends toward the inside of the housing 1 perpendicularly to the longitudinal axis A and is located at the end of an arm 36 of the cap 9. The stop projection 30 has two functions. A first function is to come into abutment against the corresponding side surface 23 of the plate 20 when the push button 13 is pressed and the slide button 14 is in its rest position, shown in FIG. 5, to prevent the piece 26 and the push button 13 from going beyond the aforementioned intermediate pressed position in which the locking member 31 still engages the locking member 32, in other words to prevent disengagement of the locking members 31, 32. The second function is to block the stop projection 25 when the slide button 14 is moved toward its operated position while the push button 13 is held in its intermediate pressed position, thereby preventing the slide button 14 from reaching its operated position.

+

When the push buttons 13 are in their rest position, the stop projections 30 do not interrupt the paths of the stop projections 25 and therefore do not hinder the movement of the slide button 14, which can thus be moved along the longitudinal axis A of the container up to its operated position. When the slide button 14 is in its operated position (FIG. 6), the stop projections 30 face the holes 24. In this configuration, if the lateral push buttons 13 are pressed, the stop projections 30 will enter the holes 24, enabling the pieces 26 and push buttons 13 to go beyond the aforementioned intermediate position and to reach their operated position, shown in FIG. 7. In this operated position, the locking members 31 are out of engagement with the locking members 32 and the tray 7 is therefore free. The tray 7 may thus be slid out to expose the blisters 8 (FIG. 8). The side surfaces 23 of the plate 20, with their holes 24 and their surfaces of contact with the stop projections 30, thus constitute locking means serving to prevent the locking members 31 from disengaging from the locking members 32 or to enable such a disengagement.

+

So long as the lateral push buttons 13 are held in their operated position, the slide button 14 is blocked in its operated position due to the cooperation between the stop projections 30 and the holes 24. Once the buttons 13, 14 have been released by the user, they are returned to their respective rest positions by the springs 28, 21. The tray 7 may be returned to its locked position merely by pushing it back toward the inside of the housing 1. The internal faces of the side walls 6 of the housing 1 have recesses 33. The locking members 31, 32 have slanted surfaces 34, 35 (see FIG. 8) that cooperate when the tray 7 is pushed back while the buttons 13 are in their rest position, causing the arms 36 of the cap 9 to deform externally into the recesses 33 until the locking members 32 recover their locked position in which they engage the locking members 31.

+

With reference to FIG. 9, a child-resistant medication container according to a second embodiment of the invention comprises a housing 40 having a top wall 41, a base wall 42 opposite to the top wall 41, a closed end 43, an open end 44 opposite to the closed end 43, and two opposite side walls 45. A tray 46 supporting blisters (not shown) is slidably guided in the housing 40 along a longitudinal axis A of the container between two guiding internal longitudinal walls 47 of the housing 40. In the illustrated example, the base wall 42 of the housing 40 is transparent and the tray 46 is therefore visible when the container is viewed from below. As in the first embodiment, the tray 46 may take a locked position (FIG. 9) corresponding to a closed position of the container, in which the tray 46 is locked inside the housing 40, preventing access to the blisters. The tray 46 may also be unlocked and slid toward the outside of the housing 40 through the open end 44 to permit access to the blisters (open position of the container). The tray 46 comprises holes 48 under the blisters through which the medication contained in the blisters may be expelled when the container is in its open position, by applying a pressure on the blisters. A cap 49 is coupled to the front end of the tray 46. The cap 49 closes the open end 44 when the tray 46 is in its locked position. The cap 49 may be of one-piece construction with the tray 46.

+

The housing 40 includes opposite openings in the side walls 45 in which push buttons 50, 51 are provided and an opening in the top wall 41 in which a slide button 52 is provided. The lateral push buttons 50, 51 are operable by being moved perpendicularly to the longitudinal axis A toward the inside of the housing 40. The slide button 52 is operable by being moved along the longitudinal axis A. To open the container, the user must perform the same sequence of operations as in the first embodiment, namely: +

    +
  • +
      +
    • operate the slide button 52,
      • +
    • then operate the lateral push buttons 50, 51 while maintaining the slide button 52 in its operated position,
      • +
    • and then pull the tray 46 while maintaining the lateral push buttons 50, 51 in their operated position.
      • +
    +
    • +
+

+

The internal mechanism allowing the above-described sequence of operations in this second embodiment is shown in FIGS. 10 to 15. The lateral push buttons 50, 51 are part of two respective pieces 53, 54. For the purpose of clarity, the pieces 53, 54 are shown with different line thicknesses in the drawings. Each piece 53, 54 comprises a pair of return springs 55, 56 extending from opposite sides of the corresponding button 50, 51. The respective free ends of the springs 55 bear against the external face of one of the guiding walls 47. The respective free ends of the springs 56 bear against the external face of the other guiding wall 47. Each piece 53, 54 comprises a U-shaped flat portion 57, 58 located inside the housing 40 on or near the internal face of the top wall 41, i.e. between the blisters and the top wall 41. The U-shaped flat portions 57, 58 are oriented along the longitudinal axis A of the container in an opposite manner to each other. Each U-shaped flat portion 57, 58 is so wide as to connect the corresponding button 50, 51 provided on one side of the tray 46 to a locking member 59, 60 of the piece 53, 54 provided on the other side of the tray 46. Each locking member 59, 60 is in the form of a hook projecting from the flat portion 57, 58 toward the base wall 42. In the closed position of the container, each locking member 59, 60 engages a respective notch 61, 62 formed in the respective lateral side of the tray 46 to lock the latter (FIGS. 9 and 10).

+

Each piece 53, 54 further comprises a portion 63, 64 located in the same plane as the U-shaped flat portion 57, 58 and projecting toward the inside of the housing 40 in a direction perpendicular to the longitudinal axis A of the container from the one of the two legs of the U-shaped flat portion 57, 58 that is closer to the button 50, 51. Each projecting portion 63, 64 is terminated by teeth 65, 66 aligned in a direction parallel to the longitudinal axis A. The slide button 52 comprises an external portion (shown in dashed line) located on the external face of the top wall 41 to be directly accessible to the user and an internal portion 67 located and guided inside the housing 40. A return spring 68 which may be of one-piece construction with the piece 54 is attached at one of its ends to the U-shaped flat portion 58 and at its other end to the internal portion 67 of the slide button 52. The internal portion 67 comprises first teeth 69 at one its lateral sides and second teeth 70 at its other lateral side. In the rest position of the slide button 52 and of the lateral buttons 50, 51, the first teeth 69 respectively face the spaces between the teeth 65 of the piece 53 but do not engage them because a distance is provided in a direction perpendicular to the longitudinal axis A between the teeth 65 and the teeth 69. Likewise, in the rest position of the slide button 52 and of the lateral buttons 50, 51, the second teeth 70 respectively face the spaces between the teeth 66 of the piece 54 but do not engage them because a distance is provided in a direction perpendicular to the longitudinal axis A between the teeth 66 and the teeth 70. In the rest position of the slide button 52 (FIG. 12), if the lateral buttons 50, 51 are pressed, the pieces 53, 54 are moved in opposite directions perpendicular to the longitudinal axis A, namely in directions in which the locking members 59, 60 start to disengage from the notches 61, 62 respectively. However, the movement of the pieces 53, 54 is stopped in an intermediate position thereof where the teeth 65, 66 have respectively engaged the teeth 69, 70, i.e. have entered the spaces between the teeth 69, 70, and rest against the bottom of said spaces (FIG. 13). In this intermediate position, the locking members 59, 60 are not fully disengaged from the notches 61, 62 and, therefore, the tray 46 remains locked. Moreover, the slide button 52 is locked by the teeth 65, 66 engaging the teeth 69, 70 and, therefore, cannot be operated by the user.

+

From the configuration of the container where the slide button 52 and the lateral buttons 50, 51 are in their rest position (FIG. 12), the slide button 52 may be operated, i.e. moved along the longitudinal axis A up to a position where it is in abutment against a bearing portion (not shown) of the top wall 41 (FIG. 14). In this operated position, the teeth 69, 70 are no longer on the path of the projecting portions 63, 64, respectively, and the pieces 53, 54 may thus be moved beyond their intermediate position if the lateral buttons are pressed (FIG. 15). The limit position of the lateral buttons 50, 51, more generally of the pieces 53, 54, is defined by the teeth 65, 66 abutting the sides of the internal portion 67 of the slide button 52 or by the lateral buttons 50, 51 abutting the internal walls 47 of the housing 40. This limit position is the operated position of the lateral buttons 50, 51. In this position, the locking members 59, 60 are fully disengaged from the notches 61, 62 respectively (FIG. 11). The tray 46 is therefore unlocked and may be pulled to the outside of the housing 40 through the open end 44.

+

One will note that full operation of the slide button 52 is necessary for unlocking the lateral buttons 50, 51, i.e. for allowing them to go beyond their intermediate position. If indeed the slide button 52 is not fully operated, some of the teeth 69 (respectively 70) will remain on the path of the projecting member 63 (respectively 64) and pressing the lateral buttons 50, 51 will result in these buttons being stopped in their intermediate position and in the slide button 52 being locked.

+

As soon as the lateral buttons 50, 51 are released from their operated position or from their intermediate position, the return springs 55, 56 bring them back to their rest position. Likewise, the slide button 52 is returned to its rest position by the return spring 68 as soon as it is released if the lateral buttons 50, 51 are in their rest position. When the lateral buttons 50, 51 are in their operated position, the slide button 52 is retained in its operated position by the projecting portions 63, 64 as shown in FIG. 15.

+

FIG. 16 shows a variant of the first and second embodiments in which the sole slide button 14, respectively 52, has been replaced by two slide buttons 14a, 14b, respectively 52a, 52b. These slide buttons are located on the top wall of the housing and are both operable along the longitudinal axis A. The internal locking/unlocking mechanism is identical to that of the first or the second embodiment described above, except that the part 20, respectively 67, is divided into two separate and independent parts rigidly connected with the slide buttons respectively and each comprising locking means for a respective lateral button.

+

In each of the first and second embodiments, although it is preferable to have two lateral buttons and two corresponding locking members, one of these buttons and the corresponding piece could be suppressed. In this case, a high level of security would nevertheless still be achieved because a specific sequence of operations, namely operating a first button and then a second button, would be required to unlock the tray. The fact that said first and second buttons are operable in non-parallel directions still increases the security or child resistance. Moreover, at least one of said first and second buttons could be concealed, for example by being recessed with respect to the corresponding wall of the housing.

+

FIG. 17 shows a child-resistant medication container according to a third embodiment of the invention. The container according to this third embodiment has a housing (not shown), a tray (not shown) for supporting blisters and an opening mechanism comprising a slide button 80 and pieces 81, 82 defining lateral push buttons 83, 84 respectively. The housing, the tray and the piece 81 are respectively identical to the housing 40, the tray 46 and the piece 53 of the second embodiment. In particular, the piece 81 comprises a projecting portion 85 terminated by teeth 86 corresponding to the projecting portion 63 and its teeth 65 of the second embodiment. The piece 82 differs from the piece 54 of the second embodiment in that it does not have the projecting portion 64 but has another projecting portion 87 terminated by teeth 88 and located on the same side of the slide button 80 as the projecting portion 85 of the other piece 81. The slide button 80 differs from the slide button 52 of the second embodiment in that it does not have the teeth 70 but comprises, in addition to teeth 89 identical to the teeth 69 of the second embodiment, teeth 90 located on the same side as the teeth 89.

+

In the rest position of the buttons 80, 83, 84, the teeth 90 are engaged by the teeth 88 so that the slide button 80 is locked. Moreover, the lateral button 83 is locked by the slide button 80, i.e. cannot be operated beyond an intermediate position where the teeth 86 engage the teeth 89 and where the corresponding locking member, designated by the reference numeral 91, still engages the corresponding locking notch of the tray. Pressing the lateral button 84 disengages the teeth 88 from the teeth 90 and frees the slide button 80 (FIG. 18). This also disengages the locking member of the piece 82, designated by the reference numeral 92, from the corresponding locking notch of the tray. However, at this stage, the tray remains locked by the locking member 91 of the piece 81 still engaging the corresponding locking notch of the tray. Operating the slide button 80 while the lateral button 84 is operated unlocks the lateral button 83 which may then be pressed beyond its intermediate position up to a position where its locking member 91 is fully disengaged from the corresponding locking notch of the tray (FIG. 19). In the configuration where both lateral buttons 83, 84 are in their operated position, the tray is unlocked and may therefore be slid out of the housing.

+

Thus, in this third embodiment, four actions have to be performed by the user, in a determined order, to unlock and move the tray. This is one action more than in the first and second embodiments. The child resistance is therefore still improved.

+

In a variant of this third embodiment, the locking member 92 could be suppressed and the tray could be locked only by the locking member 91.

+

In all three embodiments of the invention, the lateral push buttons 13, 50, 51, 83, 84 could be of one-piece construction with the housing and could be in the form of tabs defined by cut-outs made in the side walls of the housing and elastically hinged to the rest of the housing.

+

Furthermore, the housing could have another shape than a parallelepipedic one, for example a cylindrical shape. Since the buttons are operable independently of the tray and are part of respective distinct pieces that are movable relative to each other, a great flexibility is achieved in the designing of the container.

+

The medication container according to the invention may be made of plastics. Alternatively, the medication container, parts of it and/or the blisters can be made of a light-emitting material.

+

It will be appreciated that the invention is not limited to containers for medication stored in blisters. The medication could be freely disposed in a tray or other receptacle. Alternatively, the medication could be stored in blisters that are disposed in a tray or other receptacle without being fixed. It could also be envisaged to use the container according to the invention to store a liquid medication container, such as a syringe.

+

The medication container of the present invention is preferably used for dispensing medication, such as tablets, which may not be suitable or may be dangerous to children. The medication container is therefore most preferably used for anti-cancer drugs, drugs having an immediate toxic effect or drugs having an effect on the immune system, such as purine analogues, in particular Cladribine or derivatives thereof. Cladribine is a chlorinated purine analogue which has been suggested to be useful in the treatment of multiple sclerosis (EP 626 853) and cancer.

+

The present invention has been described above by way of example only. It will be apparent to the skilled person that modifications may be made without departing from the invention as claimed. In the appended claims, reference numerals in parentheses have been inserted to facilitate the reading. These reference numerals however shall in no manner be construed as limiting the scope of the claims.

+ + +The invention claimed is: + + +1. Container for the delivery of medication, comprising: +a housing having an open end, +a support for supporting medication, said support being slidably mounted in the, +first locking means for locking the support in the housing and for unlocking the support so that the support may be slid to the outside of the housing through the open end, said first locking means comprising a first locking member coupled to the housing and a second locking member coupled to the support, said first and second locking members being engageable with each other, and +at least one button operable to act on the first locking means, said at least one button comprising a first button operable to act on the first locking member to disengage the first and second locking members, +characterised by further comprising: +second locking means for maintaining engagement between the first and second locking members, arranged to block the first locking member when an attempt is made to operate the first button while the second button is in a rest position, and +a second button operable to act on the second locking means to permit disengaging the first and second locking members by operating the first button. + + + +2. Container according to claim 1, characterised in that the first and second buttons are operable in respective non-parallel directions. + + +3. Container according to claim 1, characterised in that the first and second buttons are operable independently of the support. + + +4. Container according to claim 1, characterised in that the first and second buttons are part of respective distinct pieces that are movable relative to each other. + + +5. Container according to claim 1, characterised in that the first button is a push button and the second button is a slide button. + + +6. Container according to claim 1, characterised in that the second locking means comprise a surface coupled to the second button and a stop projection coupled to the first locking member, in that said surface is arranged to block said stop projection when an attempt is made to operate the first button while the second button is in a rest position, and in that said surface comprises a hole into which the stop projection enters when the second button is in an operated position and the first button is moved to its operated position. + + +7. Container according to claim 6, characterised in that said surface further comprises a stop projection which is blocked by the stop projection coupled to the first locking member when the first button is in an intermediate position where the stop projection coupled to the first locking member is blocked by said surface, to prevent the second button from being operated. + + +8. Container according to claim 1, characterised in that the second locking means comprise first teeth coupled to the second button and second teeth coupled to the first button, in that the second teeth are out of engagement with the first teeth when the first and second buttons are in a rest position but engage the first teeth when an attempt is made to operate the first button while the second button is in a rest position, to block the first button in an intermediate position where the first locking member still engages the second locking member while locking the second button, and in that the first teeth are not on the path of the second teeth when the second button is in an operated position thus permitting the first button to be moved from its rest position to an operated position where the first locking member is disengaged from the second locking member. + + +9. Container according to claim 1, characterised in that the first button is provided at a side wall of the housing, in that said at least one button further comprises a third button provided at another, opposite side wall of the housing, in that the first locking means further comprise a third locking member coupled to the housing and a fourth locking member coupled to the support, said third and fourth locking members being engageable with each other, and in that the third button is operable to disengage the third and fourth locking members. + + +10. Container according to claim 9, characterised in that the third button is operable to act on the third locking member to disengage the third and fourth locking members. + + +11. Container according to claim 9, characterised in that the first and third buttons are arranged to unlock the support only when simultaneously in an operated position. + + +12. Container according to claim 9, characterised by further comprising third locking means for maintaining engagement between the third and fourth locking members and a fourth button operable to act on the third locking means to permit disengaging the third and fourth locking members by operating the third button. + + +13. Container according to claim 12, characterised in that the third button is operable to act on the third locking member to disengage the third and fourth locking members and the third locking means are arranged to block the third locking member when an attempt is made to operate the third button while the fourth button is in a rest position. + + +14. Container according to claim 12, characterised in that the first and third buttons are push buttons and the second and fourth buttons are slide buttons. + + +15. Container according to claim 14, characterised in that the second and fourth buttons are provided at a top wall of the housing. + + +16. Container according to claim 12, characterised in that the second locking means comprise a first surface coupled to the second button and a first stop projection coupled to the first locking member, in that the first surface is arranged to block the first stop projection when an attempt is made to operate the first button while the second button is in a rest position, in that the first surface comprises a hole into which the first stop projection enters when the second button is in an operated position and the first button is moved to its operated position, in that the third locking means comprise a second surface coupled to the fourth button and a second stop projection coupled to the third locking member, in that the second surface is arranged to block the second stop projection when an attempt is made to operate the third button while the fourth button is in a rest position, and in that the second surface comprises a hole into which the second stop projection enters when the fourth button is in an operated position and the third button is moved to its operated position. + + +17. Container according to claim 16, characterised in that the first surface further comprises a third stop projection which is blocked by the first stop projection when the first button is in an intermediate position where the first stop projection is blocked by the first surface, to prevent the second button from being operated, and in that the second surface further comprises a fourth stop projection which is blocked by the second stop projection when the third button is in an intermediate position where the second stop projection is blocked by the second surface, to prevent the fourth button from being operated. + + +18. Container according to claim 12, characterised in that the second locking means comprise first teeth coupled to the second button and second teeth coupled to the first button, in that the second teeth are out of engagement with the first teeth when the first and second buttons are in a rest position but engage the first teeth when an attempt is made to operate the first button while the second button is in a rest position, to block the first button in an intermediate position where the first locking member still engages the second locking member while locking the second button, in that the first teeth are not on the path of the second teeth when the second button is in an operated position thus permitting the first button to be moved from its rest position to an operated position where the first locking member is disengaged from the second locking member, in that the third locking means comprise third teeth coupled to the fourth button and fourth teeth coupled to the third button, in that the fourth teeth are out of engagement with the third teeth when the third and fourth buttons are in a rest position but engage the third teeth when an attempt is made to operate the third button while the fourth button is in a rest position, to block the third button in an intermediate position where the third locking member still engages the fourth locking member while locking the fourth button, and in that the third teeth are not on the path of the fourth teeth when the fourth button is in an operated position thus permitting the third button to be moved from its rest position to an operated position where the third locking member is disengaged from the fourth locking member. + + +19. Container according to claim 12, characterised in that the second and fourth buttons are one and a same button. + + +20. Container according to claim 1, characterised by further comprising third locking means for locking the second locking means and a third button operable to act on the third locking means to unlock the second locking means and permit acting on the second locking means by operating the second button. + + +21. Container according to claim 20, characterised in that the third locking means comprise a third locking member coupled to the second locking means and a fourth locking member coupled to the third button, and in that these third and fourth locking members are engaged with each other when the second and third buttons are in a rest position and may be disengaged from each other by operating the third button. + + +22. Container according to claim 21, characterised in that the third and fourth locking members each comprise teeth. + + +23. Container according to claim 20, characterised in that the first and third buttons are provided at side walls of the housing and the second button is provided at a top wall of the housing. + + +24. Container according to claim 20, characterised in that the first and third buttons are push buttons and the second button is a slide button. + + +25. Container according to claim 20, characterised in that the first locking means further comprise a fifth locking member coupled to the housing and a sixth locking member coupled to the support and the third button is arranged to also disengage the fifth and sixth locking members when operated. + + +26. Container according to claim 25, characterised in that the third button is arranged to act on the fifth locking member when operated, to disengage the fifth and sixth locking members. + + +27. Container according to claim 1, characterised in that said buttons are each subject to the action of elastic return means. + + +28. Container according to claim 1, characterised in that said buttons are each operable independently of the support. + + +29. Container according to claim 1, characterised in that said buttons are part of respective distinct pieces that are movable relative to each other. + + +30. Container according to claim 1, characterised by further comprising a cap coupled to the support and which closes the open end of the housing when the support is in its locked position. + + +31. Container according to claim 1, characterised in that the support supports at least one blister card containing said medication. + + +32. Container according to claim 31, characterised in that the blisters of said at least one blister card are fully encased in the housing when the support is in its locked position. + + +33. Container according to claim 31, characterised in that the support supports several separate blister cards containing said medication and placed side-by-side. + + +34. Container according to claim 1, characterised in that the medication is in the form of capsules or tablets. + + +35. Container according to claim 34, characterised in that it contains an even number of tablets. + + +36. Container according to claim 1, characterised in that it contains 2 to 14 tablets, preferably 6 to 10 tablets, most preferably 10 tablets. + + +37. Container according to claim 1, characterised in that said medication contains drug for the treatment of cancer, drug having an immediate toxic effect or drug having an effect on the immune system. + + +38. Container according to claim 37, characterised in that said medication comprises Cladribine or derivatives thereof. + + +39. Container according to claim 1, characterised in that it has a wallet size. + + +40. Kit comprising separately a container according to claim 1 and medication. + + +41. Kit according to claim 40, characterised by further comprising a description containing information on how to handle the container and on the administration and dosing of the medication. + + +42. Method of opening a container according to claim 19, characterised by comprising the following steps: +holding the housing, +operating the second button, +operating the first and third buttons while the second button is in its operated position, and +pulling the support while the first and third buttons are in their operated position. + + + +43. Method of opening a container according to claim 20, characterised by comprising the following steps: +holding the housing, +operating successively the third button, the second button and the first button, and +pulling the support while the first and third buttons are in their operated position. + + + + diff --git a/tests/data/uspto/ipgD0701016.xml b/tests/data/uspto/ipgD0701016.xml new file mode 100644 index 00000000..71b15228 --- /dev/null +++ b/tests/data/uspto/ipgD0701016.xml @@ -0,0 +1,1151 @@ + + + + + + +US +D0701016 +S1 +20140318 + + + + +US +29414573 +20120229 + + +29 + + +EM +001184956-0001 +20091210 + + + +14 + + +10 +0101 + + +US +D 1101 + +Cheese in form of a triangular pyramid + + + + +US +D14842 +S +Griscom, Jr. +18840300 + + +cited by examiner +USD24100 + + + + +US +D94174 +S +Vogt +19341200 + + +cited by examiner +USD 9714 + + + + +US +2819167 +A +Irmscher +19580100 + + +cited by examiner +US426 83 + + + + +US +2952394 +A +Schneider +19600900 + + +cited by examiner 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FIG. 1 is a perspective view of cheese in form of a triangular pyramid showing the new design;

