EP0719255A1 - Substituted pyridines, process for producing them and their use as pesticides and fungicides - Google Patents

Substituted pyridines, process for producing them and their use as pesticides and fungicides

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Publication number
EP0719255A1
EP0719255A1 EP94926234A EP94926234A EP0719255A1 EP 0719255 A1 EP0719255 A1 EP 0719255A1 EP 94926234 A EP94926234 A EP 94926234A EP 94926234 A EP94926234 A EP 94926234A EP 0719255 A1 EP0719255 A1 EP 0719255A1
Authority
EP
European Patent Office
Prior art keywords
halogen
alkyl
phenyl
substituted
alkoxy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94926234A
Other languages
German (de)
French (fr)
Inventor
Dieter Bernd Reuschling
Adolf Heinz Linkies
Volkmar Wehner
Rainer Preuss
Wolfgang Schaper
Harald Jakobi
Peter Braun
Werner Knauf
Burkhard Sachse
Anna Waltersdorfer
Manfred Kern
Peter Lümmen
Werner Bonin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer CropScience AG
Original Assignee
Hoechst Schering Agrevo GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hoechst Schering Agrevo GmbH filed Critical Hoechst Schering Agrevo GmbH
Publication of EP0719255A1 publication Critical patent/EP0719255A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
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    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/60—Biocides or preservatives, e.g. disinfectants, pesticides or herbicides; Pest repellants or attractants
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
    • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
    • C10M133/38—Heterocyclic nitrogen compounds
    • C10M133/40—Six-membered ring containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00—Lubricating compositions containing more than 10% water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/221—Six-membered rings containing nitrogen and carbon only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/22—Heterocyclic nitrogen compounds
    • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
    • C10M2215/226—Morpholines
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/30—Heterocyclic compounds
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    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/01—Emulsions, colloids, or micelles

Definitions

  • the invention relates to new substituted 4-amino and 4-hydroxypyridines, processes for their preparation and their use as pesticides, in particular as insecticides, acaricides and fungicides.
  • the invention therefore relates to compounds of the formula 1 and their salts, in which (1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are identical or different, is selected from the group consisting of
  • R 1 , R 2 , R 3 and R 4 which are the same or different, are selected from the group consisting of
  • Arylkyl means aryl (C r C 4 ) alkyl
  • Y - Z together means a (C 5 -C 12 ) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 is formed by heteroatom groups such as O, NR 5 , S, SO, SO 2 or SiR 6 R 7 can be replaced, where R 5 is hydrogen, (C, -C 4 ) alkyl or (C 1 -C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently of one another (C 1 -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) carbon hydrogen radical with the possible aforementioned variations (replacement by heteroatom radical (s)) optionally with one or more, preferably up to three identical or different residues from the series
  • Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, which is one or more, preferably up to three identical or different radicals from the series
  • Aryl, O-aryl or aryl- (C r C 4 ) -alkyl where aryl is a phenyl group, optionally with one or more, preferably up to five, in particular up to three identical or different radicals from the series
  • R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 3 -C 7 ) cycloalkyl, halogen (C 3 -C 7 ) cycloalkyl, (C 1 -C 7 ) -Alkoxy, phenyl or substituted phenyl;
  • R 9 , R 10 and R 1 1 are the same or different and independently of one another are (C 1 -C 4 ) alkyl, phenyl and / or substituted phenyl;
  • R 12 and R 13 are identical or different and independently of one another are hydrogen, (C r C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl;
  • R 14 represents (C.
  • CO also with one or more, preferably up to three, in the case of halogen up to the maximum number of radicals identical or different of the radicals below from the series halogen, halogen (C 1 -C 4 ) alkoxy, hydroxy, (C 3 -C 8 ) cycloalkyl, (C 3 -C 8 ) cycloalkenyl, (C, -C 4 ) acyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio and substituted phenylthio may be substituted; or (b) is (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 denotes phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cyclo
  • (C 2 -C 18 ) alkylidene is substituted and in the (C-
  • R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a); and R 16 and R 17 are identical or different and are independently hydrogen, (C-j-C6) alkyl, (C.
  • halogen means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom, in particular a fluorine or chlorine atom;
  • alkyl an unbranched or branched hydrocarbon residue such as. B. the methyl, ethyl, propyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl radical, the pentyl, 2-methylbutyl or the 1, 1-dimethylpropyl radical, the hexyl -, heptyl, octyl or 1, 1, 3,3-tetramethylbutyl, the nonyl, decyl, undecyl or dodecyl radical and the like;
  • cycloalkyl preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctenyl group;
  • alkoxy means an alkoxy group whose hydrocarbon radical has the meaning given under the term “alkyl”;
  • cycloalkoxy a cycloalkoxy group whose hydrocarbon radical has the meaning given under “cycloalkyl”
  • alkylthio means an alkylthio group whose hydrocarbon radical has the meaning given under the term “alkyl”
  • haloalkyl is one referred to under the term "(C j -C ⁇ alkyl” group in which one or more hydrogen atoms are replaced by the abovementioned halogen atoms, preferably chlorine or fluorine, is replaced, such as the trifluoromethyl group, the 2 , 2,2-trifluoroethyl group, the chloromethyl, fluoromethyl group, the difluoromethyl group or the 1, 1, 2,2-tetrafluoroethyl group (the same applies to "haloalkenyl”);
  • haloalkoxy means a haloalkoxy group whose halogenated hydrocarbon radical has the meaning given under the term "haloalkyl";
  • Substituted phenyl means a phenyl radical which has one or more, preferably up to three identical or different substituents from the series halogen, (C r C 4 ) -alkyl, halogen (C r C 4 ) -alkyl, hydroxy- (C r C 4 ) -alkyl, (C r C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, phenoxy, phenyl, nitro, hydroxy, cyano, (C 1 -C 4 ) -alkanoyl, benzoyl, (C r C 4 ) alkanoyloxy, (C 1 -C 4 ) alkoxycarbonyl;
  • substituted amino means an amino group which is substituted by one or two (C 1 -C 4 ) -alkyl groups or one (C 1 -C 4 ) -alkanoyl group;
  • a "bivalent hydrocarbon radical” means a radical derived from n-alkanes or n-alkenes by removing one hydrogen atom from each of the two terminal carbon atoms in the chain, such as methylene, ethanediyl, trimethylene, tetramethylene; "Acyl” means in particular an alkanoyl radical, such as acetyl, propionyl or butyryl, or an alkyloxycarbonyl radical.
  • the substituents on the cycloalkyl or cycloalkenyl radicals defined under (5b) can be ice or trans with respect to Y; the cis position is preferred. If only one substituent is present, it should be in cyclohexyl, preferably in the 4-position, and be cis-configured.