+

FIG. 2 is another perspective view thereof;

+

FIG. 3 is another perspective view thereof;

+

FIG. 4 is a front elevational view thereof;

+

FIG. 5 is a rear elevational view thereof;

+

FIG. 6 is a top view thereof;

+

FIG. 7 is another front view thereof; and,

+

FIG. 8 is a right side view thereof.

+

The broken lines shown in the drawings represent portions of the cheese in form of a triangular pyramid which form no part of the claimed design.

+ + + +CLAIM + + +The ornamental design for cheese in form of a triangular pyramid, as shown and described. + + + \ No newline at end of file diff --git a/tests/data/uspto/pa20010031492.xml b/tests/data/uspto/pa20010031492.xml new file mode 100644 index 00000000..f17a28f2 --- /dev/null +++ b/tests/data/uspto/pa20010031492.xml @@ -0,0 +1,447 @@ + + + + + + + + + + + +]> + + + +20010031492 +A1 +20011018 + +new + + +09728320 + +09 +20001201 + + + +9811845.8 + +19980602 +GB + + + + +C12N001/20 + + +C12N005/06 + +07 + + + + +435 +252100 + + + + +435 +325000 + + + + +435 +252330 + + + +Assay reagent + + + + + + + +09728320 +A1 +20001201 + + + + +PCT/GB99/01730 +19990601 +US + + +UNKNOWN + + + + + + + +Jay +Lewington + + + +Bisley +GB + + +INV + + + +Katherine +Isles + + + +Oxon +GB + + +INV + + + +Sandy +Primrose + + + +High Wycombe +GB + + +INV + + + +Azur Environmental +03 + + +FITCH EVEN TABIN AND FLANNERY + +
+120 SOUTH LA SALLE STREET +SUITE 1600 +CHICAGO +IL +606033406 +
+ + + +A cell-derived assay reagent prepared from cells which have been killed by treatment with an antibiotic selected from the bleomycin-phleomycin family of antibiotics but which retain a signal-generating metabolic activity such as bioluminescence. + + + +[0001] This application is a continuation of PCT/GB99/01730, filed Jun. 1, 1999 designating the United States (the disclosure of which is incorporated herein by reference) and claiming priority from British application serial no. 9811845.8, filed Jun. 2, 1998. +[0002] The invention relates to a cell-derived assay reagent, in particular to an assay reagent prepared from cells which have been killed but which retain a signal-generating metabolic activity such as bioluminescence and also to assay methods using the cell-derived reagent such as, for example, toxicity testing methods. +[0003] The use of bacteria with a signal-generating metabolic activity as indicators of toxicity is well established. UK patent number GB 2005018 describes a method of assaying a liquid sample for toxic substances which involves contacting a suspension of bioluminescent microorganisms with a sample suspected of containing a toxic substance and observing the change in the light output of the bioluminescent organisms as a result of contact with the suspected toxic substance. Furthermore, a toxicity monitoring system embodying the same assay principle, which is manufactured and sold under the Trade Mark Microtox®, is in routine use in both environmental laboratories and for a variety of industrial applications. An improved toxicity assay method using bioluminescent bacteria, which can be used in a wider range of test conditions than the method of GB 2005018, is described in International patent application number WO 95/10767. +[0004] The assay methods known in the prior art may utilize naturally occurring bioluminescent organisms, including Photobacterium phosphoreum and Vibrio fischeri. However, recent interest has focused on the use of genetically modified microorganisms which have been engineered to express bioluminescence. These genetically modified bioluminescent microorganisms usually express lux genes, encoding the enzyme luciferase, which have been cloned from a naturally occurring bioluminescent microorganism (E. A. Meighen (1994) Genetics of Bacterial Bioluminescence. Ann. Rev. Genet. 28: 117-139; Stewart, G. S. A. B. Jassin, S. A. A. and Denyer, S. P. (1993), Engineering Microbial bioluminescence and biosensor applications. In Molecular Diagnosis. Eds R. Rapley and M. R. Walker Blackwell Scientific Pubs/Oxford). A process for producing genetically modified bioluminescent microorganisms expressing lux genes cloned from Vibrio harveyi is described in U.S. Pat. No. 4,581,335. +[0005] The use of genetically modified bioluminescent microorganisms in toxicity testing applications has several advantages over the use of naturally occurring microorganisms. For example, it is possible to engineer microorganisms with different sensitivities to a range of different toxic substances or to a single toxic substance. However, genetically modified microorganisms are subject to marketing restrictions as a result of government legislation and there is major concern relating to the deliberate release of genetically modified microorganisms into the environment as components of commercial products. This is particularly relevant with regard to toxicity testing which is often performed in the field rather than within the laboratory. The potential risk from release of potentially pathogenic genetically modified microorganisms into the environment where they may continue to grow in an uncontrollable manner has led to the introduction of legal restrictions on the use of genetically modified organisms in the field in many countries. +[0006] It has been suggested, to avoid the problems discussed above, to use genetically modified bioluminescent microorganisms which have been treated so that they retain the metabolic function of bioluminescence but an no longer reproduce. The use of radiation (gamma-radiation), X-rays or an electron beam) to kill bioluminescent cells whilst retaining the metabolic function of bioluminescence is demonstrated in International patent application number WO 95/07346. It is an object of the present invention to provide an alternative method of killing bioluminescent cells whilst retaining the metabolic function of bioluminescence which does not require the use of radiation and, as such, can be easily carried out without the need for specialized radiation equipment and containment facilities and without the risk to laboratory personnel associated with the use of radiation. +[0007] Accordingly, in a first aspect the invention provides a method of making a non-viable preparation of prokaryotic or eukaryotic cells, which preparation has a signal-generating metabolic activity, which method comprises contacting a viable culture of cells with signal-generating metabolic activity with a member of the bleomycin/phleomycin family of antibiotics. +[0008] Bleomycin and phleomycin are closely related glycopeptide antibiotics that are isolated in the form of copper chelates from cultures of Streptomyces verticillus. They represent a group of proteins with molecular weights ranging from 1000 to 1000 kda that are potent antibiotics and anti-tumour agents. So far more than 200 members of the bleomycin/phleomycin family have been isolated and characterised as complex basic glycopeptides. Family members resemble each other with respect to their physicochemical properties and their structure, indicating that functionally they all behave in the same manner. Furthermore, the chemical structure of the active moiety is conserved between family members and consists of 5 amino acids, L-glucose, 3-O-carbamoyl-D-mannose and a terminal cation. The various different bleomycin/phleomycin family members differ from each other in the nature of the terminal cation moiety, which is usually an amine. A preferred bleomycin/phleomycin antibiotic for use in the method of the invention is phleomycin D1, sold under the trade name Zeocin™. +[0009] Bleomycin and phleomycin are strong, selective inhibitors of DNA synthesis in intact bacteria and in mammalian cells. Bleomycin can be observed to attack purified DNA in vitro when incubated under appropriate conditions and analysis of the bleomycin damaged DNA shows that both single-stranded and double-stranded cleavages occur, the latter being the result of staggered single strand breaks formed approximately two base pairs apart in the complementary strands. +[0010] In in vivo systems, after being taken up by the cell, bleomycin enters the cell nucleus, binds to DNA (by virtue of the interaction between its positively charged terminal amine moiety and a negatively charged phosphate group of the DNA backbone) and causes strand scission. Bleomycin causes strand scission of DNA in viruses, bacteria and eukaryotic cell systems. +[0011] The present inventors have surprisingly found that treatment of a culture of cells with signal-generating metabolic activity with a bleomycin/phleomycin antibiotic renders the culture non-viable whilst retaining a level of signal-generating metabolic activity suitable for use in toxicity testing applications. In the context of this application the term non-viable is taken to mean that the cells are unable to reproduce. The process of rendering cells non-viable whilst retaining signal-generating metabolic activity may hereinafter be referred to as ‘inactivation’ and cells which have been rendered non-viable according to the method of the invention may be referred to as ‘inactivated’. +[0012] Because of the broad spectrum of action of the bleomycin/phleomycin family of antibiotics the method of the invention is equally applicable to bacterial cells and to eukaryotic cells with signal generating metabolic activity. Preferably the signal-generating metabolic activity is bioluminescence but other signal-generating metabolic activities which are reporters of toxic damage could be used with equivalent effect. +[0013] The method of the invention is preferred for use with bacteria or eukaryotic cells that have been genetically modified to express a signal-generating metabolic activity. The examples given below relate to E. coil which have been engineered to express bioluminescence by transformation with a plasmid carrying lux genes. The eukaryotic equivalent would be cells transfected with a vector containing nucleic acid encoding a eukaryotic luciferase enzyme (abbreviated luc) such as, for example, luciferase from the firefly Photinus pyralis. A suitable plasmid vector containing cDNA encoding firefly luciferase under the control of an SV40 viral promoter is available from Promega Corporation, Madison Wis., USA. However, in connection with the present invention it is advantageous to use recombinant cells containing the entire eukaryotic luc operon so as to avoid the need to add an exogenous substrate ( e.g. luciferin) in order to generate light output. +[0014] The optimum concentration of bleomycin/phleomycin antibiotic and contact time required to render a culture of cells non-viable whilst retaining a useful level of signal-generating metabolic activity may vary according to the cell type but can be readily determined by routine experiment. In general, the lower the concentration of antibiotic used the longer the contact time required for cell inactivation. In connection with the production of assay reagents for use in toxicity testing applications, it is generally advantageous to keep the concentration of antibiotic low (e.g. around 1-1.5 mg/ml) and increase the contact time for inactivation. As will be shown in Example 1, treatment with Zeocin™ at a concentration of 1.5 mg/ml for 3 to 5 hours is sufficient to completely inactivate a culture of recombinant E. coli. +[0015] In the case of bacteria, the contact time required to inactivate a culture of bacterial cells is found to vary according to the stage of growth of the bacterial culture at the time the antibiotic is administered. Although the method of the invention can be used on bacteria at all stages of growth it is generally preferable to perform the method on bacterial cells in an exponential growth phase because the optimum antibiotic contact time has been observed to be shortest when the antibiotic is administered to bacterial cells in an exponential growth phase. +[0016] Following treatment with bleomycin/phleomycin antibiotic the non-viable preparation of cells is preferably stabilised for ease of storage or shipment. The cells can be stabilised using known techniques such as, for example, freeze drying (lyophilization) or other cell preservation techniques known in the art. Stabilization by freeze drying has the added advantage that the freeze drying procedure itself can render cells non-viable. Thus, any cells in the preparation which remain viable after treatment of the culture with bleomycin/phleomycin antibiotic will be rendered non-viable by freeze drying. It is thought that freeze drying inactivates any remaining viable cells by enhancing the effect of antibiotic, such that sub-lethally injured cells in the culture are more sensitive to the stresses applied during freeze drying. +[0017] Prior to use the stabilised cell preparation is reconstituted using a reconstitution buffer to form an assay reagent. This reconstituted assay reagent may then be used directly in assays for analytes, for example in toxicity testing applications. It is preferable that the stabilised (i.e. freeze dried) assay reagent be reconstituted immediately prior to use, but after reconstitution it is generally necessary to allow sufficient time prior to use for the reconstituted reagent to reach a stable, high level of signal-generating activity. Suitable reconstitution buffers preferably contain an osmotically potent non-salt compound such as sucrose, dextran or polyethylene glycol, although salt based stabilisers may also be used. +[0018] Whilst the assay reagent of the invention is particularly suitable for use in toxicity testing applications it is to be understood that the invention is not limited to assay reagents for use in toxicity testing. The cell inactivation method of the invention can be used to inactivate any recombinant cells (prokaryotic or eukaryotic) with a signal generating metabolic activity that is not dependent upon cell viability. +[0019] In a further aspect the invention provides a method of assaying a potentially toxic analyte comprising the steps of, +[0020] (a) contacting a sample to be assayed for the analyte with a sample of assay reagent comprising a non-viable preparation of cells with a signal-generating metabolic activity; +[0021] (b) measuring the level of signal generated; and +[0022] (c) using the measurement obtained as an indicator of the toxicity of the analyte. +[0023] In a still further aspect, the invention provides a kit for performing the above-stated assay comprising an assay reagent with signal generating metabolic activity and means for contacting the assay reagent with a sample to be assayed for an analyte. +[0024] The analytes tested using the assay of the invention are usually toxic substances, but it is to be understood that the precise nature of the analyte to be tested is not material to the invention. +[0025] Toxicity is a general term used to describe an adverse effect on biological system and the term ‘toxic substances’ includes both toxicants (synthetic chemicals that are toxic) and toxins (natural poisons). Toxicity is usually expressed as an effective concentration (EC) or inhibitory concentration (IC) value. The EC/IC value is usually denoted as a percentage response e.g. EC50, EC10 which denotes the concentration (dose) of a particular substance which affects the designated criteria for assessing toxicity (i.e. a behavioural trait or death) in the indicated proportion of the population tested. For example, an EC50 of 10 ppm indicates that 50% of the population will be affected by a concentration of 10 ppm. In the case of a toxicity assay based on the use of a bioluminescent assay reagent, the EC50 value is usually the concentration of sample substance causing a 50% change in light output. + + +[0026] The present invention will be further understood by way of the following Examples with reference to the accompanying Figures in which: +[0027] FIG. 1 is a graph to show the effect of Zeocin™ treatment on viable count and light output of recombinant bioluminescent E. coil cells. +[0028] FIG. 2 is a graph to show the light output from five separate vials of reconstituted assay reagent. The assay reagent was prepared from recombinant bioluminescent E. coil exposed to 1.5 mg/ml Zeocin™ for 300 minutes. Five vials were used to reduce discrepancies resulting from vial to vial variation. +[0029] FIGS. 3 to 8 are graphs to show the effect of Zeocin™ treatment on the sensitivity of bioluminescent assay reagent to toxicant (ZnSO4): +[0030] FIG. 3: Control cells, lag phase. +[0031] FIG. 4: Zeocin™ treated cells, lag phase. +[0032] FIG. 5: Control cells, mid-exponential growth. +[0033] FIG. 6: Zeocin™ treated cells, mid-exponential growth. +[0034] FIG. 7: Control cells, stationary phase. +[0035] FIG. 8: Zeocin™ treated cells, stationary phase. + + +
+EXAMPLE 1 +
+
+(A) Inactivation of Bioluminescent E. coil Method +[0036] 1. Bioluminescent genetically modified E. coil strain HB101 (E. coli HB101 made bioluminescent by transformation with a plasmid carrying the lux operon of Vibrio fischeri constructed by the method of Shaw and Kado, as described in Biotechnology 4: 560-564) were grown from a frozen stock in 5 ml of low salt medium (LB (5 g/ml NaCl)+glycerol+MgSO4) for 24 hours. +[0037] 2. 1 ml of the 5 ml culture was then used to inoculate 200 ml of low salt medium in a shaker flask and the resultant culture grown to an OD630 of 0.407 (exponential growth phase). +[0038] 3. 50 ml of this culture was removed to a fresh sterile shaker flask (control cells). +[0039] 4. Zeocin™ was added to the 150 ml of culture in the original shaker flash, to a final concentration of 1.5 mg/ml. At the same time, an equivalent volume of water was added to the 50 ml culture removed from the original flask (control cells). +[0040] 5. The time course of cell inactivation was monitored by removing samples from the culture at 5, 60, 120, 180, 240 and 300 minutes after the addition of Zeocin™ and taking measurements of both light output (measured using a Deltatox luminometer) and viable count (per ml, determined using the method given in Example 3 below) for each of the samples. Samples of the control cells were removed at 5 and 300 minutes after the addition of water and measurements of light output and viable count taken as for the Zeocin™ treated cells. +[0041] FIG. 1 shows the effect of Zeocin™ treatment on the light output and viable count (per ml) of recombinant bioluminescent E. coil. Zeocin™ was added to a final concentration of 1.5 mg/ml at time zero. The number of viable cells in the culture was observed to decrease with increasing contact cells with Zeocin™, the culture being completely inactivated after 3 hours. The light output from the culture was observed to decrease gradually with increasing Zeocin™ contact time. +
+
+(B) Production of Assay Reagent +[0042] Five hours after the addition of Zeocin™ or water the remaining bacterial cells in the Zeocin™ treated and control cultures were harvested by the centrifugation, washed (to remove traces of Zeocin™ from the Zeocin™ treated culture), re-centrifuged and resuspended in cryoprotectant to an OD630 of 0.25. 200 &mgr;l aliquots of the cells in cryoprotectant were dispensed into single shot vials, and freeze dried. Freeze dried samples of the Zeocin™ treated cells and control cells were reconstituted in 0.2M sucrose to form assay reagents and the light output of the assay reagents measured at various times after reconstitution. +[0043] The light output from assay reagent prepared from cells exposed to 1.5 mg/ml Zeocin™ for 5 hours was not significantly different to the light output from assay reagent prepared from control (Zeocin™ untreated) cells, indicating that Zeocin™ treatment does not affect the light output of the reconstituted freeze dried assay reagent. Both Zeocin™ treated and Zeocin™ untreated assay reagents produced stable light output 15 minutes after reconstitution. +[0044] FIG. 2 shows the light output from five separate vials of reconstituted Zeocin™ treated assay reagent inactivated according to the method of Example 1(A) and processed into assay reagent as described in Example 1(B). Reconstitution solution was added at time zero and thereafter light output was observed to increase steadily before stabilising out at around 15 minutes after reconstitution. All five vials were observed to give similar light profiles after reconstitution. +
+
+EXAMPLE 2 +
+
+Sensitivity of Zeocin™ Treated Assay Reagent to Toxicant Method +[0045] 1. Bioluminescent genetically modified E. coil strain HB101 (E. coli HB101 made bioluminescent by transformation with a plasmid carrying the lux operon of vibrio fischeri constructed by the method of Shaw and Kado, as described in Biotechnology 4: 560-564) was grown in fermenter as a batch culture in low salt medium (LB(5 g/ml NaCl)+glycerol+MgSO4). +[0046] 2. Two aliquots of the culture were removed from the fermenter into separate sterile shaker flasks at each of three different stages of growth i.e. at OD630 values of 0.038 (lag phase growth), 1.31 (mid-exponential phase growth) and 2.468 (stationary phase growth). +[0047] 3. One aliquot of culture for each of the three growth stages was inactivated by contact with Zeocin™ (1 mg Zeocin™ added per 2.5×106 cells, i.e. the concentration of Zeocin™ per cell is kept constant) for 300 minutes and then processed into assay reagent by freeze drying and reconstitution, as described in part (B) of Example 1. +[0048] 4. An equal volume of water was added to the second aliquot of culture for each of the three growth stages and the cultures processed into assay reagent as described above. +[0049] 5. Samples of each of the three Zeocin™ treated and three control assay reagents were then evaluated for sensitivity to toxicant (ZnSO4) according to the following assay protocol: +[0050] ZnSO4 Sensitivity Assay +[0051] 1. ZnSO4 solutions were prepared in pure water at 30, 10, 3, 1, 0.3 and 0.1 ppm. Pure water was also used as a control. +[0052] 2. Seven vials of each of the three Zeocin™ treated and each of the three control assay reagents (i.e. one for each of the six ZnSO4 solutions and one for the pure water control) were reconstituted using 0.5 ml of reconstitution solution (eg 0.2M sucrose) and then left to stand at room temperature for 15 minutes to allow the light output to stabilize. Base line (time zero) readings of light output were then measured for each of the reconstituted reagents. +[0053] 3. 0.5 ml aliquots of each of the six ZnSO4 solutions and the pure water control were added to separate vials of reconstituted assay reagent. This was repeated for each of the different Zeocin™ treated and control assay reagents. +[0054] 4. The vials were incubated at room temperature and light output readings were taken 5, 10, 15, 20, 25 and 30 minutes after addition of ZnSO4 solution. +[0055] 5. The % toxic effect for each sample was calculated as follows: + +1 + + + + % toxic effect + + = + + 1 + - + + + ( + + + + S + c + + × + + C + o + + + + + S + o + + × + + C + t + + + + ) + + × + 100 + + + + + + + + +[0056] where: Co=light in control at time zero +[0057] Ct=light in control at reading time +[0058] So=light in sample at time zero +[0059] St=light in sample at reading time +[0060] The results of toxicity assays for sensitivity to ZnSO4 for all the Zeocin™ treated and control assay reagents are shown in FIGS. 3 to 8: +[0061] FIG. 3: Control cells, lag phase. +[0062] FIG. 4: Zeocin™ treated cells, lag phase. +[0063] FIG. 5: Control cells, mid-exponential growth. +[0064] FIG. 6: Zeocin™ treated cells, mid-exponential growth. +[0065] FIG. 7: Control cells, stationary phase. +[0066] FIG. 8: Zeocin™ treated cells, stationary phase. +[0067] In each case, separate graphs of % toxic effect against log10 concentration of ZnSO4 were plotted on the same axes for each value of time (minutes) after addition of Zeocin™ or water. The sensitivities of the various reagents, expressed as an EC50 value for 15 minutes exposed to ZnSO4, are summarised in Table 1 below. + +1 + + + + + + + + + + + + + + + + +SENSITIVITY-EC50 VALUES + + + + + + + + + + +GROWTH STAGE OF +ZEOCIN ™ +CONTROL + + +ASSAY REAGENT +TREATED +CELLS + + + + +Lag Phase +1.445 ppm ZnSO4 +1.580 ppm ZnSO4 + + +Expotential phase +0.446 ppm ZnSO4 +0.446 ZnSO4 + + +Stationary phase +0.426 ppm ZnSO4 +0.457 ppm ZnSO4 + + + + + +
+ + +[0068] Table 1: Sensitivity of the different assay reagents to ZnSo4 expressed as EC50 values for 15 minutes exposure to ZNSO4. +[0069] The results of the toxicity assays indicate that Zeocin™ treatment does not significantly affect the sensitivity of a recombinant bioluminescent E. coli derived assay reagent to ZnSO4. Similar results could be expected with other toxic substances which have an effect on signal-generating metabolic activities. +
+
+EXAMPLE 3 +
+
+Method to Determine Viable Count +[0070] 1. Samples of bacterial culture to be assayed for viable count were centrifuged at 10,000 rpm for 5 minutes to pellet the bacterial cells. +[0071] 2. Bacterial cells were washed by resuspending in 1 ml of M9 medium, re-centrifuged at 10,000 rpm for 5 minutes and finally re-suspended in 1 ml of M9 medium. +[0072] 3. Serial dilutions of the bacterial cell suspension from 10−1 to 10−7 were prepared in M9 medium. +[0073] 4. Three separate 10 &mgr;l aliquots of each of the serial dilutions were plated out on standard agar plates and the plates incubated at 37° C. +[0074] 5. The number of bacterial colonies present for each of the three aliquots at each of the serial dilutions were counted and the values averaged. Viable count was calculated per ml of bacterial culture. +
+ + + + +1. A method of making a non-viable preparation of prokaryotic or eukaryotic cells, which preparation has a signal-generating metabolic activity, which method comprises contacting a viable culture of said cells having signal-generating metabolic activity with an antibiotic selected from the bleomycin/phleomycin family of antibiotics. + + +2. The method as claimed in claim 1 wherein following contact with antibiotic, said cells are subjected to a stabilization step. + + +3. The method as claimed in claim 2 wherein said stabilization step comprises freeze drying. + + +4. The method as claimed in claim 1 wherein said antibiotic is phleomycin D1. + + +5. The method as claimed in claim 5 wherein said signal-generating metabolic activity is bioluminescence. + + +6. The method as claimed in claim 5 wherein said cells are bacteria. + + +7. The method as claimed in claim 6 wherein said bacteria are in an exponential growth phase when contacted with said antibiotic. + + +8. The method as claimed in claim 6 wherein said bacteria are genetically modified. + + +9. The method as claimed in claim 8 wherein said genetically modified bacteria contain nucleic acid encoding luciferase. + + +10. The method as claimed in claim 9 wherein said bacteria are E. coli. + + +11. The method as claimed in claim 5 wherein said cells are eukaryotic cells. + + +12. The method as claimed in claim 11 wherein said eukaryotic cells are genetically modified. + + +13. The method as claimed in claim 12 wherein said genetically modified eukaryotic cells contain nucleic acid encoding luciferase. + + +14. A method of making a non-viable preparation of prokaryotic cells, which preparation has a signal-generating metabolic activity, which method comprises contacting a viable culture of a genetically modified E. coli strain made bioluminescent by transformation with a plasmid carrying the lux operon of Vibrio fischeri with an antibiotic selected from the bleomycin/phleomycin family of antibiotics. + + +15. The method as claimed in claim 14 wherein said cells are contacted with phleomycin D1 at a concentration of at least about 1.5 mg/ml. + + +16. The method as claimed in claim 15 wherein said contact is maintained for at least about 3 hours. + + +17. The method as claimed in claim 16 wherein said antibiotic-treated cells are harvested, washed and freeze-dried. + + + +Drawings +NONE +
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+ + \ No newline at end of file diff --git a/tests/data/uspto/pftaps057006474.txt b/tests/data/uspto/pftaps057006474.txt new file mode 100644 index 00000000..314adda2 --- /dev/null +++ b/tests/data/uspto/pftaps057006474.txt @@ -0,0 +1,1380 @@ +PATN +WKU 057006474 +SRC 8 +APN 5686806 +APT 1 +ART 189 +APD 19951207 +TTL Carbocation containing cyanine-type dye +ISD 19971223 +NCL 20 +ECL 1 +EXP Houtteman; Scott W. +NDR 1 +NFG 1 +INVT +NAM Miyazaki; Takeshi +CTY Ebina +CNT JPX +INVT +NAM Tanaka; Kazumi +CTY Yokohama +CNT JPX +INVT +NAM Santo; Tsuyoshi +CTY Yokohama +CNT JPX +INVT +NAM Ohnishi; Toshikazu +CTY Machida +CNT JPX +INVT +NAM Fukui; Tetsuro +CTY Kawasaki +CNT JPX +INVT +NAM Okamoto; Tadashi +CTY Yokohama +CNT JPX +ASSG +NAM Canon Kabushiki Kaisha +CTY Tokyo +CNT JPX +COD 03 +PRIR +CNT JPX +APD 19910621 +APN 3-150428 +PRIR +CNT JPX +APD 19911028 +APN 3-281645 +PRIR +CNT JPX +APD 19920610 +APN 4-150665 +RLAP +COD 74 +APN 900302 +APD 19920618 +PSC 01 +PNO 5512446 +CLAS +OCL 435 6 +XCL 436139 +XCL 430 93 +XCL 585 16 +XCL 585406 +XCL 260350 +EDF 6 +ICL C12Q 168 +FSC 435 +FSS 6 +FSC 436 +FSS 139;63;56 +FSC 430 +FSS 93 +FSC 585 +FSS 16;406 +FSC 260 +FSS 350 +UREF +PNO 3770383 +ISD 19731100 +NAM Price +OCL 436509 +UREF +PNO 3789116 +ISD 19740100 +NAM Kay +OCL 436800 +UREF +PNO 4738908 +ISD 19880400 +NAM Oguchi et al. +OCL 430 20 +UREF +PNO 5112960 +ISD 19920500 +NAM Bronstein et al. +OCL 536 18.1 +FREF +PNO 2191674 +ISD 19900700 +CNT JPX +OREF +PAL K. Sauda et al., "Determination of Protein in Human Serum by + High-Performance Liquid Chromatography with Semiconductor Laser + Fluorometric Detection," Analytical Chemistry, vol. 58, No. 13, Nov. 1986, + pp. 2649-2653. +PAL Derwent Abstract Accession No. 91-068399/10 (1991). +PAL Smith, et al., Nature, vol. 321 (1986), pp. 674-679. +PAL Wingrove, Organic Chemistry, pub. by Harper & Row, New York, pp. 163-166, + 1981. +PAL Mujumdar et al., Cytometry 10:11-19, 1989. +LREP +FRM Fitzpatrick, Cella, Harper & Scinto +ABST +PAL To provide a reagent with excellent stability under storage, which can + detect a subject compound to be measured with higher specificity and + sensitibity. +PAL Complexes of a compound represented by the general formula (IV): + ##STR1## +PARN +PAR This application is a division of application Ser. No. 07/900,302 filed + Jun. 18, 1992, now U.S. Pat. No. 5,512,446. +BSUM +PAC BACKGROUND OF THE INVENTION +PAR 1. Field of the Invention +PAR The present invention relates to a labeled complex for microassay using + near-infrared radiation. More specifically, the present invention relates + to a labeled complex capable of specifically detecting a certain + particular component in a complex mixture with a higher sensitivity. +PAR 2. Related Background Art +PAR On irradiating a laser beam on a trace substance labeled with dyes and the + like, information due to the substance is generated such as scattered + light, absorption light, fluorescent light and furthermore light + acoustics. It is widely known in the field of analysis using lasers, to + detect such information so as to practice microassays rapidly with a + higher precision. +PAR A gas laser represented by an argon laser and a helium laser has + conventionally been used exclusively as a laser source. In recent years, + however, a semi-conductor laser has been developed, and based on the + characteristic features thereof such as inexpensive cost, small scale and + easy output control, it is now desired to use the semiconductor laser as a + light source. +PAR If diagnostically useful substances from living organisms are assayed by + means of the wave-length in ultraviolet and visible regions as has + conventionally been used, the background (blank) via the intrinsic + fluorescence of naturally occurring products, such as flavin, pyridine + coenzyme and serum proteins, which are generally contained in samples, is + likely to increase. Only if a light source in a near-infrared region can + be used, such background from naturally occurring products can be + eliminated so that the sensitivity to substances to be measured might be + enhanced, consequently. +PAR However, the oscillation wavelength of a semiconductor laser is generally + in red and near-infrared regions (670 to 830 nm), where not too many dyes + generate fluorescence via absorption or excitation. A representative + example of such dyes is polymethine-type dye having a longer conjugated + chain. Examples of labeling substances from living organisms with a + polymethine-type dye and using the labeled substances for microanalysis + are reported by K. Sauda, T. Imasaka, et al. in the report in Anal. Chem., + 58, 2649-2653 (1986), such that plasma protein is labeled with a cyanine + dye having a sulfonate group (for example, Indocyanine Green) for the + analysis by high-performance liquid chromatography. +PAR Japanese Patent Application Laid-open No. 2-191674 discloses that various + cyanine dyes having sulfonic acid groups or sulfonate groups are used for + labeling substances from living organisms and for detecting the + fluorescence. +PAR However, these known cyanine dyes emitting fluorescence via absorption or + excitation in the near-infrared region are generally not particularly + stable under light or heat. +PAR If the dyes are used as labeling agents and bonded to substances from + living organisms such as antibodies for preparing complexes, the complexes + are likely to be oxidized easily by environmental factors such as light, + heat, moisture, atmospheric oxygen and the like or to be subjected to + modification such as generating cross-links. Particularly in water, a + modification such as hydrolysis is further accelerated, disadvantageously. + Therefore, the practical use of these complexes as detecting reagents in + carrying out the microassay of the components of living organisms has + encountered difficulties because of their poor stability under storage. +PAC SUMMARY OF THE INVENTION +PAR The present inventors have made various investigations so as to solve the + above problems, and have found that a dye of a particular structure, more + specifically a particular polymethine dye, and among others, a dye having + an azulene skelton, are extremely stable even after the immobilization + thereof as a labeling agent onto substances from living organisms. Thus, + the inventors have achieved the present invention. It is an object of the + present invention to provide a labeled complex with excellent storage + stability which can overcome the above problems. +PAR According to an aspect of the present invention, there is provided a + labeled complex for detecting a subject compound to be analyzed by means + of optical means using near-infrared radiation which complex comprises a + substance from a living organism and a labeling agent fixed onto the + substance and is bonded to the subject compound to be analyzed, wherein + the labeling agent comprises a compound represented by the general formula + (I), (II) or (III): + ##STR2## + wherein R.sub.1 through R.sub.7 are independently selected from the group + consisting of hydrogen atom, halogen atom, alkyl group, aryl group, + aralkyl group, sulfonate group, amino group, styryl group, nitro group, + hydroxyl group, carboxyl group, cyano group, or arylazo group; R.sub.1 + through R.sub.7 may be bonded to each other to form a substituted or an + unsubstituted condensed ring; R.sub.1 represents a divalent organic + residue; and X.sub.1.sup..crclbar. represents an anion; + ##STR3## + wherein R.sub.8 through R14 are independently selected from the group + consisting of hydrogen atom, halogen atom, alkyl group, aryl group, + aralkyl group, sulfonate group, amino group, styryl group, nitro group, + hydroxyl group, carboxyl group, cyano group, or arylazo group; R.sub.8 + through R14 may be bonded to each other to form a substituted or an + unsubstituted condensed ring; and R.sub.A represents a divalent organic + residue; + ##STR4## + wherein R.sub.15 through R.sub.21 are independently selected from the + group consisting of hydrogen atom, halogen atom, alkyl group, aryl group, + a substituted or an unsubstituted aralkyl group, a substituted or an + unsubstituted amino group, a substituted or an unsubstituted styryl group, + nitro group, sulfonate group, hydroxyl group, carboxyl group, cyano group, + or arylazo group; R.sub.15 through R.sub.21 may or may not be bonded to + each other to form a substituted or an unsubstituted condensed ring; + R.sub.B represents a divalent organic residue; and X.sub.1.sup..crclbar. + represents an anion. +PAR According to another aspect of the present invention, there is provided a + labeled complex for detecting a subject compound to be analyzed by means + of optical means using near-infrared radiation which complex comprises a + substance from a living organism and a labeling agent fixed onto the + substance and is bonded to the subject compound to be analyzed, wherein + the labeling agent comprises a compound represented by the general formula + (IV): + ##STR5## + wherein A, B, D and E are independently selected from the group consisting + of hydrogen atom, a substituted or an unsubstituted alkyl group having two + or more carbon atoms, alkenyl group, aralkyl group, aryl group, styryl + group and heterocyclic group; r.sub.1 ' and r.sub.2 ' are individually + selected from the group consisting of hydrogen atom, a substituted or an + unsubstituted alkyl group, cyclic alkyl group, alkenyl group, aralkyl + group and aryl group; k is 0 or 1; 1 is 0, 1 or 2; and + X.sub.2.sup..crclbar. represents an anion. +PAR According to another aspect of the present invention, there is provided a + method of detecting a subject compound to be analyzed by means of optical + means which method comprises using a labeled complex comprised of a + substance from a living organism and a labeling agent fixed onto the + substance and bonding the complex to the subject compound to be analyzed, + wherein the labeling agent comprises a compound represented by the general + formula (I), (II) or (III). +PAR According to still another aspect of the present invention, there is + provided a method of detecting a subject compound to be analyzed by means + of optical means which method comprises using a labeled complex comprised + of a substance from a living organism and a labeling agent fixed onto the + substance and bonding the complex to the subject compound to be analyzed, + wherein the labeling agent comprises a compound represented by the general + formula (iv). +DRWD +PAC BRIEF DESCRIPTION OF THE DRAWINGS +PAR FIG. 1 depicts one example of fluorescence emitting wave form of a labeling + agent. +DETD +PAC DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS +PAR The present invention will now be explained in detail hereinbelow. +PAR In accordance with the present invention, the compound of the general + formula (I), (II) or (III) is employed as a labeling agent, wherein + R.sub.1 to R.sub.21 individually represent hydrogen atom, halogen atom + (chlorine atom, bromine atom, and iodine atom) or a monovalent organic + residue, and other such functional groups described above. The monovalent + organic residue can be selected from a wide variety of such residues. +PAR The alkyl group is preferably in straight chain or branched chain, having a + carbon number of 1 to 12, such as for example methyl group, ethyl group, + n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, + iso-butyl group, t-butyl group, n-amyl group, t-amyl group, n-hexyl group, + n-octyl group, t-octyl group and the like. +PAR The aryl group preferably has a carbon number of 6 to 20, such as for + example phenyl group, naphthyl group, methoxyphenyl group, + diethylaminophenyl group, dimethylaminophenyl group and the like. +PAR The substituted aralkyl group preferably has a carbon number of 7 to 19, + such as for example carboxybenzyl group, sulfobenzyl group, hydroxybenzyl + group and the like. +PAR The unsubstituted aralkyl group preferably has a carbon number of 7 to 19, + such as for example benzyl group, phenethyl group, .alpha.-naphthylmethyl + group, .beta.-naphthylmethyl group and the like. +PAR The substituted or unsubstituted amino group preferably has a carbon number + of 10 or less, such as for example amino group, dimethylamino group, + diethylamino group, dipropylamino group, acetylamino group, benzoylamino + group and the like. +PAR The substituted or unsubstituted styryl group preferably has a carbon + number of 8 to 14, such as for example styryl group, dimethylaminostyryl + group, diethylaminostyryl group, dipropylaminostyryl group, methoxystyryl + group, ethoxystyryl group, methylstyryl group and the like. +PAR The aryl azo group preferably has a carbon number of 6 to 14, such as for + example phenylazo group, .alpha.-naphthylazo group, .beta.