  • the number x of the radicals R 1 , R 2 , R 3 and R 4 which are the same or different, is selected from the group consisting of RO-CH 2 -, RO-CO-,
  • R 1 , R 2 , R 3 and R 4 which are the same or different, are selected from the group consisting of
  • X represents O, S, NH, NR or NOR;
  • Y is a bond or a divalent hydrocarbon radical with 1 to 6 C atoms, which is one or more, preferably up to three identical or different radicals from the series:
  • Aryl, O-aryl or aryl- (C 1 -C 4 ) -alkyl where aryl is a phenyl group which may have one or more, preferably up to five, in particular up to three identical or different radicals from the Halogen series,
  • R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 5 -C 6 ) cycloalkyl, (C r
  • R 9 , R 10 and R 1 1 are identical or different and independently of one another are (CC 4 ) alkyl, phenyl and / or substituted phenyl;
  • R 12 and R 13 are identical or different and independently of one another are hydrogen, (C 1 -C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl; wherein in (CC 12 ) alkyl, (C 2 -C 12 ) alkenyl and (C 1 -C 12 ) alkoxy optionally one or more, preferably up to 3 CH 2 -
  • R 5 , R 6 and R 7 have the meaning as above under (3); the (C- C j ⁇ alkyl radical and the (C ⁇ C ⁇ j alkoxy radical with or without the abovementioned variations (replacement by heteroatom radical (s)) also with one or more, preferably up to three, in
  • Halogen halogen- (C 1 -C 4 ) alkoxy, (C 3 -C 6 ) cycloalkyl, (C 1 -C 4 ) acyl,
  • Phenoxy, substituted phenoxy, phenyl and substituted phenyl may be substituted; or halogen represents F or Cl;
  • (b) denotes (C 3 -C 6 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, it being possible for a CH 2 group of the carbocycle to be replaced by NR 15 ;
  • R 15 denotes phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl radical, optionally with one or more, preferably up to three, in the case of halogen up to the maximum number same or different residues from the series
  • Aryl- (C 1 -C 4 ) alkyloximino and (C 2 -C 18 ) alkylidene are substituted and in the (C-
  • R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
  • the number x of the radicals R 1 , R 2 , R 3 and R 4 which are the same or different, is selected from the group consisting of
  • Y - Z together means a (C 5 -C 12 ) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 have been replaced by heteroatom groups such as O, NR 5 or SiR 6 R 7 where R 5 is (C r C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently of one another are (C 1 -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) - hydrocarbon radical with the possible above-mentioned variations (replacement by heteroatom radical (s)) optionally with one or more, preferably up to three identical or different radicals from the series
  • Halogen (C 1 -C 4 ) alkyl and halogen (C 1 -C 3 ) alkoxy is substituted; or, if not covered by the above definitions,
  • Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, which is one or more, preferably up to three identical or different radicals from the series
  • Halogen (C 1 -C 3 ) alkyl and halogen (C 1 -C 3 ) alkoxy is substituted;
  • Aryl or O-aryl where aryl is a phenyl group which may be one or more, preferably up to five, in particular up to three identical or different radicals from the series
  • (C r C 7 ) alkoxy is substituted; and R 9 , R 10 and R 1 1 are identical or different and independently of one another are (C 1 -C 4 ) -alkyl, phenyl and / or substituted phenyl; where in (C-
  • (b) denotes (C 3 -C 6 ) -cycloalkyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ;
  • R 15 is phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl radical optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series
  • (C 2 -C 12 ) alkylidene is substituted and in the (C r C 12 ), (C 2 -C 12 ) and (C r C 8 ) hydrocarbon radicals mentioned one or more, preferably up to three CH 2 groups can be replaced by heteroatoms / groups such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as under (3) and moreover 3 to 6 C atoms and / or heteroatom radical (s) of these hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the variations (replacement by heteroatom radical (s) and / or cycle formation) optionally with one or more, preferably up to three, in the case of Halogen are substituted up to the maximum number of identical or different radicals from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl;
  • R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
  • the present invention relates to the compounds of formula 1 in the form of the free base or an acid addition salt.
  • Acids which can be used for salt formation are inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid or organic acids such as formic acid, acetic acid, propionic acid, malonic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid, benzenesulfonic acid or toluene .
  • Racemates and diastereomers can therefore occur.
  • the invention encompasses both the pure isomers and their mixtures.
  • the mixtures of diastereomers can according to common methods, e.g. B. by selective crystallization from suitable solvents or by chromatography in the components. Racemates can be separated into the enantiomers by customary methods, for. B. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers by means of a base.
  • the invention further relates to a process for the preparation of compounds of formula 1, which is characterized in that compounds of formula 2
  • R 1 , R 2 , R 3 and R 4 are as defined above and L is a leaving group, with the corresponding amines, alcohols, phenols or mercaptans, or to form compounds of the formula 1, in which Z is as described in (5b ) is defined, such compounds of formula 1, wherein R 1 , R 2 , R 3 , R 4 , X and Y are as defined above and Z for an unsaturated carbocyclic, such as cycloalkyl or cycloalkenyl under (5b) defined substituted radical, preferably a phenyl radical substituted in this way is hydrogenated, and the compounds of formula 1 thus obtained are optionally converted into their salt.
  • R 1 , R 2 , R 3 and R 4 are as defined above and L is a leaving group, with the corresponding amines, alcohols, phenols or mercaptans, or to form compounds of the formula 1, in which Z is as described in (5b ) is defined, such compounds of formula 1, wherein R 1 , R 2
  • the substitution reaction described above is known in principle.
  • the leaving group can be varied within wide limits and can mean, for example, a halogen atom such as fluorine, chlorine, bromine or iodine or alkylthio such as methyl or ethylthio, or alkanesulfonyloxy such as methane, trifluoromethane or ethanesulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesulfonyloxy or alkylsulfonyl such as methyl - Or ethylsulfonyl or arylsulfonyl such as phenyl or toluenesulfonyl.
  • a halogen atom such as fluorine, chlorine, bromine or iodine or alkylthio such as methyl or ethylthio
  • alkanesulfonyloxy
  • the compounds of formula 2 can be prepared by known methods [e.g. BJ Med., Chem. 32, 1970 (1989), J. Org. Chem. 2 £ 776 (1964), J. Prakt. Chem. 331. 369 (1989), J. Org. Chem. 1_4, 97 (1949), Chem. Ber. 74, 1 1 1 1 (1941)].
  • the reactions with alcohols and mercaptans are carried out in the presence of a strong base such as sodium hydride, potassium hydride or potassium tert-butoxide in an inert aprotic solvent such as DMF, NMP, DMSO, THF, dioxane or sulfolane at a temperature between 0 and 80 ° C .;
  • a strong base such as sodium hydride, potassium hydride or potassium tert-butoxide
  • an inert aprotic solvent such as DMF, NMP, DMSO, THF, dioxane or sulfolane at a temperature between 0 and 80 ° C .
  • the conditions for the reaction of 2 with amines depend on the substituents R 1 to R 4 in 2 and on the structure of the amines used; if the radicals R 1 to R 4 in 2 are inert, 2 can be converted to 1 with an excess of amine with or without solvent at temperatures between 80 and 200 ° C. The excess of amine can be reduced and the temperature lowered if acidic catalysts such as phenol [J. Amer. Chem. Soc. 73, 2623 (1951)] or salts such as triethylammonium chloride or ammonium chloride. Suitable solvents are, for. B.
  • the compounds of formula 3 can by known methods [z. B. F. Zymalkowski, Catalytic hydrogenations, p. 191, Enke Verlag, Stuttgart 1965] to catalytically hydrogenate compounds of formula 1 (Scheme 1).
  • the resulting cis / trans mixtures can be separated by crystallization or chromatography.
  • stage 1 the products of the formula 4 are reacted selectively in the presence of bases such as sodium hydride or potassium tert-butoxide with alkylating agents of the formula LYZ on the nitrogen substituent in the 4-position of the pyridine ring to give 5; in the formula LYZ, L is halogen or R-SO 3 , Y is as defined above (except aryl) and Z is as indicated above.
  • bases such as sodium hydride or potassium tert-butoxide
  • alkylating agents of the formula LYZ on the nitrogen substituent in the 4-position of the pyridine ring to give 5; in the formula LYZ, L is halogen or R-SO 3 , Y is as defined above (except aryl) and Z is as indicated above.
  • sterically uniform alkylating agents sterically uniform reaction products can also be obtained in this way.
  • Solvents such as z. B. DMF, DMSO, THF, dimethoxyethane, dioxane,
  • the compounds of the formula 5 are prepared by known methods [R. Huisgen et al. B. 101, 2559 (1968) CH Rayburn, WR Harlau, HR Haumer Am. Soc. 72, 1721 (1950)] reductively converted into the compounds of formula 1.
  • the amines, alcohols and alkylating agents used are accessible by methods known from the literature.
  • the alcohols can be prepared, for example, by reducing a carbonyl group with a suitable reducing agent, for example a complex metal hydride or, in the case of an aldehyde or ketone, also with hydrogen and a hydrogenation catalyst.
  • a suitable reducing agent for example a complex metal hydride or, in the case of an aldehyde or ketone
  • Other possibilities are the implementation of an organometallic compound with a carbonyl group or an oxirane.
  • suitable substituted phenols can also be reacted with hydrogen in the presence of a hydrogenation catalyst.
  • the amines can be prepared, for example, by reducing an oxime or a nitrile with a suitable reducing agent, for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate .
  • a suitable reducing agent for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst
  • reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate .
  • suitable substituted anilines can also be reacted with hydrogen in the presence of a hydrogenation catalyst.