-naphthylazo + group, dimethylaminophenylazo group, chlorophenylazo group, nitrophenylazo + group, methoxyphenylazo group and the like. +PAR Of the combinations of R.sub.1 and R.sub.2, R.sub.2 and R.sub.3, R.sub.3 + and R.sub.4, R.sub.4 and R.sub.5, R.sub.5 and R.sub.6, and R.sub.6 and + R.sub.7 of the general formula (I), at least one combination may form a + substituted or an unsubstituted condensed ring. The condensed ring may be + five, six or seven membered, including aromatic ring (benzene, + naphthalene, chlorobenzene, bromobenzene, methyl benzene, ethyl benzene, + methoxybenzene, ethoxybenzene and the like); heterocyclic ring (furan + ring, benzofuran ring, pyrrole ring, thiophene ring, pyridine ring, + quinoline ring, thiazole ring and the like); and aliphatic ring + (dimethylene, trimethylene, tetramethylene and the like). This is the case + with the general formulas (II) and (III). +PAR For the general formula (II), at least one combination among the + combinations of R.sub.8 and R.sub.9, R.sub.9 and R.sub.10, R.sub.10 and + R.sub.11, R.sub.11 and R.sub.12, R.sub.12 and R.sub.13, and R.sub.13 and + R.sub.14, may form a substituted or an unsubstituted condensed ring. +PAR Also for the general formula (III), at least one combination of the + combinations of R.sub.15 and R.sub.16, R.sub.16 and R.sub.17, R.sub.17 and + R.sub.18, R.sub.18 and R.sub.19, R.sub.19 and R.sub.20, and R.sub.20 and + R.sub.21, may form a substituted or an unsubstituted condensed ring. +PAR In the general formulas (I) to (IV) described above, the general formula + (I) is specifically preferable; preference is also given individually to + hydrogen atom, alkyl group and sulfonate group in the case of R.sub.1 to + R.sub.7 ; hydrogen atom, alkyl group and sulfonate group in the case of + R.sub.8 to R.sub.14 ; hydrogen atom, alkyl group and sulfonate group in + the case of R.sub.15 to R.sub.21 ; alkyl group and aryl group in the case + of A, B, D and E; hydrogen atom and alkyl group in the case Of r.sub.1 ' + to r.sub.2 '. +PAR In the general formula (I), R represents a divalent organic residue bonded + via a double bond. Specific examples of a compound containing such R to be + used in the present invention, include those represented by the following + general formulas (1) to (12), wherein Q.sup..sym. represents the following + azulenium salt nucleus and the right side excluding Q.sup..sym. + represents R. + ##STR6## + wherein the relation between the azulenium salt nucleus represented by + Q.sup..crclbar. and the azulene salt nucleus on the right side in the + formula (3) may be symmetric or asymmetric. + ##STR7## + In the above formulas (1) to (12) as in the case of R.sub.1 to R.sub.7, + R.sub.1 ' to R.sub.7 ' and R.sub.1 " to R.sub.7 " independently represent + hydrogen atom, halogen atom, alkyl group, aryl group, aralkyl group, amino + group, styryl group, nitro group, hydroxyl group, carboxyl group, cyano + group or aryl azo group, while R.sub.1 ' to R.sub.7 ' and R.sub.1 " to + R.sub.7 " independently may form a substituted or an unsubstituted + condensed ring; n is 0, 1 or 2; r is an integer of 1 to 8; S represents 0 + or 1; and t represents 1 or 2. +PAR M.sub.2 represents a non-metallic atom group required for the completion of + a nitrogen-containing heterocyclic ring. +PAR Specific examples of M.sub.2 are atom groups required for the completion of + a nitrogen-containing heterocyclic ring, including pyridine, thiazole, + benzothiazole, naphthothiazole, oxazole, benzoxazole, naphthoxazole, + imidazole, benzimidazole, naphthoimidazole, 2-quinoline, 4-quinoline, + isoquinoline or indole, and may be substituted by halogen atom (chlorine + atom, bromine atom, iodine atom and the like), alkyl group (methyl, ethyl, + propyl, butyl and the like), aryl group (phenyl, tolyl, xylyl and the + like), and aralkyl (benzene, p-trimethyl, and the like). +PAR R.sub.22 represents hydrogen atom, nitro group, sulfonate group, cyano + group, alkyl group (methyl, ethyl, propyl, butyl and the like), or aryl + group (phenyl, tolyl, xylyl and the like). R.sub.23 represents alkyl group + (methyl, ethyl, propyl, butyl and the like), a substituted alkyl group + (2-hydroxyethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-hydroxypropyl, + 3-methoxypropyl, 3-ethoxypropyl, 3-chloropropyl, 3-bromopropyl, + 3-carboxylpropyl and the like ), a cyclic alkyl group (cyclohexyl, + cyclopropyl), aryl aralkyl group (benzene, 2-phenylethyl, 3-phenylpropyl, + 3-phenylbutyl, 4-phenylbutyl, .alpha.-naphthylmethyl, + .beta.-naphthylmethyl), a substituted aralkyl group (methylbenzyl, + ethylbenzyl, dimethylbenzyl, trimethylbenzyl, chlorobenzyl, bromobenzyl + and the like), aryl group (phenyl, tolyl, xylyl, .alpha.-naphtyl, + .beta.-naphthyl) or a substituted aryl group (chlorophenyl, + dichlorophenyl, trichlorophenyl, ethylphenyl, methoxydiphenyl, + dimethoxyphenyl, aminophenyl, sulfonate phenyl, nitrophenyl, hydroxyphenyl + and the like). +PAR R.sub.24 represents a substituted or an unsubstituted aryl group or the + cation group thereof, specifically including a substituted or an + unsubstituted aryl group (phenyl, tolyl, xylyl, biphenyl, aminophenyl, + .alpha.-naphthyl, .beta.-napthyl, anthranyl, pyrenyl, methoxyphenyl, + dimethoxyphenyl, trimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, + chlorophenyl, dichlorophenyl, trichlorophenyl, bromophenyl, dibromophenyl, + tribromophenyl, ethylphenyl, diethylphenyl, nitrophenyl, aminophenyl, + dimethylaminophenyl, diethylaminophenyl, dibenzylaminophenyl, + dipropylaminophenyl, morpholinophenyl, piperidinylphenyl, + piperidinophenyl, diphenylaminophenyl, acetylaminophenyl, + benzoylaminophenyl, acetylphenyl, benzoylphenyl, cyanophenyl, sulfonate + phenyl, carboxylate phenyl and the like). +PAR R.sub.25 represents a heterocyclic ring or the cation group thereof, + specifically including a monovalent heterocyclic ring derived from cyclic + rings, such as furan, thiophene, benzofuran, thionaphthene, dibenzofuran, + carbazole, phenothiazine phenoxazine, pyridine and the like. +PAR R.sub.26 represents hydrogen atom, alkyl group (methyl, ethyl, propyl, + butyl and the like), or a substituted or an unsubstituted aryl group + (phenyl, tolyl, xylyl, biphenyl, ethylphenyl, chlorophenyl, methoxyphenyl, + ethoxyphenyl, nitrophenyl, aminophenyl, dimethylaminophenyl, + diethylaminophenyl, acetylaminophenyl, .alpha.-naphthyl, .beta.-naphthyl, + anthraryl, pyrenyl, sulfonate phenyl, carboxylate phenyl and the like. In + the formula, Z.sub.7 represents an atom group required for the completion + of pyran, thiapyran, selenapyran, telluropyran, benzopyran, + benzothiapyran, benzoselenapyran, benzotelluropyran, naphthopyran, + naphthothiapyran, or naphthoselenapyran, or naphthotelluropyran. +PAR L.sub.7 represents sulfur atom, oxygen atom or selenium atom or tellurium + atom. +PAR R.sub.27 and R.sub.28 individually represent hydrogen atom, alkoxy group, a + substituted or an unsubstituted aryl group, alkenyl group and a + heterocyclic group, +PAR More specifically, R.sub.27 and R.sub.28 individually represent hydrogen + atom, alkyl group (methyl, ethyl, propyl, butyl and the like), alkyl + sulfonate group, alkoxyl group (methoxy, ethoxy, propoxy, ethoxyethyl, + methoxyethyl and the like), aryl group (phenyl, tolyl, xylyl, sulfonate + phenyl, chlorophenyl, biphenyl, methoxyphenyl and the like), a substituted + or an unsubstituted styryl group (styryl, p-methylstyryl, o-chlorostyryl, + p-methoxystyryl and the like), a substituted or an unsubstituted 4-phenyl, + 1,3-butadienyl group (r-phenyl, 1,3-butadienyl, 4-(p-methylphenyl), + 1,3-butadienyl and the like), or a substituted or an unsubstituted + heterocyclic group (quinolyl, pyridyl, carbazoyl, furyl and the like). +PAR As in the case of R, the same is true with R.sub.A and R.sub.B of the + general formulas (II) and (III), respectively. +PAR Then, in R, the symbols R.sub.8 ' to R.sub.14 ' individually correspond to + R.sub.1 ' to R.sub.7 '; R.sub.8 " to R.sub.14 " individually correspond to + R.sub.1 " to R.sub.7 "; in R.sub.B, R.sub.14 ' to R.sub.21 " individually + correspond to R.sub.1 ' to R.sub.7 '; R.sub.14 " to R.sub.21 " + individually correspond to R.sub.1 " to R.sub.7 ". +PAR In the azulenium nucleus of the (1) to (12), described above, those + represented by the formulas (3), (9) and (10) are more preferably used; + and particularly, the formula (3) is preferable. +PAR R.sub.1 to R.sub.28, R.sub.1 ' to R.sub.21 ' and R.sub.1 " to R.sub.21 " + preferably contain one or more well-known polar groups in order to impart + water solubility to a compound (labeling agent) represented by the general + formula (I), (II) or (III). The polar groups include, for example, + hydroxyl group, alkylhydroxyl group, sulfonate group, alkylsulfonate + group, carboxylate group, alkylcarboxylate group, tetra-ammonium base and + the like. R.sub.1 to R.sub.28, R.sub.1 ' to R.sub.21 ', and R.sub.1 " to + R.sub.21 " preferably contain one or more well-known reactive groups in + order that the compound of the general formula (I) can form a covalent + bond with a substance from a living organism. +PAR The reactive groups include the reactive sites of isocyanate, + isothiocyanate, succinimide ester, sulfosuccinimide ester, imide ester, + hydrazine, nitroaryl halide, piperidine disulfide, maleimide, + thiophthalimide, acid halide, sulfonyl halide, aziridine, azide + nitrophenyl, azide amino, 3-(2-pyridyldithio) propionamide and the like. + In these reactive sites, the following spacer groups + ##STR8## + (n=0, 1 to 6) may be interposed in order to prevent steric hindrance + during on the bonding of a labeling agent and a substance from a living + organism. +PAR Preferable such reactive groups include isothiocyanate, sulfosuccinimide + ester, succinimide ester maleimide and the like X.sub.1.sup..sym. + represents an anion, including chloride ion, bromide ion, iodide ion, + perchlorate ion, benzenesulfonate ion, p-toluene sulfonate ion, + methylsulfate ion, ethylsulfate ion, propylsulfate ion, tetrafluoroborate + ion, tetraphenylborate ion, hexafluorophosphate ion, benzenesulfinic acid + salt ion, acetate ion, trifluoroacetate ion, propionate ion, benzoate ion, + oxalate ion, succinate ion, malonate ion, oleate ion, stearate ion, + citrate ion, monohydrogen diphosphate ion, dihydrogen monophosphate ion, + pentachlorostannate ion, chlorosulfonate ion, fluorosulfonate ion, + trifluoromethane sulfonate ion, hexafluoroantimonate ion, molybdate ion, + tungstate ion, titanate ion, zirconate ion and the like. +PAR Specific examples of these labeling agents are illustrated in Tables 1, 2 + and 3, but are not limited thereto. +PAR The synthetic method of these azulene dyes is described in U.S. Pat. No. + 4,738,908. +TBL3 TABLE 1 + - No. G R X.sub.1 R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6 + R.sub.7 + 1 (I) (3) R'.sub.1 = R'.sub.3 = R'.sub.5 = R'.sub.6 = HR'.sub.2 = + R'.sub.7 = CH.sub.3R'.sub.4 = CH(CH.sub.3).sub.2, R'.sub.22 = H, n = 2 + BF.sub.4 H H H + ##STR9## + H H CH.sub.3 + 2 (I) (3) R'.sub.1 = R'.sub.2 = R'.sub.4 = R'.sub.6 = H ClO.sub.4 H H + CH.sub.3 H OCH.sub.3 H CH.sub.3 + R'.sub.3 = R'.sub.7 = + CH.sub.3 R'.sub.5 = + OCH.sub.3, R'.sub.22 = H, n = + 2 3 (I) (3) R'.sub.1 = + R'.sub.2 = R'.sub.3 = R'.sub.7 = R'.sub.4 = R'.sub.6 = H I H H CH.sub.3 + H CH.sub.2 + CH.sub.2 H CH.sub.3 + R'.sub.5 = CH.sub.2 CH.sub.2 CH.sub.2 COONa CH.sub.2 CH.sub.3 + R'.sub.22 = H n = + 2 4 (I) (3) R'.sub.1 = + R'.sub.2 = R'.sub.3 = R'.sub.4 = R'.sub.6 = R'.sub.7 = H ClO.sub.4 H H' + H H C(CH.sub.2).sub.3 H H + R'.sub.5 = + C(CH.sub.2).sub.3 R'.sub.22 + = H, n = + 2 + 5 (I) (3) R'.sub.1 = R'.sub.5 = R'.sub.6 = HR'.sub.2 and R'.sub.3 + are cyclizedwith (CH.sub.2).sub.2R'.sub.4 = R'.sub.7 = CH.sub.3, + R'.sub.22 = H, n = 2 BF.sub.4 H SO.sub.3.sup..crclbar. Na.sup..sym. H + ##STR10## + H H CH.sub.3 + 6 (I) (3) + ##STR11## + BF.sub.4 H H H H C(CH.sub.2).sub.3 H H + 7 (I) (3) R'.sub.1 = R'.sub.2 = R'.sub.4 = R'.sub.6 = HR'.sub.3 = + R'.sub.5 = R'.sub.7 = CH.sub.3R'.sub.22 = H, n = + 2 + ##STR12## + H H CH.sub.3 H CH.sub.3 H CH.sub.3 + 8 (I) (9) + ##STR13## + BF.sub.4 H CH.sub.3 H R.sub.4 and R.sub.5 arecombined to formSCHC(CH.sub + .3) H CH.sub.3 + 9 (I) (10) + ##STR14## + ClO.sub.4 H SO.sub.3.sup..crclbar. Na.sup..sym. H CH(CH.sub.3).sub.2 + ##STR15## + H CH.sub.3 + 10 (I) (11) + ##STR16## + BF.sub.4 H CH.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 + 11 (I) (12) + ##STR17## + ##STR18## + H CH.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 + *G: General Formula +TBL TABLE 2 + __________________________________________________________________________ + No. + G R.sub.A R.sub.8 + R.sub.9 + R.sub.10 + R.sub.11 + R.sub.12 R.sub.13 + R.sub.14 + __________________________________________________________________________ + 12 (II) + (1) + R'.sub.8 = R'.sub.10 = R'.sub.12 = R'.sub.13 = H + H SO.sub.3.sup..crclbar. Na.sup..sym. + H CH(CH.sub.3).sub.2 + H H CH.sub.3 + R'.sub.9 = R'.sub.14 = CH.sub.3 + R'.sub.11 = CH(CH.sub.3).sub.2 + 13 (II) + (1) + R'.sub.8 = R'.sub.12 = R'.sub.13 = R'.sub.14 = H + H CH.sub.3 + SCHC(CH.sub.3) + H H H + R'.sub.10 < R'.sub.11CSCHC(CH.sub.3) + 14 (II) + (2) + R'.sub.8 = R'.sub.10 = R'.sub.12 = R'.sub.13 = H + H SO.sub.3.sup..crclbar. Na.sup..sym. + H CH(CH.sub.3).sub.2 + H H CH.sub.3 + R'.sub.9 = R'.sub.14 = CH.sub.3 + R'.sub.11 = CH(CH.sub.3).sub.2 + 15 (II) + (2) + R'.sub.8 = R'.sub.9 = R'.sub.11 = R'.sub.13 = H R'.sub.10 = + R'.sub.14 = CH.sub.3 R'.sub.12 = OC.sub.2 H.sub.5 + H H CH.sub.3 + H + ##STR19## H CH.sub.3 + __________________________________________________________________________ + *G: General Formula +TBL3 TABLE 3 + - No. G R.sub.B X.sub.1 R.sub.15 R.sub.16 R.sub.17 R.sub.18 R.sub.19 + R.sub.20 R.sub.21 + 16 (III) (10) + ##STR20## + BF.sub.4 H CH.sub.3 H formation ofSCHC H CH.sub.3 + 1 + 7 (III) (4) R'.sub.15 = R'.sub.16 = R'.sub.18 = R'.sub.20 = H I H + SO.sub.3.sup..crclbar. + Na.sup..sym. H H CH.sub.3 H CH.sub.3 R'.sub.17 = + R'.sub.19 = R'.sub.21 = + CH.sub.3 r = + 1 + 18 (III) (10) + R'.sub.15 = R'.sub.18 = R'.sub.20 = HR'.sub.16 = NO.sub.2R'.sub.17 = + R'.sub.19 = R'.sub.21 = CH.sub.3r = + 3 + ##STR21## + H NO.sub.2 CH.sub.3 H CH.sub.3 H CH.sub.3 + 19 (III) (5) R'.sub.15 = R'.sub.16 = R'.sub.17 = R'.sub.18 = HR'.sub.19 + = R'.sub.20 = R'.sub.21 = HR".sub.15 = R".sub.17 = R".sub.18 = R".sub.19 + =R".sub.20 = R".sub.21 = H ClO.sub.4 H SO.sub.3.sup..crclbar. + Na.sup..sym. H H + ##STR22## + H H + 20 (III) (8) + ##STR23## + ##STR24## + H CH.sub.3 H CH(CH.sub.3).sub.2 H H CH.sub.3 + 21 (III) (9) + ##STR25## + BF.sub.4 H SO.sub.3.sup..crclbar. Na.sup..sym. H H n-C.sub.8 H.sub.17 H + H + 22 (III) (10) + ##STR26## + ##STR27## + H SO.sub.3.sup..crclbar. Na.sup..sym. H CH(CH.sub.3).sub.2 H H CH.sub.3 + 23 (III) (12) + ##STR28## + I H CH.sub.3 H CH(CH.sub.3).sub.2 + ##STR29## + H CH.sub.3 + No. G R X.sub.1 R.sub.1 R.sub.2 R.sub.3 R.sub.4 R.sub.5 R.sub.6 + R.sub.7 + 24 I (6) + ##STR30## + I H H H + ##STR31## + H H CH.sub.3 + 25 I (7) + ##STR32## + BF.sub.4 H H H CH(CH.sub.3).sub.2 H H CH.sub.3 + 26 I (3) R'.sub.1 = R'.sub.3 = R'.sub.5 = R'.sub.6 = HR'.sub.2 = + SO.sub.3.sup..crclbar. Na.sup..sym.R'.sub.7 = CH.sub.3 R'.sub.22 = + HR'.sub.4 = CH(CH.sub.3).sub.2n = + 2 I H H CH.sub.3 + ##STR33## + H H CH.sub.3 + 27 I (3) R'.sub.1 = R'.sub.3 = R'.sub.4 = R'.sub.6 = R'.sub.7 = + HR'.sub.2 = SO.sub.3.sup..crclbar. Na.sup..sym.R'.sub.5 = + (CH.sub.2).sub.3COO.sup..crclbar. + Na.sup..sym. BF.sub.4 H SO.sub.3.sup..crclbar. + Na.sym. H H + ##STR34## + H H + *G: General Formula +PAR These illustrated labeling agents absorb light in a near-infrared + wavelength region of 670 to 900 nm, and the molar absorption coefficient + .epsilon. is in the region of 50,000 to 300,000 1/mol.cm. The illustrated + labeling agents include those generating strong fluorescence. +PAR Table 4 shows the maximum absorption wavelength (.lambda.max) and maximum + fluorescence wavelength of (.lambda.em) each of the labeling agents + generating fluorescence in the region of the semiconductor laser + wavelength (medium: ethanol/dichloromethane=1/4). +TBL TABLE 4 + ______________________________________ + Maximum absorption + Maximum fluorescence + No. wavelength (.lambda. max) + wavelength (.lambda. em) + ______________________________________ + 2 828 863 + 3 833 871 + 4 825 857 + 6 825 851 + 7 830 871 + 16 790 828 + 27 826 870 + ______________________________________ +PAR FIG. 1 shows the fluorescence emitting wave form on the incidence of + semiconductor laser beam (10 mW) of 830 nm into a labeling agent No. 3. + The apparatus for measurement is IMUC-7000 manufactured by Otsuka Electron + Co., Ltd. +PAR In FIG. 1, curve A shows incident wave form of semiconductor laser beam. + Curve B shows A fluorescence emitting wave form of a labeling agent No. 3. +PAR Alternatively, the labeling agent to be used in the present invention is a + compound of the general formula (IV), wherein A, B, D and E individually + represent hydrogen atom or alkyl group (for example, ethyl group, n-propyl + group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, + t-butyl group, n-amyl group, t-amyl group, n-hexyl group, n-octyl group, + t-octyl group and the like); and additionally, other alkyl groups such as + for example a substituted alkyl group (for example, 2-hydroxyethyl group, + 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, + carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, + 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfate + propyl group, 4-sulfate butyl group, N-(methylsulfonyl)-carbamylmethyl + group, 3-(acetyl-sulfamyl)propyl group, 4-(acetylsulfamyl)butyl group and + the like); cyclic alkyl groups (for example cyclohexyl group), allyl group + (CH.sub.2 .dbd.CH--CH.sub.2 --), alkenyl group (vinyl group, propenyl + group, butenyl group, pentenyl group, hexenyl group, heptenyl group, + octenyl group, dodecyl group, prenyl group and the like), aralkyl group + (for example, benzyl group, phenethyl group, .alpha.-naphthylmethyl group, + .beta.-naphthylmethyl group and the like), a substituted aralkyl group + (for example, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group + and the like), a substituted or an unsubstituted aryl group (for example, + phenyl group, aminophenyl group, naphthyl group, tolyl group, xylyl group, + methoxyphenyl group, dimethoxyphenyl group, trimethoxyphenyl group, + ethoxyphenyl group, dimethylaminophenyl group, diethylaminophenyl group, + dipropylaminophenyl group, dibenzylaminophenyl group, diphenylaminophenyl + group, sulfonate phenyl group, carboxylate phenyl group and the like), a + substituted or an unsubstituted heterocyclic group (for example, pyridyl + group, quinolyl group, lepidyl group, methylpyridyl group, furyl group, + phenyl group, indolyl group, pyrrolle group, carbazolyl group, + N-ethylcarbazolyl group and the like), or a substituted or an + unsubstituted styryl group (for example, styryl group, methoxystyryl + group, dimethoxystyryl group, trimethoxystyryl group, ethoxystyryl group, + aminostyryl group, dimethylaminostyryl group, diethylaminostyryl group, + dipropylaminostyryl group, dibenzylaminostyryl group, diphenylaminostyryl + group, 2,2-diphenylvinyl group, 2-phenyl-2-methylvinyl group, + 2-(dimethylamino-phenyl)-2-phenylvinyl group, + 2-(diethylaminophenyl)-2-phenylvinyl group, + 2-(dibenzylaminophenyl)-2-phenylvinyl group, 2,2-di(diethylaminophenyl + )vinyl group, 2,2-di(methoxyphenyl)vinyl group, 2,2-di(ethoxylphenyl)vinyl + group, 2-(dimethylaminophenyl)-2-methylvinyl group, + 2-(diethylaminophenyl)-2-ethylvinyl group, and the like). +PAR r.sub.1 ' and r.sub.2 ' individually represent hydrogen atom or alkyl group + (for example, methyl group, ethyl group, n-propyl group, iso-propyl group, + n-butyl group, sec-butyl group, iso-butyl group, t-butyl group, n-amyl + group, t-amyl group, n-hexyl group, n-octyl group, t-octyl group and the + like); and additionally, other alkyl groups such as for example a + substituted alkyl group (for example, 2-hydroxyethyl group, + 3-hydroxypropyl group, 4-hydroxybutyl group, 2-acetoxyethyl group, + carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, + 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-sulfate + propyl group, 4-sulfate butyl group, N-(methylsulfonyl)-carbamylmethyl + group, 3-(acetylsulfamyl)propyl group, 4-(acetylsulfamyl)butyl group and + the like); cyclic alkyl group (for example, cyclohexyl group), allyl group + (CH.sub.2 .dbd.CH--CH.sub.2 --), alkenyl group (vinyl group, propenyl + group, butenyl group, pentenyl group, hexenyl group, heptenyl group, + octenyl group, dodecyl group, prenyl group and the like), aralkyl group + (for example, benzyl group, phenethyl group, .alpha.-naphthylmethyl group, + .beta.-naphthylmethyl group and the like), and a substituted aralkyl group + (for example, carboxybenzyl group, sulfobenzyl group, hydroxybenzyl group + and the like). +PAR A, B, D, r.sub.1 ' and r.sub.2 ' preferably contain one or more well-known + polar groups in order to impart water solubility to the labeling agent + (dye) of the general formula (IV). The reactive group includes for example + hydroxyl group, alkylhydroxyl group, sulfone group, alkyl sulfone group, + carboxyl group, alkylcarboxyl group, tetra-ammonium base and the like. A, + B, D, r.sub.1 ' and r.sub.2 ' preferably contain one or more well-known + reactive groups in order that the labeling agent of the general formula + (IV) can form a covalent bond with a substance from a living organism. +PAR The reactive group includes the reactive sites of isocyanate, + isothiocyanate, succinimide ester, sulfosuccinimide ester, imide ester, + hydrazine, nitroaryl halide, piperidine disulfide, maleimide, thiophthal + imide, acid halide, sulfonyl halide, aziridine, azide nitrophenyl, azide + amino, 3-(2-pyridyldithio) propionamide and the like. In these reactive + sites, the following spacer groups + ##STR35## + (n=0, 1 to 16) may be interposed in order to prevent the steric hindrance + on the bonding of a labeling agent and a substance from a living organism. +PAR Preferable such reactive groups include isothiocyanate, sulfosuccinimide + ester, succinimide ester, maleimide and the like. +PAR The k in the general formula (IV) is 0 or 1 and 1 is 1 or 2. +PAR X.sub.2.sup..crclbar. represents an anion including chlorine ion, bromine + ion, iodine ion, perchlorate ion, benzenesulfonate ion, p-toluene + sulfonate ion, methylsulfate ion, ethylsulfate ion, propylsulfate ion, + tetrafluoroborate ion, tetraphenylborate ion, hexafluorophosphate ion, + benzenesulfinic acid ion, acetate ion, trifluoroacetate ion, propionate + ion, benzoate ion, oxalate ion, succinate ion, malonate ion, oleate ion, + stearate ion, citrate ion, monohydrogen diphosphate ion, dihydrogen + monophosphate ion, pentachlorostannate a ion, chlorosulfonate ion, + fluorosulfonate ion, trifluoromethane sulfonate ion, hexafluoroantimonate + ion, molybdate ion, tungstate ion, titanate ion, zirconate ion and the + like. +PAR Specific examples of these labeling agents are illustrated in Table 5, but + are not limited thereto. +TBL3 TABLE 5 + - No A B D E r.sub.1 ' r.sub.2 + ' X.sub.2 + 28 ph .rarw. .rarw. + ##STR36## + -- -- BF.sub.4 k = 0,l = + 1 + 29 + ##STR37## + .rarw. .rarw. + ##STR38## + -- -- BF.sub.4 k = 0,l = + 1 + 30 + ##STR39## + ##STR40## + (CH.sub.3).sub.2N + ##STR41## + -- -- I k = 0,l = + 1gleaming + 31 + ##STR42## + ##STR43## + (C.sub.2 H.sub.5).sub.2 + N + ##STR44## + H CH.sub.3 AsF.sub.6 k = 1,l = + 0 + 32 + ##STR45## + .rarw. .rarw. + ##STR46## + -- -- FSO.sub.3 k = 0,l = + 1 + 33 + ##STR47## + ##STR48## + ##STR49## + ##STR50## + -- -- + ##STR51## + k = 0,l = + 1 + 34 + ##STR52## + Ph + ##STR53## + ##STR54## + -- -- + ##STR55## + k = 0,l = + 1 + 35 + ##STR56## + .rarw. .rarw. .rarw. H + ##STR57## + BF.sub.4 k = 1,l = + 0 + 36 + ##STR58## + H + ##STR59## + .rarw. -- -- AsF.sub.6 k = 0l = + 0 + 37 + ##STR60## + .rarw. .rarw. .rarw. H + ##STR61## + BF.sub.4 k = 1,l = + 0 + 38 + ##STR62## + .rarw. + ##STR63## + .rarw. -- -- FSO.sub.3 k = 0,l = + 1 + 39 + ##STR64## + .rarw. .rarw. .rarw. H C.sub.2 H.sub.5 BF.sub.4 k = 1,l = + 0 + 40 + ##STR65## + .rarw. .rarw. + ##STR66## + -- -- BF.sub.4 k = 0,l = + 1 + 41 + ##STR67## + .rarw. .rarw. .rarw. H + ##STR68## + BF.sub.4 k = 1,l = + 0 + 42 + ##STR69## + CH.sub.3 + ##STR70## + CH.sub.3 H CH.sub.3 FSO.sub.3 k = 1,l = + 0 + 43 + ##STR71## + C.sub.3 + H.sub.7 + ##STR72## + C.sub.3 + H.sub.7 H + ##STR73## + BF.sub.4 k = 1,l = + 0 + 44 + ##STR74## + ##STR75## + ##STR76## + ##STR77## + -- -- + ##STR78## + k = 0,l = + 1 + 45 + ##STR79## + ##STR80## + ##STR81## + ##STR82## + -- -- AsF.sub.6 k = 0,l = + 1 + 46 + ##STR83## + ##STR84## + ##STR85## + ##STR86## + -- + ##STR87## + I k = 0,l = + 1 + 47 + ##STR88## + ##STR89## + ##STR90## + ##STR91## + -- + ##STR92## + I k = 1,l = + 0 + 48 + ##STR93## + ##STR94## + ##STR95## + ##STR96## + -- -- BF.sub.4 k = 0,l = + 1 +PAR These illustrated labeling agents absorb light in a near-infrared + wavelength region of 670 to 900 nm, and the molar absorption coefficient e + is in the region of 50,000 to 300,000 1/mol.cm. Some of the illustrated + labeling agents generate intense fluorescence. +PAR The dye No. 30 illustrated in Table 5 exhibits the maximum absorption at a + wavelength of 819 nm in a near-infrared region and emits fluorescence. The + maximum fluorescence wavelength (.lambda.em) is 864 nm (medium; + dichloromethane). +PAR In accordance with the present invention, the labeling agents described + above are immobilized onto a substance from a living organism, but the + substance from a living organism to be immobilized is selectively + determined based on a substance to be analyzed or a subject sample. That + is, if a substance is selected from a living organism having a biological + specificity to a subject sample, the substance to be analyzed can be + detected with specificity. By the term "substance from a living organism" + is meant naturally occurring or synthetic peptides, proteins, enzymes, + sugars, rectins, viruses, bacteria, nucleic acids, DNA, RNA, antigens + (including for example recombinant antigens), antibodies and the like. The + substances specifically useful in terms of clinical pathology include the + following; immunoglobulin such as IgG, IgM, IgE and the like; plasma + proteins and antibodies thereof, such as compliments, CRP, ferritin, + .alpha.1-microglobulin, .beta.2-microglobulin, and the like; tumor markers + and antibodies thereof, such as .alpha.-fetoprotein, carcinoembryonic + antigen (CEA), prostate acid phosphatase (PAP), CA19-9, CA-125 and the + like; hormones and antibodies thereof such as luteinizing hormone (LH), + follicle stimulating hormone (FSH), human chorionic gonadotropin (hCG), + estrogen, insulin and the like; substances in relation with virus + infection and antibodies thereof, such as HBV-related antigens (HBs, HBe, + HBc), HIV, ATL and the like; bacteria and antibodies thereof, such as + Corynebacterium diphteriae, Clostridium botulinum, mycoplasma, Treponema + pallidum and the like; protozoae and antibodies thereof such as Toxoplasma + gondii, Trichomonas, Leishmania, Tripanozoma, malaria protozoa and the + like; pharmaceutical agents and antibodies thereof, such as antileptic + agents including phenytoin, phenobarbital and the like, cardiovascular + agents including quinidine and digoxin, antasthmatic agents including + theophylline, antibiotics including chloramphenicol and gentamycin; as + well as, enzymes, enterotoxin (streptolysin O) and the antibodies thereof. + Depending on the type of sample, a substance which can incur the + antigen-antibody reaction with a substance to be measured in a sample is + appropriately selected for use. +PAR In accordance with the present invention, the following known method can be + utilized in order to immobilize a labeling agent onto a substance from a + living organism such as a physiological active substance. +PAR There are illustrated for example i) ion bonding method, ii) physical + absorption method, iii) covalent bonding method and the like. +PAR The ion bonding method comprises electrostatically bonding a labelling + agent having principally a positive charge to a substance from a living + organism such as proteins, DNA, RNA and the like. +PAR The physical absorption method comprises utilizing the hydrophobic bond + between the lipophilic part of a labeling agent and the lipophilic part of + a protein. +PAR The reaction process of bonding is simple in accordance with the ion + bonding method and physical absorption method, but the bonding strength of + a labeling agent and a substance from a living organism is weak. +PAR On contrast, the covalent bonding method comprises bonding a highly + reactive functional group to at least one of a labeling agent and a + substance from a living organism, and covalently bonding the two through + the functional group whereby a highly intense bonding strength can be + generated. In bonding a labeling agent with a substance from a living + organism such as physiological active substances via covalent bonds, the + functional groups being present in the substance from a living organism + and which can be involved in the bonding, include free amino group, + hydroxyl group, phosphate group, carboxyl group, the sulfhydryl group of + cysteine, the imidazole group of histidine, phenol group of tyrosine, the + hydroxyl group of serine and threonine, and the like. +PAR These functional groups react with a variety of diazonium salts, acid + amides, isocyanate, active-type halogenated alkyl groups, active-type + ester groups and the like. Therefore, by a variety of methods, dyes can be + immobilized onto a substance from a living organism by introducing these + functional groups into a labeling agent. Alternatively, the conformation + of a substance from a living organism, specifically that of proteins, is + readily damaged because it is retained through relatively weak bonds such + as hydrogen bond, hydrophobic bond, ion bond and the like. Thus, the + immobilization with a labeling agent preferably should be carried out + under mild conditions, without processing by means of high temperatures, + strong acids and strong alkalis. +PAR One method of carrying out the immobilization under mild conditions + includes the use of bifunctional cross-linking agents which react with a + labeling agent and with the functional groups of a substance from a living + organism. The bifunctional cross-linking agents include, for example, + carbodiimide represented by the general formula R--N.dbd.C.dbd.N--R', + dialdehyde represented by the general formula CHO--R--CHO, diisocyanate + represented by O.dbd.C.dbd.N--R--N.dbd.C.dbd.O (wherein R and R' represent + individually the same or a different substituted or unsubstituted alkyl + group, aryl group alkylaryl group or aryl alkyl group), and the like. +PAR The analysis of a certain particular objective substance is conducted by + using the resulting labeled complex in which a labeling agent is + immobilized onto a substance from a living organism. +PAR If a target (analytical subject) is one species of cell, the labeled + complex is bonded to a specific substance on the cell complimentary to the + substance from a living organism bonded to the labeled complex via a + specific bonding such as an antigen-antibody reaction or the hydrogen + bonding between nucleic acids. Then, the amount of such antigen, antibody + or nucleic acids can be measured based on the fluorescence or absorbance + of the system. +PAR If the analysis is effected of a target in relation with an antigen and an + antibody, a complex bonded through the labeling agent to an antigen (or an + antibody) and an antibody (an antigen if a labeling agent is immobilized + onto the antibody) to be measured are subjected to antigen-antibody + reaction. The complex (B; bonded type) bonded to the antibody (antigen) is + then separated from the complex (F; free type) which is not bonded to the + antibody (antigen) (B/F separation). Thereafter, the amount of the complex + (B) is determined based on the fluorescence or absorbance. The technique + utilizing the antigen-antibody reaction described above is described in + details in "Examination and Technology", Vol. 16, No. 7 (1988). +PAR In terms of detection sensitivity, furthermore, it is preferable that two + or more, preferably 10 or more labeling agents are bonded to one molecule + of a substance from a living organism. In terms of synthesis and + sensitivity, preferably 10 to 100, more preferably 20 to 50 such agents + may be bonded to one molecule thereof. +PAR The present invention will now be explained with reference to examples. +PAC EXAMPLE 1 +PAR Anti-human CRP sheep serum (IgG fraction; manufactured by Cooper Biomedical + Inc.) was diluted with phosphate buffer, pH 8.0, to a concentration of 0.5 + mg/ml, to prepare an antibody solution. To 8 ml of the antibody solution + were added 0.2 mg of a labeling agent No. 3 of Table 1 (.lambda.max=833 + nm) and 0.09 g of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide + hydrochloride (referred to as WSC hereinafter) (manufactured by Dojin + Chemicals, Co. Ltd.) for reaction at room temperature for three hours, to + generate a labeling agent-antibody complex. The labeling agent-antibody + complex was separated and purified from unreacted substances by gel + filtration chromatography on a column packed with Sepharose 6B. The + bonding molar ratio of the labeling agent and the antibody in the complex + thus obtained was 2.1:1. By using a spectrophotometer Shimadzu UV-3100S, + the absorbance of the complex was measured at wavelengths .lambda.=833 nm + and .lambda.=280 nm, separately, to calculate the molar ratio of the + labeling agent and the antibody. +PAC EXAMPLE 2 +PAR Rectin. Concanavalin A (manufactured by E. Y. Laboratories Co. Ltd.) was + diluted with phosphate buffer, pH 8.2, to a concentration of 0.2 mg/ml, to + prepare a rectin solution. +PAR With 10 ml of the rectin solution was reacted 0.2 mg of a labeling agent + No. 6 of Table 1 (.lambda.max=825 nm) at room temperature for three hours. + The labeling agent-rectin complex was separated and purified on a gel + filtration chromatocolumn packed with Sepharose 6B. The molar ratio of the + labeling agent and the rectin in the complex obtained was 3.7:1. The + absorbances at wavelengths .lambda.=825 and .lambda.=280 nm were measured + by a spectrophotometer Shimadzu UV-3100S, to calculate the molar ratio of + the labeling agent and the rectin. +PAC EXAMPLE 3 +PAR Anti-human HCG monoclonal antibody (manufactured by ZyMED Lab. Inc.) was + diluted with phosphate buffered physiological saline (PBS), pH 7.2, to a + concentration of 0.2 mg/ml, to prepare a monoclonal antibody solution. +PAR To 8 ml of the antibody solution was added 0.3 mg of a labeling agent No. + 12 of Table 1 (.lambda.max=705 nm) for agitation at room temperature for + three hours. The labeling agent-antibody complex was separated and + purified by gel filtration chromatography on a column packed with + Sepharose 6B. +PAR The molar ratio of the labeling agent and the antibody in the labeling + agent-antibody complex thus obtained was 1.7:1. By using a + spectrophotometer 1 Shimadzu UV-3100S, the absorbance of the complex was + measured at wavelengths .lambda.=705 nm and .lambda.=280 nm, separately, + to calculate the molar ratio of the labeling agent and the antibody. +PAC EXAMPLE 4 +PAR M13mp18 single-strand DNA (7249 bases) (manufactured by TAKARA Liquor KK.) + (0.1 mg) was diluted with 5 mmol phosphate buffer, pH 6, to prepare a DNA + solution. A labeling agent No. 5 (0.1 mg) shown in Table 1 + (.lambda.max=796 nm) was dissolved in 5 ml of distilled water, and + subsequently, 5 ml of the DNA solution was gradually added dropwise to the + resulting dye solution. Agitation was further effected at room temperature + for 2 hours, to produce a DNA-labeling agent complex. +PAR To the solution of the DNA-labeling agent complex described above was added + further 40 ml of ethanol, to precipitate the DNA-labeling agent complex. + The DNA-labeling agent complex was separated on a filter, followed by + washing with ethanol. The DNA-labeling agent complex after the washing was + again dissolved in 2 ml of the phosphate buffer, pH 6. The amount of the + labeling agent bonded to that of the DNA was 0.5 .mu.g per .mu.g.DNA. The + absorbance of the complex was measured at wavelengths .lambda.=705 nm and + .lambda.=280 nm, separately, to calculate the concentrations of the + labeling agent and the DNA. +PAC EXAMPLE 5 +PAR A 20-mer oligonucleotide having a base sequence partially complimentary to + the base sequence of a model target nucleic acid M13mp18 ss DNA was + synthesized by a DNA synthesizer 381 A, manufactured by ABI Co. Ltd. Then, + a primary amine was introduced into the 5' terminus of the oligonucleotide + by using a N-MMT-hexanol amine linker manufactured by Milligen Co. Ltd., + instead of general amidide reagents. A predetermined protocol was followed + to perform cutting out from the CPG-support, deprotection (including the + deprotection of monomethoxytrityl group as a protective group of the + primary amine), and the purification by high-performance liquid + chromatography. +PAR After mixing together 200 .mu.g of the oligonucleotide, 100 .mu.l of 1M + sodium carbonate buffer, pH 9.0, and 700 .mu.l of water, 2 mg of a + labeling agent No. 27 (.lambda.max=826 nm) shown in Table 1, which had + preliminarily been dissolved in 200 .mu.l of dimethyl formamide, was + gradually added under agitation. After the reaction at room temperature + for 24 hours, the peak of the nucleic acid was decreased on a + high-performance liquid chromatogram, whereas a new peak having the + absorbances of the nucleic acid and the labeling agent developed. Thus, + the reaction solution was nearly purified on a gel filtration column, + NAP-50, manufactured by Pharmacia, which was then purified by HPLC to + obtain 175 .mu.g of the nucleic acid-labeling agent complex. +PAC COMPARATIVE EXAMPLE 1 +PAR The chemical structure of a well-known cyanine-type near-infrared + absorption dye NK-1967 (manufactured by Nippon Photosensitive Dye Research + Institute) is depicted hereinbelow. + ##STR97## +PAR To 5 ml of the antibody solution prepared in Example 1 was added 0.3 mg of + the cyanine dye, and agitated at room temperature for 3 hours, to generate + a labeling agent-antibody complex. +PAR The labeling agent-antibody complex was separated and purified by gel + filtration chromatography on a column packed with Sepharose 6B. +PAR The molar ratio of the labeling agent and the antibody was 1.7:1. The + absorbances at wavelength p=747 nm and p=280 nm were measured by a + spectrophotometer Shimadzu UV-3100S to calculate the molar ratio of the + labeling agent and the antibody. Complex stability under storage +PAR In order to examine the complex stability under storage, the following + experiments were carried out. +PAR The labeled complexes prepared in Examples 1 to 5 and Comparative Example 1 + were prepared to predetermined concentrations with 10 mmol phosphate + buffer, pH 7.2. The solutions of the labeled complexes were kept in dark + at 7.degree. C. for three days. At the initiation and termination of the + test of complex stability under storage, the absorbance was measured at + predetermined wavelengths to calculate the ratio of the absorbance at the + termination, provided that the absorbance at the initiation was designated + as 100. +PAR For the complexes exhibiting fluorescence, the ratio of the fluorescence + intensity at the termination was calculated, provided that the + fluorescence intensity at the initiation was designated as 100. +PAR The results are shown in Table 6. +TBL TABLE 6 + ______________________________________ + Stability under storage of labeled complexes + Change in + Change in fluorescence + absorbance* + intensity** + (wavelength + (wavelength + Concentration + in nm) in nm) + ______________________________________ + Example + 1 0.4 g/ml 93.4 (833) + 94 (875) + 2 0.4 g/ml 91.9 (825) + 90 (870) + 3 0.5 g/ml 94.2 (705) + -- + 4 0.4 g/ml 95.1 (796) + -- + 5 0.5 g/ml 96.1 (826) + 93 (870) + Comparative + Example + 1 0.5 g/ml 71.2 (747) + 63 (820) + ______________________________________ + *The initial absorbance was designated as 100. + **The initial fluorescence was designated as 100. +PAR As is shown in Table 6, the labeled complexes of the present invention + showed lower change of the absorbance or fluorescence intensity in water + than those of Comparative Example. +PAC EXAMPLE 6 +PAR Anti-human CRP sheep serum (IgG fraction; manufactured by Cooper Biomedical + Inc.) was diluted with PBS, pH 7.2, to a concentration of 0.5 mg/ml, to + prepare an antibody solution. To 8 ml of the antibody solution were added + 0.2 mg of a labeling agent No. 29 of Table 5 (.lambda.max=819 nm) and 0.09 + g of WSC for reaction at room temperature for three hours, to generate a + dye-antibody complex. The dye-antibody complex was separated and purified + from unreacted substances by gel filtration chromatography on a column + packed with Sepharose 6B. The molar ratio of the dye and the antibody in + the complex thus obtained was 2.5:1. By using a spectrophotometer, + Shimadzu UV-3100S, the absorbance of the complex was measured at + wavelength .lambda.=819 nm and .lambda.=280 nm, separately, to calculate + the molar ratio of the dye and the antibody. +PAC EXAMPLE 7 +PAR Anti-human HCG monoclonal antibody (manufactured by ZyMED Lab, Inc.) was + diluted with PBS to a concentration of 0.4 mg/ml, to prepare a monoclonal + antibody solution. To 2 ml of the monoclonal antibody solution were added + 0.3 mg of a dye No. 32 of Table 5 (.lambda.max=825 nm) and 0.10 g of + Woodward reagent (manufactured by Tokyo Chemicals, Co. Ltd.) for reaction + at room temperature for three hours. The dye-antibody complex was + separated and purified by gel filtration chromatography on a column packed + with Sepharose 6B. The molar ratio of the dye and the antibody in the + dye-antibody complex thus obtained was 3.1:1. By using a spectrophotometer + Shimadzu UV-3100S, the absorbance of the complex was measured at + wavelengths .lambda.=825 nm and .lambda.=280 nm, separately, to calculate + the molar ratio of the dye and the antibody. +PAC EXAMPLE 8 +PAR Rectin.Concanavalin A (manufactured by E. Y. Laboratories Co. Ltd.) was + diluted with PBS to a concentration of 0.2 mg/ml, to prepare a rectin + solution. With 10 ml of the rectin solution were added 0.2 mg of a dye No. + 40 of Table 5 (.lambda.max=805 nm) and 10 ml of 0.05 M sodium borate + buffer, pH 8.0 containing 1% glutaraldehyde at room temperature for one + hour. The dye-rectin complex was separated and purified on a gel + filtration chromatocolumn packed with Sepharose 6B. The molar ratio of the + dye and the rectin in the complex obtained was 1.7:1. The absorbances at + wavelengths .lambda.=805 and .lambda.=280 nm were measured by a + spectrophotometer Shimadzu UV-3100S, to calculate the molar ratio of the + dye and the rectin. +PAC EXAMPLE 9 +PAR M13mp18 single-strand DNA (7249 bases) (manufactured by TAKARA Liquor KK.) + (0.1 mg) was diluted with 5 mmol phosphate buffer, pH 6, to prepare a DNA + solution. A dye No. 35 (0.1 mg) shown in Table 5 (.lambda.max=780 nm) was + dissolved in 2 ml of ethanol, followed by gradual dropwise addition of 5 + ml of the DNA solution to the resulting dye solution under stirring. + Agitation was further effected at room temperature for 2 hours, to produce + a DNA-dye complex. +PAR To the solution of the DNA-dye complex described above was added further 40 + ml of ethanol, to precipitate the DNA-dye complex. The DNA-dye complex was + separated on a filter, followed by washing several times with ethanol. The + DNA-dye complex after the washing was again dissolved in 2 ml of the + phosphate buffer, pH 6. The amount of the dye bonded to that of the DNA + was 0.5 .mu.g per .mu.g.DNA. The absorbance of the complex was measured at + wavelengths .lambda.=780 nm and .lambda.