  • the compounds of formula 1 according to the invention are distinguished by an excellent fungicidal action. Fungal pathogens that have already penetrated into the plant tissue can be successfully combated curatively. This is particularly important and advantageous in the case of those fungal diseases which can no longer be effectively combated with the usual fungicides after infection has occurred.
  • the spectrum of activity of the claimed compounds covers various economically important phytopathogenic fungi, such as. B. Phytophthora infestans, Plasmopara viticola, but also Erysiphe graminis and Pyrenophora teres.
  • the compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives, in sealants, in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.
  • the invention also relates to compositions which contain the compounds of the formula 1 in addition to suitable formulation auxiliaries.
  • the agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formula 1.
  • WP wettable powder
  • EC emulsifiable concentrates
  • SC aqueous dispersions based on oil or water
  • SC suspoemulsions
  • DP dusts
  • mordants granules in the form of water-dispersible granules (WG)
  • ULV formulations microcapsules, waxes or baits.
  • fertilizers and / or growth regulators can also be prepared, e.g. B. in the form of a finished formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, are also a wetting agent, in addition to a diluent or inert substance.
  • Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • Alkylarylsulfonic acid calcium salts such as cadodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters,
  • Alkylaryl polyglycol ether fatty alcohol polyglycol ether, propylene oxide-ethylene oxide-sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite or pyropyllite or diatomaceous earth.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • the active ingredient concentration is e.g. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be approximately 5 to 80% by weight.
  • Dust-like formulations usually contain 5 to 20% by weight.
  • the active ingredient content depends in part on whether the active compound is liquid or solid and which compound is liquid or solid and which granulation aids, fillers etc. are used.
  • the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
  • the concentrates present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with microgranules using water.
  • Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
  • the application rate required varies with the external conditions such as temperature, humidity and others. It can fluctuate within wide limits, e.g. B. between 0.005 and 10.0 kg / ha or more of active substance, but it is preferably between 0.01 and 5 kg / ha.
  • the active compounds according to the invention can be used in their commercially available formulations either alone or in combination with other fungicides known from the literature.
  • the active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides or herbicides.
  • Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms and the like.
  • Preferred mix partners are:
  • Dicrotoph O-1, 2,2,2-tetrachloroethylphosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isozophos, Isioophos, Isio Isoxathion, Malathion, Methacrifos, Methamidophos, Methidation, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profi
  • BPMC 2-sec-butylphenylmethylcarbamate
  • Drug concentration of use forms can range from 0.0001 to
  • active ingredient 95% by weight of active ingredient, preferably between 0.001 and 1% by weight.
  • the active substances are suitable for controlling animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids used in agriculture animal breeding, in forests, in the protection of stocks and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as all or individual stages of development.
  • the pests mentioned above include:
  • Rhipicephalus spp. Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
  • Periplaneta americana Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,
  • Thysanoptera z From the order of the Thysanoptera z.
  • Trialeurodes vaporariorum Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus sp aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of the Lepidoptera z. B.
  • the invention also relates to insecticidal and acaricidal compositions which comprise the compounds of the formula I in addition to suitable formulation auxiliaries.
  • the agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formulas I.
  • WP wettable powder
  • SC aqueous solutions
  • SC emulsions
  • sprayable solutions dispersions based on oil or water
  • SC suspoemulsions
  • DP dusts
  • WP wettable powder
  • SC emulsifiable concentrates
  • SC aqueous solutions
  • SC emulsions
  • DP dusts
  • WG water-dispersible granules
  • ULV formulations microcapsules, waxes or baits.
  • combinations with other pesticidally active substances, fertilizers and / or growth regulators can also be prepared, e.g. B. in the form of a finished formulation or as a tank mix.
  • Spray powders are preparations which are uniformly dispersible in water.
  • Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers.
  • organic solvent e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons.
  • alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzene sulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl poiyethers, sorbitan fatty acid esters, polyoxyethylene ester or polyoxyethylene sorbitan polyethylenesorbitan-polyoxyethylene sorbitan or fatty acid polyoxyethylene sorbitan or fatty acid polyoxyethylene sorboxes.
  • alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzene sulfonate
  • nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl poiyethers,
  • Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.
  • Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material.
  • Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
  • the active ingredient concentration is e.g. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components.
  • the active substance concentration can be approximately 5 to 80% by weight.
  • Dust-like formulations usually contain 5 to 20 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%.
  • the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, fillers, etc. are used.
  • the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
  • the concentrates present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
  • the required application rate varies. It can fluctuate within wide limits, e.g. B. between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
  • the active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
  • the pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, etc.
  • Preferred mixing partners are
  • BPMC 2-sec-butylphenylmethylcarbamate
  • the active substance content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
  • the application takes place in a customary manner adapted to the application forms.
  • the active compounds according to the invention are also suitable for combating endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry.
  • the active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, dipping (dipping), spraying (spraying), pouring on (pour-on and spot) -on) and powdering and by parenteral use in the form of, for example, injection.
  • novel compounds of the formula I according to the invention can accordingly also be used particularly advantageously in animal husbandry (for example cattle, sheep, pigs and poultry such as chickens, geese, etc.).
  • animal husbandry for example cattle, sheep, pigs and poultry such as chickens, geese, etc.
  • the animals are given the new compounds, if appropriate in suitable formulations (see above) and if appropriate with the drinking water or feed orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way.
  • the appropriate dosages and formulations depend in particular on the type and stage of development of the livestock and also on the infestation pressure and can be easily determined and determined using the usual methods.
  • the new compounds in cattle z. B. in doses of 0.01 to 1 mg / kg body weight.
  • Example 2 was prepared analogously to Example 5 from 4- [O-benzyl-N- (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-methoxy-methylpyridine (Example 2) Yield: 90%
  • Example 4 was prepared analogously to Example 5 from 4- [O-benzyl-N- (4-cis-tert.-amylcyclohexyl)] - hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 4).
  • the free base was released from the solution of the hydrochloride in methylene chloride by shaking with sodium bicarbonate solution.
  • Example 1 2-methoxymethyl-3-methoxy-4- (4-cis-tert-butyl-cyclohexyloxy) pyridine
  • Example 8 was prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 2- (2,4-dimethylphenoxy) ethylamine.
  • Example 2 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-ethoxyphenyl) -1-tosyloxycyclohexane. Yield: 46% 1 H-NMR (CDCI3. 100 MHz): ⁇ : 8.2 (d, 1 H), 7.3 (m, 6H), 7.0 (m, 4H), 4.7 (s, 2H), 4.6 (s, 2H), 4.0 (q, 2H), 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.8 ( m, 1H), 1.4 (t, 3H), 1.4-2.3 (m, 8H) ppm.
  • Example 1 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methylpyridine (Example 1) and dodecyl bromide. Yield: 80%
  • Example 24 was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis- (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 24). Yield: 74% 1H NMR (100 MHz, CDCI 3 ): ⁇ : 8.1 (d, 1H), 6.9 (m, 4H), 6.5 (d, 1H), 4.9
  • Example 25 was prepared analogously to Example 5 from 4- (O-benzyl-N-decylhydroxylamino) -3-methoxy-2-methoxymethylpyridine (Example 25). Yield: 84%
  • Example 1 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4 (2 (2,5,5-trimethyl-1,5-dioxane-2- yl) -ethoxy) phenyl) -1-tosyloxy-cyclohexane.
  • Example 2 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 ⁇ 4 (tetrahydrofur (2) yl-methoxyjphenyl> -1-tosyloxy-cyclohexane.
  • Example 1 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4 (dimethyl-tert-butylsilyloxy) phenyl) -1-tosyloxy-cyclohexane.
  • Example 2 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4 (4 (2,2-dimethoxyethoxy) phenyl) -1-tosyloxy-cyclohexane.
  • Example 1 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4-but-2-oxy-phenyl) -1-tosyloxy-cyclohexane
  • Example 2 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 [4 (2-ethoxyethoxy) phenyl] -1-tosyloxy-cyclohexane.
  • Example 2 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4- [4 (2 (2-methoxyethoxy) ethoxy) phenyl] -1-tosyloxy -cyclohexane.