=260 nm, separately, to calculate + the concentrations of the dye and the DNA. +PAC EXAMPLE 10 +PAR A 20-mer oligonucleotide having a base sequence partially complimentary to + the base sequence of a model target nucleic acid M13mp18 ss DNA was + synthesized by a DNA synthesizer 381 A, manufactured by ABI Co. Ltd. Then, + a primary amine was introduced into the 5' terminus of the oligonucleotide + by using a N-MMT-hexanol amine linker manufactured by Milligen Co. Ltd., + instead of general amidide reagents. A predetermined protocol was followed + to perform cutting out from the CPG-support, deprotection (including the + deprotection of monomethoxytrityl group as a protective group of the + primary amine), and the purification by high-performance liquid + chromatography. +PAR After mixing together 200 .mu.g of the oligonucleotide, 100 .mu.l of 1M + sodium carbonate buffer, pH 9.0, and 700 .mu.l of water, 2 mg of a dye No. + 46 (.lambda.max=810 nm) shown in Table 5, which had preliminarily been + dissolved in 200 N1 of dimethyl formamide, was gradually added under + agitation. After the reaction at room temperature for 24 hours, the peak + of the nucelic acid was decreased on a high-performance liquid + chromatogram, whereas a new peak having the absorbances of the nucleic + acid and the dye developed. Thus, the reaction solution was nearly + purified on a gel filtration column, NAP-50, manufactured by Pharmacia, + which was then purified by HPLC to obtain 175 .mu.g of the nucleic + acid-dye complex. Complex stability under storage +PAR In order to examine the stability under storage of dye complexes, the + following experiments were carried out. +PAR The labeled dye complexes prepared in Examples 6 to 10 were prepared to + predetermined concentrations with 10 mmol phosphate buffer, pH 7.2. The + solutions of the labeled complexes were kept in dark at 7.degree. C. for + three days. At the initiation and termination of the test of complex + stability under storage, the absorbance was measured at predetermined + wavelengths. Then, the ratio of the absorbance at the termination was + calculated, provided that the absorbance at the initiation was designated + as 100. +PAR The results are shown in Table 7. +TBL TABLE 7 + ______________________________________ + Stability under storage of labeled dye complexes + Change in absorbance + Wavelength + (initial absorbance + for was designated + Example + Concentration + measurement + as 100) + ______________________________________ + 6 0.5 g/ml 819 95.1 + 7 0.5 g/ml 825 94.5 + 8 0.5 g/ml 805 91.3 + 9 0.4 g/ml 780 95.7 + 10 0.4 g/ml 810 93.9 + ______________________________________ +PAR As is shown in Table 7, the labeled dye complexes of the present invention + showed lower change of the absorbance in water than those of Comparative + Example. +PAC EXAMPLE 11 +PAR A 20-mer oligonucleotide having a base sequence partially complimentary to + the base sequence of a model target nucleic acid M13mp18 ss DNA was + synthesized by a DNA synthesizer 381 A, manufactured by ABI Co. Ltd. Then, + by using a deoxyuridylic acid derivative monomer: + ##STR98## + with an amino group introduced, instead of general amidide reagents, 20 + such deoxyuridylic acid derivatives each having a primary amine group were + added to the 5' terminus of the oligonucleotide. Routine method was + followed to perform cutting out from the CPG-support, deprotection + (including the deprotection of trifluoroacetyl group as a protective group + of the primary amine), and the purification by high-performance liquid + chromatography. +PAR After mixing together 200 .mu.g of the oligonucleotide bonding the primary + amines, 100 .mu.l of 1M sodium carbonate buffer, pH 9.0, and 700 .mu.l of + water, 5 mg of a dye No. 27 (.lambda.max=826 nm) shown in Table 1, which + had preliminarily been dissolved in 200 .mu.l of dimethyl formamide, was + gradually added under agitation. After the reaction at 40.degree. C. for + 24 hours, the peak of the nucleic acid was decreased on a high-performance + liquid chromatogram, whereas a new peak having the absorbances of the + nucleic acid and the labeling agent developed. Thus, the reaction solution + was nearly purified on a gel filtration column, NAP-50, manufactured by + Pharmacia, which was then purified by HPLC to obtain 350 .mu.g of the + nucleic acid-labeling agent complex. The absorbance of the nucleic + acid-labeling agent complex at 826 nm had the intensity about 20-fold that + of the nucleic acid-labeling agent shown in Example 5. +PAR In accordance with the present invention, a stable complex can be formed + with less decomposition of dyes, and hence with less change in absorbance + or with less change in fluorescence, by bonding a labeling agent of a + particular structure to a substance from a living organism. +PAR Therefore, the complex of the present invention can provide a reagent with + excellent stability under storage for the application to microanalysis. +CLMS +STM What is claimed is: +NUM 1. +PAR 1. A labeled complex for detecting a subject compound to be analyzed by + means of optical means using near-infrared radiation which complex + comprises a substance from a living organism and a labeling agent fixed + onto the substance, the substance capable of specifically binding to the + subject compound, wherein the labeling agent comprises a compound + represented by the general formula (IV): + ##STR99## + wherein A, B, D and E are independently selected from the group consisting + of hydrogen atom, a substituted or an unsubstituted alkyl group having two + or more carbon atoms, alkenyl group, aralkyl group, aryl group, styryl + group and heterocyclic group, and at least one of A and B is a substituted + or unsubstituted aryl group, and at least one of D and E is a substituted + or unsubstituted aryl group; +PA1 r.sub.1 ' and r.sub.2 ' are individually selected from the group consisting + of hydrogen atom, a substituted or an unsubstituted alkyl group, cyclic + alkyl group, alkenyl group, aralkyl group and aryl group; k is 0 or 1; is + 0, 1 or 2; and X.sub.2.sup..crclbar. represents an anion. +NUM 2. +PAR 2. The labeled complex according to claim 1, wherein the substance from a + living organism is an antibody or an antigen. +NUM 3. +PAR 3. The labeled complex according to claim 1, wherein the substance from a + living organism is a nucleic acid. +NUM 4. +PAR 4. The labeled complex according to claim 1, wherein the substituted aryl + group constituting at least one of A and B is phenyl group substituted by + dialkylamino group. +NUM 5. +PAR 5. The labeled complex according to claim 1, wherein the substituted aryl + group constituting at least one of D and E is phenyl group substituted by + dialkylamino group. +NUM 6. +PAR 6. The labeled complex according to claim 4 or 5, wherein the dialkylamino + group is a diethylamino group. +NUM 7. +PAR 7. The labeled complex according to claim 1, wherein each of A, B and D is + dimethylaminophenyl group, E is aminophenyl group, k is 0 and l is 1. +NUM 8. +PAR 8. The labeled complex according to claim 1, wherein each of A, B and D is + diethylaminophenyl group, E is phenyl group substituted by carboxyl group, + k is 0 and l is 1. +NUM 9. +PAR 9. The labeled complex according to claim 1, wherein each of A, B, D and E + is diethylaminophenyl group, k is 1 and l is 0. +NUM 10. +PAR 10. The labeled complex according to claim 1, wherein each of A, B, and D + is diethylaminophenyl group, E is aminophenyl group, K is 0 and l is 1. +NUM 11. +PAR 11. The labeled complex according to claim 1, wherein A is + dimethylaminophenyl group, each of B and E is ethoxyphenyl group, k is 0, + 1 is l and D is represented by the following formula: + ##STR100## +NUM 12. +PAR 12. A method of detecting a subject compound to be analyzed in a sample + comprising the steps of: +PA1 providing a labeled complex comprising a substance from a living organisms + and a labeling agent fixed onto the substance, the substance being capable + of specifically binding to the subject compound; +PA1 binding the labeled complex to the subject compound; and +PA1 detecting the labeled complex to which the subject compound is bonded by + means of optical means, wherein the labeling agent comprises a compound + represented by the general formula (IV): + ##STR101## + wherein A, B, D and E are independently selected from the group consisting + of hydrogen atom, a substituted or an unsubstituted alkyl group having two + or more carbon atoms, alkenyl group, aralkyl group, aryl group, styryl + group and heterocyclic group, and at least one of A and B is a substituted + or unsubstituted aryl group, and at least one of D and E is a substituted + or unsubstituted aryl group; +PA1 r.sub.1 ' and r.sub.2 ' are individually selected from the group consisting + of hydrogen atom, a substituted or an unsubstituted alkyl group, cyclic + alkyl group, alkenyl group, aralkyl group and aryl group; k is 0 or 1; is + 0, 1 or 2; and X.sub.2.sup..crclbar. represents an anion. +NUM 13. +PAR 13. The method according to claim 12, wherein the substance from a living + organism is an antibody or an antigen. +NUM 14. +PAR 14. The method according to claim 12, wherein the substance from a living + organism is a nucleic acid. +NUM 15. +PAR 15. The analyzing method according to any one of claims 12, 13 and 14, + wherein the optical means is an optical means using near-infrared ray. +NUM 16. +PAR 16. The method according to claim 12, wherein each of A, B and D is + dimethylaminophenyl group, E is aminophenyl group, k is 0 and l is 1. +NUM 17. +PAR 17. The method according to claim 12, wherein each of A, B and D is + diethylaminophenyl group, E is phenyl group substituted by carboxyl group, + k is 0 and l is 1. +NUM 18. +PAR 18. The method according to claim 12, wherein each of A, B, D and E is + diethylaminophenyl group, k is 1 and l is 0. +NUM 19. +PAR 19. The method according to claim 12, wherein each of A, B and D is + diethylaminophenyl group, E is aminophenyl group, k is 0 and l is 1. +NUM 20. +PAR 20. The method according to claim 12, wherein A is dimethylaminophenyl + group, each of B and E is ethoxyphenyl group, k is 0, l is 1 and D is + represented by the following formula: + ##STR102## diff --git a/tests/data/uspto/pg06442728.xml b/tests/data/uspto/pg06442728.xml new file mode 100644 index 00000000..8c33f953 --- /dev/null +++ b/tests/data/uspto/pg06442728.xml @@ -0,0 +1,3091 @@ + + + + + + + + + + + +]> + + + +06442728 +B1 +20020827 +US + + +09263431 +09 +19990304 + + + +H03M 1300 +7 + + +714786 +714755 +714790 + +Methods and apparatus for turbo code + + + +4394642 +19830700 +A + + +Currie + + + + + +5742612 +19980400 +A + + +Gourge + + + +“Computer Dictionary” Microsoft Press, Second Edition, 1994, pp. 218-219.* +Interleaver design for turbo codes with reduced memory requirement, ETSI SMG2 UMTS L1 Expert Group, Tdoc SMG2 UMTS L1 510-98, Nov. 1998. +Description of the GF Interleaver for Turbo Codes, ETSI SMG2 UMTS L1 Expert Group, Tdoc SMG2 UMTS-L1 765/98, Jan. 1999. +Algebraic interleavers for turbo codes: Precisions on complexity and interleaver generation, ETSI SMG2 UMTS L1 Expert Group, Tdoc SMG2 UMTS-L1 721-98, Dec. 1998. +A Proposal for Turbo Code Interleaving, mschaff1@email.mot.com, Motorola, Inc. 1998. +Turbo Interleaver Performance Evaluation, brownta@cig.mot.com, Motorola, Inc., 1998. +A new Low-Complexity TurboCode Interleaver Employing Linear Congruential Sequences (Revised), fling@qualcomm.com, Qualcomm, Inc., 1998. +New Interleaver Proposals from Lucent Technologies. + + +35 +1 + + +714786 +714790 +714756 +714755 + +55 + + + +60/1153941999011100 + + + + + +JianCui + +Nepean +CA + + + + + +BinLi + +Ottawa +CA + + + + + +WengTong + +Ottawa +CA + + + + + +Rui R.Wang + +Ottawa +CA + + + + + + + +Nortel Networks Limited +St. LaurentCA + + + +03 + + + + + +Cobrin & Gittes + + + + + + +Phung M.Chung + + +2133 + + + + + +An interleaver receives incoming data frames of size N. The interleaver indexes the elements of the frame with an N1×N2 index array. The interleaver then effectively rearranges (permutes) the data by permuting the rows of the index array. The interleaver employs the equation I(j,k)=I(j,&agr;jk+&bgr;j)modP) to permute the columns (indexed by k) of each row (indexed by j). P is at least equal to N2, &bgr;j is a constant which may be different for each row, and each &agr;j is a relative prime number relative to P. After permuting, the interleaver outputs the data in a different order than received (e.g., receives sequentially row by row, outputs sequentially each column by column). + + + + + +CROSS-REFERENCE TO RELATED APPLICATIONS +This application claims the benefit of U.S. Provisional Application No. 60/115,394 filed Jan. 11, 1999. + + + + +FIELD OF THE INVENTION +This invention relates generally to communication systems and, more particularly, to interleavers for performing code modulation. +BACKGROUND OF THE INVENTION +Techniques for encoding communication channels, known as coded modulation, have been found to improve the bit error rate (BER) of electronic communication systems such as modem and wireless communication systems. Turbo coded modulation has proven to be a practical, power-efficient, and bandwidth-efficient modulation method for “random-error” channels characterized by additive white Gaussian noise (AWGN) or fading. These random-error channels can be found, for example, in the code division multiple access (CDMA) environment. Since the capacity of a CDMA environment is dependent upon the operating signal to noise ratio, improved performance translates into higher capacity. +An aspect of turbo coders which makes them so effective is an interleaver which permutes the original received or transmitted data frame before it is input to a second encoder. The permuting is accomplished by randomizing portions of the signal based upon one or more randomizing algorithms. Combining the permuted data frames with the original data frames has been shown to achieve low BERs in AWGN and fading channels. The interleaving process increases the diversity in the data such that if the modulated symbol is distorted in transmission the error may be recoverable with the use of error correcting algorithms in the decoder. +A conventional interleaver collects, or frames, the signal points to be transmitted into an array, where the array is sequentially filled up row by row. After a predefined number of signal points have been framed, the interleaver is emptied by sequentially reading out the columns of the array for transmission. As a result, signal points in the same row of the array that were near each other in the original signal point flow are separated by a number of signal points equal to the number of rows in the array. Ideally, the number of columns and rows would be picked such that interdependent signal points, after transmission, would be separated by more than the expected length of an error burst for the channel. +Non-uniform interleaving achieves “maximum scattering” of data and “maximum disorder” of the output sequence. Thus the redundancy introduced by the two convolutional encoders is more equally spread in the output sequence of the turbo encoder. The minimum distance is increased to much higher values than for uniform interleaving. A persistent problem for non-uniform interleaving is how to practically implement the interleaving while achieving sufficient “non-uniformity,” and minimizing delay compensations which limit the use for applications with real-time requirements. +Finding an effective interleaver is a current topic in the third generation CDMA standard activities. It has been determined and generally agreed that, as the frame size approaches infinity, the most effective interleaver is the random interleaver. However, for finite frame sizes, the decision as to the most effective interleaver is still open for discussion. +Accordingly there exists a need for systems and methods of interleaving codes that improve non-uniformity for finite frame sizes. +There also exists a need for such systems and methods of interleaving codes which are relatively simple to implement. +It is thus an object of the present invention to provide systems and methods of interleaving codes that improve non-uniformity for finite frame sizes. +It is also an object of the present invention to provide systems and methods of interleaving codes which are relatively simple to implement. +These and other objects of the invention will become apparent to those skilled in the art from the following description thereof. +SUMMARY OF THE INVENTION +The foregoing objects, and others, may be accomplished by the present invention, which interleaves a data frame, where the data frame has a predetermined size and is made up of portions. An embodiment of the invention includes an interleaver for interleaving these data frames. The interleaver includes an input memory configured to store a received data frame as an array organized into rows and columns, a processor connected to the input memory and configured to permute the received data frame in accordance with the equation D(j,k)=D (j, (&agr;jk+&bgr;j)modP), and a working memory in electrical communication with the processor and configured to store a permuted version of the data frame. The elements of the equation are as follows: D is the data frame, j and k are indexes to the rows and columns, respectively, in the data frame, &agr; and &bgr; are sets of constants selected according to the current row, and P and each &agr;j are relative prime numbers. (“Relative prime numbers” connotes a set of numbers that have no common divisor other than 1. Members of a set of relative prime numbers, considered by themselves, need not be prime numbers.) +Another embodiment of the invention includes a method of storing a data frame and indexing it by an N1×N2 index array I, where the product of N1 and N2 is at least equal to N. The elements of the index array indicate positions of the elements of the data frame. The data frame elements may be stored in any convenient manner and need not be organized as an array. The method further includes permuting the index array according to I(j,k)=I(j,(&agr;jk+&bgr;j)modP), wherein I is the index array, and as above j and k are indexes to the rows and columns, respectively, in the index array, &agr; and &bgr; are sets of constants selected according to the current row, and P and each &agr;j are relative prime numbers. The data frame, as indexed by the permuted index array I, is effectively permuted. +Still another embodiment of the invention includes an interleaver which includes a storage device for storing a data frame and for storing an N1×N2 index array I, where the product of N1 and N2 is at least equal to N. The elements of the index array indicate positions of the elements of the data frame. The data frame elements may be stored in any convenient manner and need not be organized as an array. The interleaver further includes a permuting device for permuting the index array according to I(j,k)=I(j,(&agr;jk+&bgr;j)modP), wherein I is the index array, and as above j and k are indexes to the rows and columns, respectively, in the index array, &agr; and &bgr; are sets of constants selected according to the current row, and P and each &agr;j are relative prime numbers. The data frame, as indexed by the permuted index array I, is effectively permuted. +The invention will next be described in connection with certain illustrated embodiments and practices. However, it will be clear to those skilled in the art that various modifications, additions and subtractions can be made without departing from the spirit or scope of the claims. + + + + +BRIEF DESCRIPTION OF THE DRAWINGS +The invention will be more clearly understood by reference to the following detailed description of an exemplary embodiment in conjunction with the accompanying drawings, in which: +FIG. 1 depicts a diagram of a conventional turbo encoder. +FIG. 2 depicts a block diagram of the interleaver illustrated in FIG. 1; +FIG. 3 depicts an array containing a data frame, and permutation of that array; +FIG. 4 depicts a data frame stored in consecutive storage locations; +FIG. 5 depicts an index array for indexing the data frame shown in FIG. 4, and permutation of the index array. + + + + +DETAILED DESCRIPTION OF THE INVENTION +FIG. 1 illustrates a conventional turbo encoder. As illustrated, conventional turbo encoders include two encoders 20 and an interleaver 100. An interleaver 100 in accordance with the present invention receives incoming data frames 110 of size N, where N is the number of bits, number of bytes, or the number of some other portion the frame may be separated into, which are regarded as frame elements. The interleaver 100 separates the N frame elements into sets of data, such as rows. The interleaver then rearranges (permutes) the data in each set (row) in a pseudo-random fashion. The interleaver 100 may employ different methods for rearranging the data of the different sets. However, those skilled in the art will recognize that one or more of the methods could be reused on one or more of the sets without departing from the scope of the invention. After permuting the data in each of the sets, the interleaver outputs the data in a different order than received. +The interleaver 100 may store the data frame 110 in an array of size N1×N2 such that N1*N2=N. An example depicted in FIG. 3 shows an array 350 having 3 rows (N1=3) of 6 columns (N2=6)for storing a data frame 110 having 18 elements, denoted Frame Element 00 (FE00) through FE17 (N=18). While this is the preferred method, the array may also be designed such that N1*N2 is a fraction of N such that one or more of the smaller arrays is/are