  • Example 2 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-propoxyphenyl) -1-tosyloxy-cyclohexane. Yield: 50.3%
  • Example 2 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-isopropoxyphenyl) -1-tosyloxycyclohexane Yield: 54.6%
  • 1 H-NMR 100 MHz, CDCI 3 ): ⁇ : 8.2 (d, 1H), 7.1-7.4 (m, 9H), 6.8 (d, 1H), 4.7 (s , 2H), 4.6 (s, 2H), 4.5 (m, 1H), 3.9 (s, 3H), 3.5 (s, 3H), 2.8 (m, 1H), 1 , 5-2.2 (m, 8H), 1.3-1.4 (d, 6H) ppm.
  • Example 1 was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4- (4-butoxyphenyl) -1-tosyloxycyclohexane
  • Example 20 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-bromo-2-methoxymethylpyridine (Example 20) and trans-4 (1,1,3, 3-tetramethylbutyl) -1-tosyloxy-cyclohexane.
  • Example 19 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-ethoxy-2-ethoxymethylpyridine (Example 19) and trans-4 (4-ethoxyphenyl) -1-tosyloxycyclohexane Yield: 15.9%
  • Example 21 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-allyloxymethylpyridine (Example 21) and 4-trans-tert-butyl-1-tosyloxy-cyclohexane.
  • 1 H NMR 100 MHz, CDCI 3 ): ⁇ : 8.3 (s, 1 H), 7.3 (s, 5H), 7.4 (d, 1 H), 5.8-6.2 (m, 1H), 5.1 -5.4 (m, 2H), 4.7 (d, 2H), 4.1 (m, 2H), 3.9 (s, 3H), 3.8 m (1H), 1, 0-2, 1 (m, 9H), 0.9, (s, 9H) ppm.
  • Example 54 was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-allyloxymethylpyridine (Example 21) and 4-phenyl-1-tosyloxy-cyclohexane. Yield: 33.7% H-NMR (100 MHz, CDCI 3 ): ⁇ : 8.2 (d, 1 H), 7.2 (m, 6H), 5.8-6.2 (m, 1 H) ), 5.1 -5.4 (m, 2H), 4.7 (d, 2H), 4.1-4.2 (m, 2H), 3.9 (s, 3H), 3.9 ( m, 1H), 2.9 (m, 1H), 1.4-2.3 (m, 8H) ppm.
  • Example 54 Example 54
  • Example 56 The preparation was carried out analogously to Example 57 from 4- (4-oxocyclohexylamino) -3-methoxy-2-methoxymethylpyridine (Example 56) and O-benzylhydroxylamine.
  • Example 42 was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis- (4-propoxyphenyl) cyclohexyl) hydroxyamino] -3-methoxy-2-methoxymethyl-pyridine (Example 42). Yield: 75%
  • Example 70 4- (Spiro [5,5] undecan (3) yl) amino-3-chloro-2-methoxymethyl-pyridine
  • Example 47 was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 47)
  • Example 48 was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 48). Yield: 76.3%
  • Example 53 was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine (Example 53)
  • Example 52 was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine (Example 52) Yield: 79.1%
  • Example 31 was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 31). Yield: 36%
  • Example 32 was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 32)
  • Example 45 was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert.-amylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 45) Yield: 52.3%
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis-but (2) yl-cyclohexylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-trans-but (2) -yl-cyclohexylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis-cyclohexyl-cyclohexylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-trans-cyclohexyl-cyclohexylamine.
  • Example 89 was prepared analogously to Example 89 from 2-methoxymethyl-3,4-dichloropyridine and 3-isoamyl-cyclopentylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4- [4- (2-ethoxyethoxy) ethoxy] phenyl-cyclohexylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2- (2,4-dimethyl) phenoxypropylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 1- (4-difluoromethoxyphenyl) propylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2-methyl-3- (4-tert-butylphenyl) propylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2 (2,3-dimethyl-4-ethoxyethyl) phenoxyethylamine.
  • Example 89/90 were prepared analogously to Example 89/90 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis / trans-butyl-cyclohexylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2-methyl-3 (4-isopropylphenyl) propylamine.
  • Example 84 was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4 [4 (4-fluorobenzylidene)] cyclohexylamine.
  • Phosphorus oxychloride was distilled off in vacuo, ice water was added to the residue, the aqueous solution was adjusted to pH 7.5-8 with 32% sodium hydroxide solution and the reaction product was extracted with ethyl acetate. The purification is carried out by column chromatography.
  • a dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.
  • a wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as the inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill.
  • a dispersion concentrate which is easily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.
  • An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and
  • Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand.
  • a suspension of the wettable powder from example b) having a solids content of 30 is expediently used and is sprayed onto the surface of an attapulgite granulate, dried and mixed intimately.
  • the proportion by weight of the wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate.
  • Tomato plants of the "Rheinlands Ruhm” cultivar were wetted to drip wet levels in the 3 to 4 leaf stage with aqueous suspensions of the claimed compounds. After drying, the plants were inoculated with a zoosporangia suspension of Phytophthora infestans and kept in a climatic chamber for 2 days under optimal infection conditions. The plants were then cultivated further in the greenhouse until the symptoms developed. The infection was assessed approximately 1 week after inoculation. The degree of infestation of the plants was expressed in% infected leaf area in comparison to the untreated, 100% infected control plants.
  • the plants were again placed in the climatic chamber overnight in order to stimulate the sporulation of the fungus. The infestation was then assessed. The degree of infestation was expressed in% affected leaf area compared to the untreated, 100% infected control plants.
  • Barley plants of the "Igri" variety were treated to runoff with an aqueous suspension of the claimed compounds at the 2-leaf stage. After the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of Pyrenophora teres and for 16 hours in a climatic chamber at 100% rel. Incubated humidity. The infected plants were then in a greenhouse at 25 ° C and 80% rel. Humidity continued to be cultivated.
  • Barley plants were heavily inoculated in the 3-leaf stage with conidia of barley mildew (Erysiphe graminis f. Sp. Hordei) and placed in a greenhouse at 20 ° C and a relative humidity of 90 to 95%. 24 hours after inoculation, the plants were wetted uniformly with the compounds listed below in the stated active compound concentrations. After an incubation period of 10 days, the plants were examined for infestation with barley mildew. The degree of infestation was expressed in% infected leaf area compared to untreated, 100% infected control plants.
  • barley mildew Erysiphe graminis f. Sp. Hordei
  • the number x of the radicals R 1 , R 2 , R 3 and R 4 which are the same or different, is selected from the group consisting of
  • R 1 , R 2 , R 3 and R 4 which are the same or different, are selected from the group consisting of

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Abstract

The invention relates to compounds of formula (1) and their salts, in which 1, 2, 3 or 4 of the radicals R?1, R2, R3 and R4¿ are an aliphatic, alicyclic or araliphatic radical bonded via -O-CH¿2?- or -O-CO- and the remainder of these radicals are H, halogen, an aliphatic or an aromatic radical, X is O, S or possibly substituted imino, Y is a bond or a bivalent radical and Z is an aromatic radical or possibly substituted cycloalkyl or cycloalkenyl. The invention also relates to processes for their production and their use as pesticides, in particular insecticides, miticides and fungicides.

Description

Beschreibungdescription
Substituierte Pyridine, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel und FungizideSubstituted pyridines, processes for their preparation and their use as pesticides and fungicides
Die Erfindung betrifft neue substituierte 4-Amino- und 4-Hydroxypyridine, Verfahren zu ihrer Herstellung und ihre Verwendung als Schädlingsbekämpfungsmittel, insbesondere als Insektizide, Akarizide und Fungizide.The invention relates to new substituted 4-amino and 4-hydroxypyridines, processes for their preparation and their use as pesticides, in particular as insecticides, acaricides and fungicides.
Es ist bereits bekannt, daß bestimmte substituierte 4-Amino- und 4-Hydroxypyridine eine fungizide, akarizide und insektizide Wirkung zeigen (vgl. WO 93/05050). Die biologische Wirkung dieser Verbindungen ist jedoch insbesondere bei niedrigen Aufwandmengen und Konzentrationen nicht in allen Anwendungsbereichen zufriedenstellend.It is already known that certain substituted 4-amino and 4-hydroxypyridines have a fungicidal, acaricidal and insecticidal action (cf. WO 93/05050). However, the biological activity of these compounds is not satisfactory in all areas of application, in particular at low application rates and concentrations.