operated on in accordance with the present invention and the results from each of the smaller arrays are later combined. +To permute array 350 according to the present invention, each row j of array 350 is individually operated on, to permute the columns k of each row according to the equation: +D1(j,k)=D(j,(&agr;k+&bgr;)modP) +where: +j and k are row and column indices, respectively, in array 350; +P is a number greater than or equal to N2; +&agr;j and P arc relative prime numbers (one or both can be non-prime numbers, but the only divisor that they have in common is 1); +&bgr;j is a constant, one value associated with each row. +Once the data for all of the rows are permuted, the new array is read out column by column. Also, once the rows have been permuted, it is possible (but not required) to permute the data grouped by column before outputting the data. In the event that both the rows and columns are permuted, the rows, the columns or both may be permuted in accordance with the present invention. It is also possible to transpose rows of array, for example by transposing bits in the binary representation of the row index j. (In a four-row array, for example, the second and third rows would be transposed under this scheme.) It is also possible that either the rows or the columns, but not both may be permuted in accordance with a different method of permuting. Those skilled in the art will recognize that the system could be rearranged to store the data column by column, permute each set of data in a column and read out the results row by row without departing from the scope of the invention. +These methods of interleaving are based on number theory and may be implemented in software and/or hardware (i.e. application specific integrated circuits (ASIC), programmable logic arrays (PLA), or any other suitable logic devices). Further, a single pseudo random sequence generator (i.e. m-sequence, M-sequence, Gold sequence, Kasami sequence . . . ) can be employed as the interleaver. +In the example depicted in FIG. 3, the value selected for P is 6, the values of &agr; are 5 for all three rows, and the values of &bgr; are 1, 2, and 3 respectively for the three rows. (These are merely exemplary. Other numbers may be chosen to achieve different permutation results.) The values of &agr; (5) are each relative prime numbers relative to the value of P (6), as stipulated above. +Calculating the specified equation with the specified values for permuting row 0 of array D 350 into row 0 of array D1 360 proceeds as: + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 0 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 0 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 1 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 1 + + ) + + + = + FE01 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 1 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 1 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 6 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 0 + + ) + + + = + FE00 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 2 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 2 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 11 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 5 + + ) + + + = + FE05 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 3 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 3 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 16 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 4 + + ) + + + = + FE04 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 4 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 4 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 21 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 3 + + ) + + + = + FE03 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 0 + , + 5 + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + + + 5 + * + 5 + + + + 1 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + + + ( + 26 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 2 + + ) + + + = + FE02 + + + + + + + + + + + + + + Thus  row  0  becomes: + + ⁢ + +   + + ⁢ + FE01 + ⁢ + +   + + ⁢ + FE00 + ⁢ + +   + + ⁢ + FE05 + ⁢ + +   + + ⁢ + FE04 + ⁢ + +   + + ⁢ + FE03 + ⁢ + +   + + ⁢ + FE02 + + + + + + + For  row  1  the  equations  become: + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 0 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 0 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 2 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + 2 + + ) + + + = + FE08 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 1 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 1 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 7 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + 1 + + ) + + + = + FE07 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 2 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 2 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 12 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + 0 + + ) + + + = + FE06 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 3 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 3 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 17 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + 5 + + ) + + + = + FE11 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 4 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 4 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 22 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + 4 + + ) + + + = + FE10 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 1 + , + 5 + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + + + 5 + * + 5 + + + + 2 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 1 + , + + + ( + 27 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 3 + + ) + + + = + FE09 + + + + + + + + + + + + + + Thus  row  1  becomes: + + ⁢ + +   + + ⁢ + FE08 + ⁢ + +   + + ⁢ + FE07 + ⁢ + +   + + ⁢ + FE06 + ⁢ + +   + + ⁢ + FE11 + ⁢ + +   + + ⁢ + FE10 + ⁢ + +   + + ⁢ + FE09 + + + + + + + For  row  2  the  equations  become: + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 0 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 0 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 3 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + 3 + + ) + + + = + FE15 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 1 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 1 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 8 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + 2 + + ) + + + = + FE14 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 2 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 2 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 13 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + 1 + + ) + + + = + FE13 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 3 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 3 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 18 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + 0 + + ) + + + = + FE12 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 4 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 4 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 23 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + 5 + + ) + + + = + FE17 + + + + + + + + + + + + D + 1 + + ⁡ + + ( + + 2 + , + 5 + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + + + 5 + * + 5 + + + + 3 + + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 2 + , + + + ( + 28 + ) + + ⁢ + mod6 + + + ) + + + = + + + D + ⁡ + + ( + + 0 + , + 4 + + ) + + + = + FE16 + + + + + + + + + + + + + + Thus  row  2  becomes: + + ⁢ + +   + + ⁢ + FE15 + ⁢ + +   + + ⁢ + FE14 + ⁢ + +   + + ⁢ + FE13 + ⁢ + +   + + ⁢ + FE12 + ⁢ + +   + + ⁢ + FE17 + ⁢ + +   + + ⁢ + FE16 + + + + + + + +and the permuted data frame is contained in array D1 360 shown in FIG. 3. Outputting the array column by column outputs the frame elements in the order: +1,8,15,0,7,14,5,6,13,4,11,12,3,10,17,2,9,16. +In an alternative practice of the invention, data frame 110 is stored in consecutive storage locations, not as an array or matrix, and a separate index array is stored to index the elements of the data frame, the index array is permuted according to the equations of the present invention, and the data frame is output as indexed by the permuted index array. +FIG. 4 depicts a block 400 of storage 32 elements in length (thus having offsets of 0 through 31 from a starting storage location). A data frame 110, taken in this example to be 22 elements long and thus to consist of elements FE00 through FE21, occupies offset locations 00 through 21 within block 400. Offset locations 22 through 31 of block 400 contain unknown contents. A frame length of 22 elements is merely exemplary, and other lengths could be chosen. Also, storage of the frame elements in consecutive locations is exemplary, and non-consecutive locations could be employed. +FIG. 5 depicts index array I 550 for indexing storage block 400. It is organized as 4 rows of 8 columns each (N1=4, N2=8, N=N1*N2=32). Initial contents are filled in to array I 550 as shown in FIG. 5 sequentially. This sequential initialization yields the same effect as a row-by-row read-in of data frame 110. +The index array is permuted according to +I1(j,k)=I(j,(&agr;j*k+&bgr;j)modP) +where +&agr;=1, 3, 5, 7 +&bgr;=0, 0, 0, 0 +P=8 +These numbers are exemplary and other numbers could be chosen, as long as the stipulations are observed that P is at least equal to N2 and that each value of &agr; is a relative prime number relative to the chosen value of P. +If the equation is applied to the columns of row 2, for example, it yields: + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 0 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 0 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 0 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 0 + + ) + + + = + 16 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 1 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 1 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 5 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 5 + + ) + + + = + 21 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 2 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 2 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 10 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 2 + + ) + + + = + 18 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 3 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 3 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 15 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 7 + + ) + + + = + 23 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 4 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 4 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 20 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 4 + + ) + + + = + 20 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 5 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 5 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 25 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 1 + + ) + + + = + 17 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 6 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 6 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 30 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 6 + + ) + + + = + 22 + + + + + + + + + + + + I + 1 + + ⁡ + + ( + + 2 + , + 7 + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + + 5 + * + 7 + + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + + + ( + 35 + ) + + ⁢ + mod8 + + + ) + + + = + + + I + ⁡ + + ( + + 2 + , + 3 + + ) + + + = + 19 + + + + + + + + + + + + + +Applying the equation comparably to rows 0, 1, and 3 produces the permuted index array I1 560 shown in FIG. 5. +The data frame 110 is read out of storage block 400 and output in the order specified in the permuted index array I1 560 taken column by column. This would output storage locations in offset order: +0,8,16,24,1,11,21,31,2,14,18,30,3,9,23,29,4,12,20,28,5,15,17,27,6,10,22,26,7,13,19,25. +However, the example assumed a frame length of 22 elements, with offset locations 22-31 in block 400 not being part of the data frame. Accordingly, when outputting the data frame it would be punctured or pruned to a length of 22; i.e., offset locations greater than 21 are ignored. The data frame is thus output with an element order of 0,8,16,1,11,21,2,14,18,3,9,4,12,20,5,15,17,6,10,7,13,19. +In one aspect of the invention, rows of the array may be transposed prior to outputting, for example by reversing the bits in the binary representations of row index j. +There are a number of different ways to implement the interleavers 100 of the present invention. FIG. 2 illustrates an embodiment of the invention wherein the interleaver 100 includes an input memory 300 for receiving and storing the data frame 110. This memory 300 may include shift registers, RAM or the like. The interleaver 100 may also include a working memory 310 which may also include RAM, shift registers or the like. The interleaver includes a processor 320 (e.g., a microprocessor, ASIC, etc.) which may be configured to process I(j,k) in real time according to the above-identified equation or to access a table which includes the results of I(j,k) already stored therein. Those skilled in the art will recognize that memory 300 and memory 310 may be the same memory or they may be separate memories. +For real-time determinations of I(j,k), the first row of the index array is permuted and the bytes corresponding to the permuted index are stored in the working memory. Then the next row is permuted and stored, etc. until all rows have been permuted and stored. The permutation of rows may be done sequentially or in parallel. +Whether the permuted I(j,k) is determined in real time or by lookup, the data may be stored in the working memory in a number of different ways. It can be stored by selecting the data from the input memory in the same order as the I(j,k)s in the permuted index array (i.e., indexing the input memory with the permuting function) and placing them in the working memory in sequential available memory locations. It may also be stored by selecting the bytes in the sequence they were stored in the input memory (i.e., FIFO) and storing them in the working memory directly into the location determined by the permuted I(j,k)s (i.e., indexing the working memory with the permuting function). Once this is done, the data may be read out of the working memory column by column based upon the permuted index array. As stated above, the data could be subjected to another round of permuting after it is stored in the working memory based upon columns rather than on rows to achieve different results. +If the system is sufficiently fast, one of the memories could be eliminated and as a data element is received it could be placed into the working memory, in real time or by table lookup, in the order corresponding to the permuted index array. +The disclosed interleavers are compatible with existing turbo code structures. These interleavers offer superior performance without increasing system complexity. +In addition, those skilled in the art will realize that de-interleavers can be used to decode the interleaved data frames. The construction of de-interleavers used in decoding turbo codes is well known in the art. As such they are not further discussed herein. However, a de-interleaver corresponding to the embodiments can be constructed using the permuted sequences discussed above. +Although the embodiment described above is a turbo encoder such as is found in a CDMA system, those skilled in the art realize that the practice of the invention is not limited thereto and that the invention may be practiced for any type of interleaving and de-interleaving in any communication system. +It will thus be seen that the invention efficiently attains the objects set forth above, among those made apparent from the preceding description. In particular, the invention provides improved apparatus and methods of interleaving codes of finite length while minimizing the complexity of the implementation. +It will be understood that changes may be made in the above construction and in the foregoing sequences of operation without departing from the scope of the invention. It is accordingly intended that all matter contained in the above description or shown in the accompanying drawings be interpreted as illustrative rather than in a limiting sense. +It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention as described herein, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween. + + + + +Having described the invention, what is claimed as new and secured by Letters Patent is: + + +1. A method of interleaving elements of frames of signal data communication channel, the method comprising; +storing a frame of signal data comprising a plurality of elements as an array D having +N1 rows enumerated as 0, 1, . . . N1−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1; and +permuting array D into array D1 according to +D1(j,k)=D(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays D and D1; +k is an index through the columns of arrays D and D1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P. + + +2. The method according to claim 1 wherein said elements of array D are stored in accordance with a first order and wherein said elements of array D1 are output in accordance with a second order. + + +3. The method according to claim 2 wherein elements of array D are stored row by row and elements of array D1 are output column by column. + + +4. The method according to claim 1 further including outputting of array D1 and wherein the product of N1 and N2 is greater than the number of elements in the frame and the frame is punctured during outputting to the number of elements in the frame. + + +5. A method of interleaving elements of frames of signal data communication channel, the method comprising; +creating and storing an index array I having +N1 rows enumerated as 0, 1, . . . N1−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1, +storing elements of a frame of signal data in each of a plurality of storage locations; +storing in row-by-row sequential positions in array I values indicative of corresponding locations of frame elements; and +permuting array I into array I1 according to +I1(j,k)=I(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays I and I1; +k is an index through the columns of arrays I and I1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P, whereby the frame of signal data as indexed by array I1 is effectively permuted. + + +6. The method according to claim 5 further including permuting said stored elements according to said permuted index array I1. + + +7. The method according to claim 5 wherein said elements of the frame of data are output as indexed by entries of array I1 taken other than row by row. + + +8. The method according to claim 7 wherein elements of the frame of data are output as indexed by entries of array I1 taken column by column. + + +9. The method according to claim 5 including the step of transposing rows of array I prior to the step of permuting array I. + + +10. The method according to claim 5 wherein N1 is equal to 4, N2 is equal to 8, P is equal to 8, and the values of &agr;j are different for each row and are chosen from a group consisting of 1, 3, 5, and 7. + + +11. The method according to claim 10 wherein the values of &agr;j are 1, 3, 5, and 7 for j=0, 1, 2, and 3 respectively. + + +12. The method according to claim 11 wherein all values of &bgr; are zero. + + +13. The method according to claim 10 wherein the values of &agr;j are 1, 5, 3, and 7 for j=0, 1, 2, and 3 respectively. + + +14. The method according to claim 13 wherein all values of &bgr; are zero. + + +15. The method according to claim 5 wherein all values of &bgr; are zero. + + +16. The method according to claim 5 wherein at least two values of &bgr; are the same. + + +17. The method according to claim 5 further including outputting of the frame of data and wherein the product of N1 and N2 is greater than the number of elements in the frame of data and the frame of data is punctured during outputting to the number of elements in the frame of data. + + +18. An interleaver for interleaving elements of frames of data, the interleaver comprising; +storage means for storing a frame of data comprising a plurality of elements as an array D having +N1 rows enumerated as 0, 1, . . . N2−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1, and permuting means for permuting array D into array D1 according to +D1(j,k)=D(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays D and D1; +k is an index through the columns of arrays D and D1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P. + + +19. The interleaver according to claim 18 including means for storing said elements of array D in accordance with a first order and means for outputting said elements of array D1 in accordance with a second order. + + +20. The interleaver according to claim 19 wherein said means for storing said elements of array D stores row by row and said means for outputting elements of array D1 outputs column by column. + + +21. The interleaver according to claim 18 including means for outputting said array D1 and for puncturing said array D1 