Es wurden neue substituierte 4-Amino- und 4-Hydroxypyridine der allgemeinen Formel 1 gefunden, die biologisch aktiv sind.New substituted 4-amino and 4-hydroxypyridines of the general formula 1 have been found which are biologically active.
Die Erfindung betrifft daher Verbindungen der Formel 1 und deren Salze, worin (1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend ausThe invention therefore relates to compounds of the formula 1 and their salts, in which (1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are identical or different, is selected from the group consisting of
R-O-CH2-,RO-CH 2 -,
R-O-CO-,R-O-CO-,
Halogen-(C1-C4)-alkoxymethyl,Halogen (C 1 -C 4 ) alkoxymethyl,
Halogen-(CrC4)-alkenyloxymethyl, Halogen-(C1-C4)-alkoxycarbonyl, Halogen-IC-, -C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist;Halogen (C r C 4 ) alkenyloxymethyl, Halogen (C 1 -C 4 ) alkoxycarbonyl, halogen IC, -C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4;
und die übrigen 4-x Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt werden aus der Gruppe bestehend ausand the remaining 4-x radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, are selected from the group consisting of
(CrC4)-Alkyl,(C r C 4 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(CrC4)-Alkoxy,(C r C 4 ) alkoxy,
(C2-C4)-Alkenyloxy,(C 2 -C 4 ) alkenyloxy,
Halogen-(CrC4)-alkyl,Halogen (C r C 4 ) alkyl,
Halogen-(C2-C4)-alkenyl,Halogen (C 2 -C 4 ) alkenyl,
Halogen-(C1-C4)-alkoxy,Halogen (C 1 -C 4 ) alkoxy,
Halogen-(C2-C4)-alkenyloxyHalogen (C 2 -C 4 ) alkenyloxy
(CrC4)-Alkylthio,(C r C 4 ) alkylthio,
(CrC4)-Alkylsulfinyl,(C r C 4 ) alkylsulfinyl,
(CrC4)-Alkylsulfonyl,(C r C 4 ) alkylsulfonyl,
Aryl, substituiertes Amino,Aryl, substituted amino,
Halogen undHalogen and
Wasserstoff; R (CrC10)-Alkyl,Hydrogen; R (C r C 10 ) alkyl,
(C2-C10)-Alkenyl,(C 2 -C 10 ) alkenyl,
(C2-C10)-Alkinyl,(C 2 -C 10 ) alkynyl,
(C3-C8)-Cycloalkyl oder(C 3 -C 8 ) cycloalkyl or
Aralkyl bedeutet; Aryl wie unten unter (5a) definiert ist;Aralkyl; Aryl as defined below under (5a);
Arylkyl Aryl-(CrC4)-alkyl bedeutet;Arylkyl means aryl (C r C 4 ) alkyl;
(2) X O, S, NH, NR oder NOR bedeutet und R wie oben unter (1 ) definiert ist. (3) Y - Z zusammen einen (C5-C12) Kohlenwasserstoff rest bedeutet, der unverzweigt oder verzweigt ist und bei dem eine oder mehrere, vorzugsweise bis zu drei CH2 durch Heteroatomgruppen wie O, NR5, S, SO, SO2 oder SiR6R7 ersetzt sein können, wobei R5 Wasserstoff, (C,-C4)- Alkyl oder (C1-C4)-Acyl, und R6 und R7, die gleich oder verschieden sind, unabhängig voneinander (C1-C4)-Alkyl, Phenyl oder substituiertes Phenyl bedeuten, und wobei dieser (C5-C12)-Kohlen Wasserstoff rest mit den möglichen vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) gegebenenfalls mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe(2) XO, S, NH, NR or NOR means and R is as defined in (1) above. (3) Y - Z together means a (C 5 -C 12 ) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 is formed by heteroatom groups such as O, NR 5 , S, SO, SO 2 or SiR 6 R 7 can be replaced, where R 5 is hydrogen, (C, -C 4 ) alkyl or (C 1 -C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently of one another (C 1 -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) carbon hydrogen radical with the possible aforementioned variations (replacement by heteroatom radical (s)) optionally with one or more, preferably up to three identical or different residues from the series
(CrC7)-Alkyl, (C2-C4)-Alkenyl, (C2-C4)-Alkinyl, (C3-C7)-Cycloalkyl, (C3-C7)-Cycloalkenyl, Halogen,(C r C 7 ) alkyl, (C 2 -C 4 ) alkenyl, (C 2 -C 4 ) alkynyl, (C 3 -C 7 ) cycloalkyl, (C 3 -C 7 ) cycloalkenyl, halogen ,
Halogen-(CrC4)-alkyl, Halogen-(C1-C4)-alkoxy, Hydroxy undHalogen (C r C 4 ) alkyl, halogen (C 1 -C 4 ) alkoxy, hydroxy and
(C1-C4)-Acyl, substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt,(C 1 -C 4 ) acyl is substituted; or, if not covered by the above definitions,
(4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe(4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, which is one or more, preferably up to three identical or different radicals from the series
(CrC7)-Alkyl,(C r C 7 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(C3-C7)-Alkinyl,(C 3 -C 7 ) alkynyl,
(C3-C7)-Cycloalkyl,(C 3 -C 7 ) cycloalkyl,
(C3-C7)-Cycloalkenyl,(C 3 -C 7 ) cycloalkenyl,
Halogen,Halogen,
Halogen-(CrC4)-alkyl, Halogen-(C-|-C4)-alkoxy,Halogen (C r C 4 ) alkyl, Halogen (C- | -C 4 ) alkoxy,
Hydroxy undHydroxy and
(C1-C4)-Acyl substituiert ist; und(C 1 -C 4 ) acyl is substituted; and
(5) Z(5) Z
(a) Aryl, O-Aryl oder Aryl-(CrC4)-alkyl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu fünf, insbesondere bis zu drei gleichen oder verschiedenen Resten aus der Reihe(a) Aryl, O-aryl or aryl- (C r C 4 ) -alkyl, where aryl is a phenyl group, optionally with one or more, preferably up to five, in particular up to three identical or different radicals from the series
Halogen,Halogen,
(C3-C8)-Cycloalkyl,(C 3 -C 8 ) cycloalkyl,
(C3-C8)-Cycloalkenyl,(C 3 -C 8 ) cycloalkenyl,
Phenoxy, substituiertes Phenoxy,Phenoxy, substituted phenoxy,
Phenylthio, substituiertes Phenylthio,Phenylthio, substituted phenylthio,
Phenyl, substitutiertes Phenyl,Phenyl, substituted phenyl,
NO2, O -C "-R 88,NO 2 , O -C "-R 8 8 ,
Acetoxy,Acetoxy,
Hydroxy,Hydroxy,
Cyano,Cyano,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
O-SiR9R10R1 1 ,O-SiR 9 R 10 R 1 1 ,
NR12R13 NR 12 R 13
S(O)R14,S (O) R 14 ,
SO2R14,SO 2 R 14 ,
(CrC12)-Alkyl,(C r C 12 ) alkyl,
(C2-C12)-Alkenyl,(C 2 -C 12 ) alkenyl,
(C-|-Cι2)-Alkoxy und substituiert ist; und(C- | -Cι 2 ) alkoxy and is substituted; and
R8 (CrC7)-Alkyl, Halogen-(CrC7)-alkyl, (C3-C7)-Cycloalkyl, Halogen-(C3-C7)-cycloalkyl, (C1-C7)-Alkoxy, Phenyl oder substituiertes Phenyl bedeutet;R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 3 -C 7 ) cycloalkyl, halogen (C 3 -C 7 ) cycloalkyl, (C 1 -C 7 ) -Alkoxy, phenyl or substituted phenyl;
R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C1-C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten;R 9 , R 10 and R 1 1 are the same or different and independently of one another are (C 1 -C 4 ) alkyl, phenyl and / or substituted phenyl;
R12 und R13 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (CrC4)-Alkyl und/oder (C1-C4)-Acyl bedeuten;R 12 and R 13 are identical or different and independently of one another are hydrogen, (C r C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl;
R14 (C.|-C10)-Alkyl, Phenyl oder substituiertes Phenyl bedeutet; wobei in (C C12)-Alkyl, (C2-C12)-Alkenyl, (CrC12)-Alkoxy und (C1-C12)-Alkylthio gegebenenfalls eine oder mehrere, vorzugsweise bis zu 3 CH2-Gruppen durch CO und/oder Heteroatome/Gruppen, wie O, S, SO, SO2, NR5 oder SiR6R7 ersetzt sind; R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (C.ι-C.| )-Alkylrest, der (C.,-C1 )-Alkoxyrest und der (C.ι-C12)- Alkylthiorest mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e) bzw. CO) außerdem mit einer oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur maximalen Anzahl an Resten gleichen oder verschiedenen der nachstehenden Resten aus der Reihe Halogen, Halogen-(C.,-C4)- alkoxy, Hydroxy, (C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkenyl, (C,-C4)- Acyl, Phenoxy, substituiertes Phenoxy, Phenyl, substituiertes Phenyl, Phenylthio und substituiertes Phenylthio substituiert sein können; oder (b) (C3-C8)-Cycloalkyl oder (C5-C8)-Cycloalkenyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl- oder (C5-C8)-Cycloalkenyl-Rest gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenenR 14 represents (C. | -C 10 ) alkyl, phenyl or substituted phenyl; where in (CC 12 ) alkyl, (C 2 -C 12 ) alkenyl, (C r C 12 ) alkoxy and (C 1 -C 12 ) alkylthio optionally one or more, preferably up to 3 CH 2 groups are replaced by CO and / or heteroatoms / groups such as O, S, SO, SO 2 , NR 5 or SiR 6 R 7 ; R 5 , R 6 and R 7 have the meaning as above under (3); the (C.ι-C. | ) -alkyl radical, the (C., -C 1 ) -alkoxy radical and the (C.ι-C 12 ) -alkylthio radical with or without the abovementioned variations (replacement by heteroatom radical (s) or . CO) also with one or more, preferably up to three, in the case of halogen up to the maximum number of radicals identical or different of the radicals below from the series halogen, halogen (C 1 -C 4 ) alkoxy, hydroxy, (C 3 -C 8 ) cycloalkyl, (C 3 -C 8 ) cycloalkenyl, (C, -C 4 ) acyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio and substituted phenylthio may be substituted; or (b) is (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 denotes phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl radical, optionally with one or more, preferably up to three, in the case of Halogen up to the maximum number of the same or different
Resten aus der Reihe (CrC18)-Alkyl, (C2-C18)-Alkenyl, (CrC12)-Alkoxy, (C2-C12)-Acyl, (C-, -C, 2)-Alky l-oxycarbonyl, SiR9R10R1 1, NR16R17, Hydroxyl, Oxo, Halogen, Aryl,Residues from the series (C r C 18 ) -alkyl, (C 2 -C 18 ) -alkenyl, (C r C 12 ) -alkoxy, (C 2 -C 12 ) -acyl, (C-, -C, 2 ) -Alky l-oxycarbonyl, SiR 9 R 10 R 1 1 , NR 16 R 17 , hydroxyl, oxo, halogen, aryl,
(C C18)-Alkandiyl, (Cι-C18)-Alkandiyldioxy, (C.,-C13)-Alkyl-oxiιτιino, Aryl-(C-|-C4)-alkyl-oximino und(CC 18 ) -alkanediyl, (-C-C 18 ) -alkanediyldioxy, (C., - C 13 ) -alkyl-oxiιτιino, aryl- (C- | -C 4 ) -alkyl oximino and
(C2-C18)-Alkyliden substituiert ist und in den genannten (C-|-Cι8)-, (C2-C18)-, (C-|-C1 )-, (C -C12)- und (C-|-C13)- Kohlenwasserstoff-Resten eine oder mehrere, vorzugsweise bis zu drei CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 8, vorzugsweise 3 bis 6 C-Atome dieser Kohlenwasserstoff- Reste und gegebenenfalls Heteroatomreste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl, substituiertes Phenyl, Phenylthio und substituiertes Phenylthio substituiert sind;(C 2 -C 18 ) alkylidene is substituted and in the (C- | -Cι 8 ) -, (C 2 -C 18 ) -, (C- | -C 1 ) -, (C -C 12 ) - and (C- | -C 13 ) - hydrocarbon radicals one or more, preferably up to three, CH 2 groups can be replaced by heteroatoms / groups, such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as under (3) and, in addition, 3 to 8, preferably 3 to 6, carbon atoms of these hydrocarbon radicals and, if appropriate, heteroatom radicals can form a cycle and these hydrocarbon radicals with or without the variations (replaced by Heteroatom radical (s) and / or cycle formation) optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl, substituted Phenyl, phenylthio and substituted phenylthio are substituted;
R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben; und R16 und R17 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (C-j-C6)-Alkyl, (C.|-C6)-R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a); and R 16 and R 17 are identical or different and are independently hydrogen, (C-j-C6) alkyl, (C. | -C6) -
Alkoxy, (CrC4)-Acyl, (C3-C6)-Cycloalkyl, Phenyl und substituiertes Phenyl bedeuten.Alkoxy, (C r C 4 ) acyl, (C 3 -C 6 ) cycloalkyl, phenyl and substituted phenyl.
In der obigen Formel 1 ist unter "Halogen" ein Fluor-, Chlor-, Brom- oder lodatom, vorzugsweise ein Fluor-, Chlor- oder Bromatom, insbesondere ein Fluor- oder Chloratom, zu verstehen;In the above formula 1, "halogen" means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom, in particular a fluorine or chlorine atom;
unter dem Ausdruck "Alkyl" ein unverzweigter oder verzweigter Kohlenwasserstoff rest wie z. B. der Methyl-, Ethyl-, Propyl-, 1-Methylethyl-, 1 -Methylpropyl-, 2-Methylpropyl- oder 1 ,1-Dimethylethylrest, der Pentyl, 2-Methylbutyl- oder der 1 ,1 -Dimethylpropylrest, der Hexyl-, Heptyl-, Octylrest oder 1 , 1 ,3,3-Tetramethylbutylrest, der Nonyl-, Decyl-, Undecyl- oder Dodecylrest und dergleichen;under the term "alkyl" an unbranched or branched hydrocarbon residue such as. B. the methyl, ethyl, propyl, 1-methylethyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl radical, the pentyl, 2-methylbutyl or the 1, 1-dimethylpropyl radical, the hexyl -, heptyl, octyl or 1, 1, 3,3-tetramethylbutyl, the nonyl, decyl, undecyl or dodecyl radical and the like;
unter "Alkenyl" und "Alkinyl" von dessen Alkylresten abgeleitete ungesättigte Reste;under "alkenyl" and "alkynyl" unsaturated radicals derived from its alkyl radicals;
unter dem Ausdruck "Cycloalkyl" vorzugsweise Cyclopropyl-, Cyclobutyl-, Cyclopentyl-, Cyclohexyl-, Cycloheptyl- oder Cyclooctenylgruppe; unter dem Ausdruck "Alkoxy" eine Alkoxygruppe, deren Kohlenwasserstoffrest die unter dem Ausdruck "Alkyl" angegebene Bedeutung hat;under the expression "cycloalkyl" preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctenyl group; the term "alkoxy" means an alkoxy group whose hydrocarbon radical has the meaning given under the term "alkyl";
unter dem Ausdruck "Cycloalkoxy" eine Cycloalkoxygruppe, deren Kohlenwasserstoffrest die unter "Cycloalkyl" angegebene Bedeutung hat; unter dem Ausdruck "Alkylthio" eine Alkylthiogruppe, deren Kohlenwasserstoffrest die unter dem Ausdruck "Alkyl" angegebene Bedeutung hat;under the term "cycloalkoxy" a cycloalkoxy group whose hydrocarbon radical has the meaning given under "cycloalkyl"; the term "alkylthio" means an alkylthio group whose hydrocarbon radical has the meaning given under the term "alkyl";