to the number of elements in the frame when the product of N1 and N2 is greater than the number of elements in the frame. + + +22. An interleaver for interleaving elements of frames of data, the interleaver comprising; +means for storing an index array I having +N1 rows enumerated as 0, 1, . . . N1−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1, and +means for receiving a frame of data and storing elements of the frame of data in each of a plurality of storage locations; +means for storing in row-by-row sequential positions in array I values indicative of corresponding locations of frame elements; and +means for permuting array I into array I1 according to: +I1(j,k)=I(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays I and I1; +k is an index through the columns of arrays I and I1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P, whereby the frame of data as indexed by array I1 is effectively permuted. + + +23. The interleaver according to claim 22 further including means for permuting said stored elements according to said permuted index array I1. + + +24. The interleaver according to claim 22 including means for outputting frame elements as indexed by entries of array I1 taken other than row by row. + + +25. The interleaver according to claim 24 including means for outputting frame elements as indexed by entries of array I1 taken column by column. + + +26. The interleaver according to claim 22 wherein the product of N1 and N2 is greater than the number of elements in the frame and the frame is punctured by the means for outputting to the number of elements in the frame. + + +27. An interleaver for interleaving elements of frames of data, the interleaver comprising; +an input memory for storing a received frame of data comprising a plurality of elements as an array D having +N1 rows enumerated as 0, 1, . . . N1−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1; +a processor coupled to said input memory for permuting array D into array D1 according to +D1(j,k)=D(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays D and D1; +k is an index through the columns of arrays D and D1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P, and a working memory coupled to said processor and configured to store the permuted array D1. + + +28. The interlcavcr according to claim 27 wherein said input memory stores said elements of array D in accordance with a first order and said working memory outputs said elements of array D1 in accordance with a second order. + + +29. The interleaver according to claim 28 wherein said input memory stores elements of array D row by row and said working memory outputs elements of array D1 column by column. + + +30. The interleaver according to claim 27 said working memory punctures said array D1 to the number of elements in the frame when the product of N1 and N2 is greater than the number of elements in the frame. + + +31. An interleaver for interleaving elements of frames of data, the interleaver comprising; +a memory for storing an index array I having +N1 rows enumerated as 0, 1, . . . N1−1; and +N2 columns enumerated as 0, 1, . . . N2−1, +wherein N1 and N2 are positive integers greater than 1, and +said memory also for storing elements of a received frame of data in each of a plurality of storage locations; +a processor coupled to said memory for storing in row-by-row sequential positions in array I values indicative of corresponding locations of frame elements; and +said processor also for permuting array I into array I1 stored in said memory according to: +I1(j,k)=I(j,(&agr;jk+&bgr;j)modP) +wherein +j is an index through the rows of arrays I and I1; +k is an index through the columns of arrays I and I1; +&agr;j and &bgr;j are integers predetermined for each row j; +P is an integer at least equal to N2; and +each &agr;j is a relative prime number relative to P, and whereby the frame of data as indexed by array I1 is effectively permuted. + + +32. The interleaver according to claim 31 wherein said processor permutes said stored elements according to said permuted index array I1. + + +33. The interleaver according to claim 31 wherein said memory outputs frame elements as indexed by entries of array I1 taken other than row by row. + + +34. The interleaver according to claim 33 wherein said memory outputs frame elements as indexed by entries of array I1 taken column by column. + + +35. The interleaver according to claim 31 wherein said memory punctures the frame of data to the number of elements in the frame of data when the product of N1 and N2 is greater than the number of elements in the frame of data. + + + + + + + + + + + + \ No newline at end of file diff --git a/tests/data/uspto/tables_ipa20180000016.xml b/tests/data/uspto/tables_ipa20180000016.xml new file mode 100644 index 00000000..28133649 --- /dev/null +++ b/tests/data/uspto/tables_ipa20180000016.xml @@ -0,0 +1,186 @@ + + + + + + + + + + + +TABLE 1 + + + + + + + + + +Fluorescent material + + + + + + +(parts by mass) +Photon flux +Ratio of + + + + + + + + + + + + + + +First fluorescent +Second fluorescent +density +photon +Fresh weight +Nitrate nitrogen + + + +material +material +(μmol · m−2 · s−1) +flux densities +(Edible part) +content + + + + + + + + + + + + + + + + + +(MGF/CASN = 95:5) +(YAG: Ce, Cr) +B +R +FR +R/B +R/FR +(g) +(mg/100 g) + + + + + + + + + + + + + + + + + + + + +Comparative +— +— +35.5 +88.8 +0.0 +2.5 +— +26.2 +361.2 + + +Example 1 + + +Example 1 +60 +— +31.5 +74.9 +12.6 +2.4 +6.0 +35.4 +430.8 + + +Example 2 +50 +10 +28.5 +67.1 +21.7 +2.4 +3.1 +34.0 +450.0 + + +Example 3 +40 +20 +25.8 +62.0 +28.7 +2.4 +2.2 +33.8 +452.4 + + +Example 4 +30 +30 +26.8 +54.7 +33.5 +2.0 +1.6 +33.8 +345.0 + + +Example 5 +25 +39 +23.4 +52.8 +38.1 +2.3 +1.4 +28.8 +307.2 + + + + + + +
\ No newline at end of file diff --git a/tests/test_backend_patent_uspto.py b/tests/test_backend_patent_uspto.py new file mode 100644 index 00000000..466568ac --- /dev/null +++ b/tests/test_backend_patent_uspto.py @@ -0,0 +1,464 @@ +"""Test methods in module docling.backend.patent_uspto_backend.py.""" + +import json +import logging +import os +import unittest +from pathlib import Path +from tempfile import NamedTemporaryFile + +import pytest +import yaml +from docling_core.types import DoclingDocument +from docling_core.types.doc import DocItemLabel, TableData, TextItem + +from docling.backend.xml.uspto_backend import PatentUsptoDocumentBackend, XmlTable +from docling.datamodel.base_models import InputFormat +from docling.datamodel.document import ( + ConversionResult, + InputDocument, + SectionHeaderItem, +) +from docling.document_converter import DocumentConverter + +GENERATE: bool = True +DATA_PATH: Path = Path("./tests/data/uspto/") +GT_PATH: Path = Path("./tests/data/groundtruth/docling_v2/") + + +def _generate_groundtruth(doc: DoclingDocument, file_stem: str) -> None: + with open(GT_PATH / f"{file_stem}.itxt", "w", encoding="utf-8") as file_obj: + file_obj.write(doc._export_to_indented_text()) + doc.save_as_json(GT_PATH / f"{file_stem}.json") + doc.save_as_markdown(GT_PATH / f"{file_stem}.md") + + +@pytest.fixture(scope="module") +def patents() -> list[tuple[Path, DoclingDocument]]: + patent_paths = ( + sorted(DATA_PATH.glob("ip*.xml")) + + sorted(DATA_PATH.glob("pg*.xml")) + + sorted(DATA_PATH.glob("pa*.xml")) + + sorted(DATA_PATH.glob("pftaps*.txt")) + ) + patents: list[dict[Path, DoclingDocument]] = [] + for in_path in patent_paths: + in_doc = InputDocument( + path_or_stream=in_path, + format=InputFormat.XML_USPTO, + backend=PatentUsptoDocumentBackend, + ) + backend = PatentUsptoDocumentBackend(in_doc=in_doc, path_or_stream=in_path) + logging.info(f"Converting patent from file {in_path}") + doc = backend.convert() + assert doc, f"Failed to parse document {in_path}" + patents.append((in_path, doc)) + + return patents + + +@pytest.fixture(scope="module") +def groundtruth() -> list[tuple[Path, str]]: + patent_paths = ( + sorted(GT_PATH.glob("ip*")) + + sorted(GT_PATH.glob("pg*")) + + sorted(GT_PATH.glob("pa*")) + + sorted(GT_PATH.glob("pftaps*")) + ) + groundtruth: list[tuple[Path, str]] = [] + for in_path in patent_paths: + with open(in_path, encoding="utf-8") as file_obj: + content = file_obj.read() + groundtruth.append((in_path, content)) + + return groundtruth + + +@pytest.fixture(scope="module") +def tables() -> list[tuple[Path, TableData]]: + table_paths = sorted(DATA_PATH.glob("tables*.xml")) + tables: list[tuple[Path, TableData]] = [] + for in_path in table_paths: + with open(in_path, encoding="utf-8") as file_obj: + content = file_obj.read() + parser = XmlTable(content) + parsed_table = parser.parse() + assert parsed_table + tables.append((in_path, parsed_table)) + + return tables + + +@pytest.mark.skip("Slow test") +def test_patent_export(patents): + for _, doc in patents: + with NamedTemporaryFile(suffix=".yaml", delete=False) as tmp_file: + doc.save_as_yaml(Path(tmp_file.name)) + assert os.path.getsize(tmp_file.name) > 0 + + with NamedTemporaryFile(suffix=".html", delete=False) as tmp_file: + doc.save_as_html(Path(tmp_file.name)) + assert os.path.getsize(tmp_file.name) > 0 + + with NamedTemporaryFile(suffix=".md", delete=False) as tmp_file: + doc.save_as_markdown(Path(tmp_file.name)) + assert os.path.getsize(tmp_file.name) > 0 + + +def test_patent_groundtruth(patents, groundtruth): + gt_stems: list[str] = [item[0].stem for item in groundtruth] + gt_names: dict[str, str] = {item[0].name: item[1] for item in groundtruth} + for path, doc in patents: + if path.stem not in gt_stems: + continue + md_name = path.stem + ".md" + if md_name in gt_names: + pred_md = doc.export_to_markdown() + assert ( + pred_md == gt_names[md_name] + ), f"Markdown file mismatch against groundtruth {md_name}" + json_name = path.stem + ".json" + if json_name in gt_names: + pred_json = json.dumps(doc.export_to_dict(), indent=2) + assert ( + pred_json == gt_names[json_name] + ), f"JSON file mismatch against groundtruth {json_name}" + itxt_name = path.stem + ".itxt" + if itxt_name in gt_names: + pred_itxt = doc._export_to_indented_text() + assert ( + pred_itxt == gt_names[itxt_name] + ), f"Indented text file mismatch against groundtruth {itxt_name}" + + +def test_tables(tables): + """Test the table parser.""" + # CHECK table in file tables_20180000016.xml + file_name = "tables_ipa20180000016.xml" + file_table = [item[1] for item in tables if item[0].name == file_name][0] + assert file_table.num_rows == 13 + assert file_table.num_cols == 10 + assert len(file_table.table_cells) == 130 + + +def test_patent_uspto_ice(patents): + """Test applications and grants Full Text Data/XML Version 4.x ICE.""" + + # CHECK application doc number 20200022300 + file_name = "ipa20200022300.xml" + doc = [item[1] for item in patents if item[0].name == file_name][0] + if GENERATE: + _generate_groundtruth(doc, Path(file_name).stem) + + assert doc.name == file_name + texts = doc.texts + assert len(texts) == 78 + assert isinstance(texts[0], TextItem) + assert ( + texts[0].text + == "SYSTEM FOR CONTROLLING THE OPERATION OF AN ACTUATOR MOUNTED ON A SEED PLANTING IMPLEMENT" + ) + assert texts[0].label == DocItemLabel.TITLE + assert texts[0].parent.cref == "#/body" + assert isinstance(texts[1], TextItem) + assert texts[1].text == "ABSTRACT" + assert texts[1].label == DocItemLabel.SECTION_HEADER + assert texts[1].parent.cref == "#/texts/0" + assert isinstance(texts[2], TextItem) + assert texts[2].text == ( + "In one aspect, a system for controlling an operation of an actuator mounted " + "on a seed planting implement may include an actuator configured to adjust a " + "position of a row unit of the seed planting implement relative to a toolbar " + "of the seed planting implement. The system may also include a flow restrictor" + " fluidly coupled to a fluid chamber of the actuator, with the flow restrictor" + " being configured to reduce a rate at which fluid is permitted to exit the " + "fluid chamber in a manner that provides damping to the row unit. Furthermore," + " the system may include a valve fluidly coupled to the flow restrictor in a " + "parallel relationship such that the valve is configured to permit the fluid " + "exiting the fluid chamber to flow through the flow restrictor and the fluid " + "entering the fluid chamber to bypass the flow restrictor." + ) + assert texts[2].label == DocItemLabel.PARAGRAPH + assert texts[2].parent.cref == "#/texts/1" + assert isinstance(texts[3], TextItem) + assert texts[3].text == "FIELD" + assert texts[3].label == DocItemLabel.SECTION_HEADER + assert texts[3].parent.cref == "#/texts/0" + assert isinstance(texts[4], TextItem) + assert texts[4].text == ( + "The present disclosure generally relates to seed planting implements and, " + "more particularly, to systems for controlling the operation of an actuator " + "mounted on a seed planting implement in a manner that provides damping to " + "one or more components of the seed planting implement." + ) + assert texts[4].label == DocItemLabel.PARAGRAPH + assert texts[4].parent.cref == "#/texts/3" + assert isinstance(texts[5], TextItem) + assert texts[5].text == "BACKGROUND" + assert texts[5].label == DocItemLabel.SECTION_HEADER + assert texts[5].parent.cref == "#/texts/0" + assert isinstance(texts[6], TextItem) + assert texts[6].text == ( + "Modern farming practices strive to increase yields of agricultural fields. In" + " this respect, seed planting implements are towed behind a tractor or other " + "work vehicle to deposit seeds in a field. For example, seed planting " + "implements typically include one or more ground engaging tools or openers " + "that form a furrow or trench in the soil. One or more dispensing devices of " + "the seed planting implement may, in turn, deposit seeds into the furrow(s). " + "After deposition of the seeds, a packer wheel may pack the soil on top of the" + " deposited seeds." + ) + assert texts[6].label == DocItemLabel.PARAGRAPH + assert texts[6].parent.cref == "#/texts/5" + assert isinstance(texts[7], TextItem) + assert texts[7].text == ( + "In certain instances, the packer wheel may also control the penetration depth" + " of the furrow. In this regard, the position of the packer wheel may be moved" + " vertically relative to the associated opener(s) to adjust the depth of the " + "furrow. Additionally, the seed planting implement includes an actuator " + "configured to exert a downward force on the opener(s) to ensure that the " + "opener(s) is able to penetrate the soil to the depth set by the packer wheel." + " However, the seed planting implement may bounce or chatter when traveling at" + " high speeds and/or when the opener(s) encounters hard or compacted soil. As " + "such, operators generally operate the seed planting implement with the " + "actuator exerting more downward force on the opener(s) than is necessary in " + "order to prevent such bouncing or chatter. Operation of the seed planting " + "implement with excessive down pressure applied to the opener(s), however, " + "reduces the overall stability of the seed planting implement." + ) + assert texts[7].label == DocItemLabel.PARAGRAPH + assert texts[7].parent.cref == "#/texts/5" + assert isinstance(texts[8], TextItem) + assert texts[8].text == ( + "Accordingly, an improved system for controlling the operation of an actuator " + "mounted on s seed planting implement to enhance the overall operation of the " + "implement would be welcomed in the technology." + ) + assert texts[8].label == DocItemLabel.PARAGRAPH + assert texts[8].parent.cref == "#/texts/5" + assert isinstance(texts[9], TextItem) + assert texts[9].text == "BRIEF DESCRIPTION" + assert texts[9].label == DocItemLabel.SECTION_HEADER + assert texts[9].parent.cref == "#/texts/0" + assert isinstance(texts[15], TextItem) + assert texts[15].text == "BRIEF DESCRIPTION OF THE DRAWINGS" + assert texts[15].label == DocItemLabel.SECTION_HEADER + assert texts[15].parent.cref == "#/texts/0" + assert isinstance(texts[17], TextItem) + assert texts[17].text == ( + "FIG. 1 illustrates a perspective view of one embodiment of a seed planting " + "implement in accordance with aspects of the present subject matter;" + ) + assert texts[17].label == DocItemLabel.PARAGRAPH + assert texts[17].parent.cref == "#/texts/15" + assert isinstance(texts[27], TextItem) + assert texts[27].text == "DETAILED DESCRIPTION" + assert texts[27].label == DocItemLabel.SECTION_HEADER + assert texts[27].parent.cref == "#/texts/0" + assert isinstance(texts[57], TextItem) + assert texts[57].text == ( + "This written description uses examples to disclose the technology, including " + "the best mode, and also to enable any person skilled in the art to practice " + "the technology, including making and using any devices or systems and " + "performing any incorporated methods. The patentable scope of the technology " + "is defined by the claims, and may include other examples that occur to those " + "skilled in the art. Such other examples are intended to be within the scope " + "of the claims if they include structural elements that do not differ from the" + " literal language of the claims, or if they include equivalent structural " + "elements with insubstantial differences from the literal language of the " + "claims." + ) + assert texts[57].label == DocItemLabel.PARAGRAPH + assert texts[57].parent.cref == "#/texts/27" + assert isinstance(texts[58], TextItem) + assert texts[58].text == "CLAIMS" + assert texts[58].label == DocItemLabel.SECTION_HEADER + assert texts[58].parent.cref == "#/texts/0" + assert isinstance(texts[77], TextItem) + assert texts[77].text == ( + "19. The system of claim 18, wherein the flow restrictor and the valve are " + "fluidly coupled in a parallel relationship." + ) + assert texts[77].label == DocItemLabel.PARAGRAPH + assert texts[77].parent.cref == "#/texts/58" + + # CHECK application doc number 20180000016 for HTML entities, level 2 headings, tables + file_name = "ipa20180000016.xml" + doc = [item[1] for item in patents if item[0].name == file_name][0] + if GENERATE: + _generate_groundtruth(doc, Path(file_name).stem) + + assert doc.name == file_name + texts = doc.texts + assert len(texts) == 183 + assert isinstance(texts[0], TextItem) + assert texts[0].text == "LIGHT EMITTING DEVICE AND PLANT CULTIVATION METHOD" + assert texts[0].label == DocItemLabel.TITLE + assert texts[0].parent.cref == "#/body" + assert isinstance(texts[1], TextItem) + assert texts[1].text == "ABSTRACT" + assert texts[1].label == DocItemLabel.SECTION_HEADER + assert texts[1].parent.cref == "#/texts/0" + assert isinstance(texts[2], TextItem) + assert texts[2].text == ( + "Provided is a light emitting device that includes a light emitting element " + "having a light emission peak wavelength ranging from 380 nm to 490 nm, and a " + "fluorescent material excited by light from the light emitting element and " + "emitting light having at a light emission peak wavelength ranging from 580 nm" + " or more to less than 680 nm. The light emitting device emits light having a " + "ratio R/B of a photon flux density R to a photon flux density B ranging from " + "2.0 to 4.0 and a ratio R/FR of the photon flux density R to a photon flux " + "density FR ranging from 0.7 to 13.0, the photon flux density R being in a " + "wavelength range of 620 nm or more and less than 700 nm, the photon flux " + "density B being in a wavelength range of 380 nm or more and 490 nm or less, " + "and the photon flux density FR being in a wavelength range of 700 nm or more " + "and 780 nm or less." + ) + assert isinstance(texts[3], TextItem) + assert texts[3].text == "CROSS-REFERENCE TO RELATED APPLICATION" + assert texts[3].label == DocItemLabel.SECTION_HEADER + assert texts[3].parent.cref == "#/texts/0" + assert isinstance(texts[4], TextItem) + assert texts[5].text == "BACKGROUND" + assert texts[5].label == DocItemLabel.SECTION_HEADER + assert texts[5].parent.cref == "#/texts/0" + assert isinstance(texts[6], TextItem) + assert texts[6].text == "Technical Field" + assert texts[6].label == DocItemLabel.SECTION_HEADER + assert texts[6].parent.cref == "#/texts/0" + assert isinstance(texts[7], TextItem) + assert texts[7].text == ( + "The present disclosure relates to a light emitting device and a plant " + "cultivation method." + ) + assert texts[7].label == DocItemLabel.PARAGRAPH + assert texts[7].parent.cref == "#/texts/6" + assert isinstance(texts[8], TextItem) + assert texts[8].text == "Description of Related Art" + assert texts[8].label == DocItemLabel.SECTION_HEADER + assert texts[8].parent.cref == "#/texts/0" + assert isinstance(texts[63], TextItem) + assert texts[63].text == ( + "wherein r, s, and t are numbers satisfying 0≦r≦1.0, 0≦s≦1.0, 0Docling parses documents' + ) + doc_path = temp_dir / "docling_test.xml" + doc_path.write_text(xml_content, encoding="utf-8") + assert dci._guess_format(doc_path) == None + buf = BytesIO(Path(doc_path).open("rb").read()) + stream = DocumentStream(name="docling_test.xml", stream=buf) + assert dci._guess_format(stream) == None + + # Invalid USPTO patent (as plain text) + stream = DocumentStream(name="pftaps057006474.txt", stream=BytesIO(b"xyz")) + assert dci._guess_format(stream) == None + doc_path = temp_dir / "pftaps_wrong.txt" + doc_path.write_text("xyz", encoding="utf-8") + assert dci._guess_format(doc_path) == None + + def _make_input_doc(path): in_doc = InputDocument( path_or_stream=path,