unter dem Ausdruck "Halogenalkyl" eine unter dem Ausdruck "(C-j-C^-Alkyl" genannte Alkylgruppe, in der eines oder mehrere Wasserstoffatome durch die obengenannten Halogenatome, bevorzugt Chlor oder Fluor, ersetzt wird, wie beispielsweise die Trifluormethylgruppe, die 2,2,2-Trifluorethylgruppe, die Chlormethyl-, Fluormethylgruppe, die Difluormethylgruppe oder die 1 ,1 ,2,2- tetrafluorethylgruppe (entsprechendes gilt für "HalogenalkenyP);the term "haloalkyl" is one referred to under the term "(C j -C ^ alkyl" group in which one or more hydrogen atoms are replaced by the abovementioned halogen atoms, preferably chlorine or fluorine, is replaced, such as the trifluoromethyl group, the 2 , 2,2-trifluoroethyl group, the chloromethyl, fluoromethyl group, the difluoromethyl group or the 1, 1, 2,2-tetrafluoroethyl group (the same applies to "haloalkenyl");
unter dem Ausdruck "Halogenalkoxy" eine Halogenalkoxygruppe, deren Halogen-Kohlenwasserstoffrest die unter dem Ausdruck "Halogenalkyl" angegebene Bedeutung hat;the term "haloalkoxy" means a haloalkoxy group whose halogenated hydrocarbon radical has the meaning given under the term "haloalkyl";
auch bei den anderen, hier im einzelnen nicht aufgeführten Resten mit dem Zusatz "Halogen" bedeutet dieser Zusatz, daß in diesen Resten ein, mehrere oder alle Wasserstoffatome durch Halogenatome ersetzt sind;also in the case of the other radicals not specifically listed here with the addition "halogen", this addition means that one, more or all of the hydrogen atoms in these radicals have been replaced by halogen atoms;
unter "substituiertem Phenyl" einen Phenylrest, der einen oder mehrere, vorzugsweise bis zu drei gleiche oder verschiedene Substituenten aus der Reihe Halogen, (CrC4)-Alkyl, Halogen-(CrC4)-alkyl, Hydroxy-(CrC4)-alkyl, (CrC4)- Alkoxy, Halogen-(C1-C4)-alkoxy, Phenoxy, Phenyl, Nitro, Hydroxy, Cyano, (C1-C4)-Alkanoyl, Benzoyl, (CrC4)-Alkanoyloxy, (C1-C4)-Alkoxycarbonyl trägt;"Substituted phenyl" means a phenyl radical which has one or more, preferably up to three identical or different substituents from the series halogen, (C r C 4 ) -alkyl, halogen (C r C 4 ) -alkyl, hydroxy- (C r C 4 ) -alkyl, (C r C 4 ) -alkoxy, halogen- (C 1 -C 4 ) -alkoxy, phenoxy, phenyl, nitro, hydroxy, cyano, (C 1 -C 4 ) -alkanoyl, benzoyl, (C r C 4 ) alkanoyloxy, (C 1 -C 4 ) alkoxycarbonyl;
unter "substituiertem Amino" eine Aminogruppe, die mit eifner oder zwei (C1-C4)-Alkylgruppen oder einer (C1-C4)-Alkanoylgruppe substituiert ist;"substituted amino" means an amino group which is substituted by one or two (C 1 -C 4 ) -alkyl groups or one (C 1 -C 4 ) -alkanoyl group;
unter einem "bivalenten Kohlenwasserstoffrest" einen von n-Alkanen oder n-Alkenen durch Entfernen je eines Wasserstoffatoms von den beiden endständigen Kohlenstoffatomen der Kette abgeleiteter Rest, wie Methylen, Ethandiyl, Trimethylen, Tetramethylen; unter "Acyl" insbesondere einen Alkanoylrest, wie Acetyl, Propionyl oder Butyryl, oder einen Alkyloxycarbonylrest.a "bivalent hydrocarbon radical" means a radical derived from n-alkanes or n-alkenes by removing one hydrogen atom from each of the two terminal carbon atoms in the chain, such as methylene, ethanediyl, trimethylene, tetramethylene; "Acyl" means in particular an alkanoyl radical, such as acetyl, propionyl or butyryl, or an alkyloxycarbonyl radical.
Die oben gegebene Erläuterung gilt entsprechend für Homologe bzw. deren abgeleitete Reste.The explanation given above applies accordingly to homologs or their derived residues.
Die Substituenten an den unter (5b) definierten Cycloalkyl- oder Cycloalkenylresten können eis oder trans bezüglich Y stehen; bevorzugt ist die cis-Stellung. Wenn nur ein Substituente vorhanden ist, sollte er in Cyclohexyl, vorzugsweise in der 4-Position stehen und cis-konfiguiert sein.The substituents on the cycloalkyl or cycloalkenyl radicals defined under (5b) can be ice or trans with respect to Y; the cis position is preferred. If only one substituent is present, it should be in cyclohexyl, preferably in the 4-position, and be cis-configured.
Bevorzugt sind Verbindungen der Formel 1 und deren Salze, worinCompounds of formula 1 and their salts are preferred, wherein
(1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend aus R-O-CH2-, R-O-CO-,(1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, is selected from the group consisting of RO-CH 2 -, RO-CO-,
Halogen-(C1-C )-alkoxymethyl, Halogen-(C1-C4)-alkenyloxymethyl, Halogen-(C1-C4)-alkoxycarbonyl, Halogen-(C,-C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist;Halogen (C 1 -C) alkoxymethyl, halogen (C 1 -C 4 ) alkenyloxymethyl, halogen (C 1 -C 4 ) alkoxycarbonyl, halogen (C, -C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4;
und die übrigen 4-x Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt werden aus der Gruppe bestehend ausand the remaining 4-x radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, are selected from the group consisting of
(CrC4)-Alkyl,(C r C 4 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(CrC4)-Alkoxy,(C r C 4 ) alkoxy,
(C2-C4)-Alkenyloxy,(C 2 -C 4 ) alkenyloxy,
Halogen-(CrC4)-alkyl,Halogen (C r C 4 ) alkyl,
Halogen-(C2-C4)-alkenyl, Halogen-(C1-C4)-alkoxy, Halogen-(C2-C4)-alkenyloxy Halogen und Wasserstoff; R (CrC7)-Alkyl,Halogen (C 2 -C 4 ) alkenyl, Halogen (C 1 -C 4 ) alkoxy, halogen (C 2 -C 4 ) alkenyloxy halogen and hydrogen; R (C r C 7 ) alkyl,
(C2-C7)-Alkenyl, (C2-C7)-Alkinyl oder (C3-C6)-Cycloalkyl bedeutet;Is (C 2 -C 7 ) alkenyl, (C 2 -C 7 ) alkynyl or (C 3 -C 6 ) cycloalkyl;
(2) X O, S, NH, NR oder NOR bedeutet;(2) X represents O, S, NH, NR or NOR;
(3) Y - Z zusammen wie oben definiert ist und gegebenenfalls mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe(3) Y - Z together as defined above and optionally with one or more, preferably up to three identical or different radicals from the series
(CrC7)-Alkyl, Halogen,(C r C 7 ) alkyl, halogen,
Halogen-(CrC4)-alkyl, Halogen-(C1-C4)-alkoxy, undHalogen (C r C 4 ) alkyl, halogen (C 1 -C 4 ) alkoxy, and
(C1-C4)-Acyl substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt,(C 1 -C 4 ) acyl is substituted; or, if not covered by the above definitions,
(4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe:(4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 C atoms, which is one or more, preferably up to three identical or different radicals from the series:
(CrC7)-Alkyl, Halogen,(C r C 7 ) alkyl, halogen,
Halogen-(C1-C4)-alkyl und Halogen-(CrC4)-alkoxy, substituiert ist; und (5) ZHalogen (C 1 -C 4 ) alkyl and halogen (C r C 4 ) alkoxy is substituted; and (5) Z
(a) Aryl, O-Aryl oder Aryl-(C1-C4)-alkyl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu fünf, insbesondere bis zu drei gleichen oder verschiedenen Resten aus der Reihe Halogen,(a) Aryl, O-aryl or aryl- (C 1 -C 4 ) -alkyl, where aryl is a phenyl group which may have one or more, preferably up to five, in particular up to three identical or different radicals from the Halogen series,
(C3-C8)-Cycloalkyl, (C3-C8)-Cycloalkenyl, Phenoxy, substituiertes Phenoxy, Phenyl, substitutiertes Phenyl, O(C 3 -C 8 ) cycloalkyl, (C 3 -C 8 ) cycloalkenyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, O
-C '-R 88,-C '-R 8 8 ,
SiR9Rl0R1 1 ,SiR 9 R 10 R 1 1 ,
O-SiR9R10R1 1 ,O-SiR 9 R 10 R 1 1 ,
NR12R13 NR 12 R 13
(CrC12)-Alkyl,(C r C 12 ) alkyl,
(C2-C12)-Alkenyl und(C 2 -C 12 ) alkenyl and
(C,-C12)-Alkoxy substituiert ist; und(C, -C 12 ) alkoxy is substituted; and
R8 (CrC7)-Alkyl, Halogen-(CrC7)-alkyl, (C5-C6)-Cycloalkyl, (Cr R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 5 -C 6 ) cycloalkyl, (C r
C7)-Alkoxy, Phenyl oder substituiertes Phenyl bedeutet;C 7 ) alkoxy, phenyl or substituted phenyl;
R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten;R 9 , R 10 and R 1 1 are identical or different and independently of one another are (CC 4 ) alkyl, phenyl and / or substituted phenyl;
R12 und R13 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (C1-C4)-Alkyl und/oder (C1-C4)-Acyl bedeuten; wobei in (C C12)-Alkyl, (C2-C12)-Alkenyl und (Cl-C12)-Alkoxy gegebenenfalls eine oder mehrere, vorzugsweise bis zu 3 CH2-R 12 and R 13 are identical or different and independently of one another are hydrogen, (C 1 -C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl; wherein in (CC 12 ) alkyl, (C 2 -C 12 ) alkenyl and (C 1 -C 12 ) alkoxy optionally one or more, preferably up to 3 CH 2 -
Gruppen durch CO und/oder Heteroatome/Gruppen, wie O, S, SO, SO2, NR5 oder SiR6R7 ersetzt sind;Groups by CO and / or heteroatoms / groups, such as O, S, SO, SO 2 , NR 5 or SiR 6 R 7 are replaced;
R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (C- Cj^-Alkylrest und der (C^C^j-Alkoxyrest mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) außerdem mit einer oder mehreren, vorzugsweise bis zu drei, imR 5 , R 6 and R 7 have the meaning as above under (3); the (C- C j ^ alkyl radical and the (C ^ C ^ j alkoxy radical with or without the abovementioned variations (replacement by heteroatom radical (s)) also with one or more, preferably up to three, in
Falle von Halogen bis zur maximalen Anzahl an Resten gleichen oder verschiedenen der nachstehenden Resten aus der ReiheIn the case of halogen up to the maximum number of residues of the same or different of the residues below from the series
Halogen, Halogen-(C1-C4)-alkoxy, (C3-C6)-Cycloalkyl, (C1-C4)-Acyl,Halogen, halogen- (C 1 -C 4 ) alkoxy, (C 3 -C 6 ) cycloalkyl, (C 1 -C 4 ) acyl,
Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sein können; oder Halogen F oder Cl bedeutet;Phenoxy, substituted phenoxy, phenyl and substituted phenyl may be substituted; or halogen represents F or Cl;
(b) (C3-C6)-Cycloalkyl oder (C5-C8)-Cycloalkenyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl- oder (C5-C8)-Cycloalkenyl-Rest gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe(b) denotes (C 3 -C 6 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, it being possible for a CH 2 group of the carbocycle to be replaced by NR 15 ; R 15 denotes phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl radical, optionally with one or more, preferably up to three, in the case of halogen up to the maximum number same or different residues from the series
(CrC18)-Alkyl,(C r C 18 ) alkyl,
(C2-C18)-Alkenyl,(C 2 -C 18 ) alkenyl,
(CrC12)-Alkoxy,(C r C 12 ) alkoxy,
(C2-C12)-Acyl,(C 2 -C 12 ) acyl,
(C-,-C12)-Alkyl-oxycarbonyl,(C -, - C 12 ) alkyl oxycarbonyl,
SiR9R10R1 1,SiR 9 R 10 R 1 1 ,
Hydroxyl,Hydroxyl,
Oxo,Oxo,
Halogen,Halogen,
Aryl,Aryl,
(CrC18)-Alkandiyl,(C r C 18 ) alkanediyl,
(C C18)-Alkandiyldioxy(CC 18 ) alkanediyl dioxy
(C-|-C13)-Alkyl-oximino,(C- | -C 13 ) alkyl oximino,
Aryl-(C1-C4)-alkyloximino und (C2-C18)-Alkyliden substituiert sind und in den genannten (C-|-C18)-, (C2-C-| 8)-, (C-,-C12)-, (C2-C-| 2)- und (Cι-C-,3)- Kohlenwasserstoff-Resten eine oder mehrere, vorzugsweise bis zu drei CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 6 C-Atome und gegebenenfalls Heteroatomreste dieser Kohlenwasserstoff-Reste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sind;Aryl- (C 1 -C 4 ) alkyloximino and (C 2 -C 18 ) alkylidene are substituted and in the (C- | -C 18 ) -, (C 2 -C- | 8 ) -, (C -, - C 12 ) -, (C 2 - C- | 2 ) - and (-C-C-, 3 ) - hydrocarbon radicals one or more, preferably up to three, CH 2 groups can be replaced by heteroatoms / groups, such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as under (3) and in addition 3 to 6 carbon atoms and optionally heteroatom radicals of these hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the variations (replacement by Heteroatomrest (e) and / or cycle formation) optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl are substituted;
R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben.R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
Besonders bevorzugt sind daher Verbindungen der Formel 1 und deren Salze, worinCompounds of formula 1 and their salts, in which
(1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend aus(1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, is selected from the group consisting of
R-O-CH2-,RO-CH 2 -,
R-O-CO-,R-O-CO-,
Halogen-(C.,-C4)-alkoxymethyl,Halogen- (C., - C 4 ) -alkoxymethyl,
Halogen-(C1-C4)-alkenyloxymethyl,Halogen (C 1 -C 4 ) alkenyloxymethyl,
Halogen-(C1-C4)-alkoxycarbonyl,Halogen (C 1 -C 4 ) alkoxycarbonyl,
Halogen-(C1-C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist; und die übrigen 4-x der Reste R1, R2, R3 und R4 unabhängig voneinander für gleiche oder verschiedene Reste aus der ReiheHalogen (C 1 -C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4; and the remaining 4-x of the radicals R 1 , R 2 , R 3 and R 4 independently of one another for identical or different radicals from the series
(CrC3)-Alkyl,(C r C 3 ) alkyl,
(C2-C3)-Alkenyl,(C 2 -C 3 ) alkenyl,
(CrC3)-Alkoxy,(C r C 3 ) alkoxy,
(C -C3)-Alkenyloxy,(C -C 3 ) alkenyloxy,
Halogen-fCj-C^-alkyl,Halogen fC j -C ^ alkyl,
Halogen-(C2-C9)-alkenyl,Halogen (C 2 -C 9 ) alkenyl,
Halogen-(C-|-C3)-alkoxy,Halogen- (C- | -C 3 ) -alkoxy,
Halogen-(C2-C3)-alkenyloxyHalogen (C 2 -C 3 ) alkenyloxy
Halogen undHalogen and
Wasserstoff stehen; R (CrC5)-Alkyl,Stand hydrogen; R (C r C 5 ) alkyl,
(C2-C5)-Alkenyl oder(C 2 -C 5 ) alkenyl or
(C3-C6)-Cycloalkyl bedeutet;Is (C 3 -C 6 ) cycloalkyl;
(2) X O oder NH bedeutet;(2) X represents O or NH;
(3) Y - Z zusammen einen (C5-C12) Kohlenwasserstoffrest bedeutet, der unverzweigt oder verzweigt ist und bei dem eine oder mehrere, vorzugsweise bis zu drei CH2 durch Heteroatomgruppen wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5 (CrC4)-Acyl, und R6 und R7, die gleich oder verschieden sind, unabhängig voneinander (C1-C4)-Alkyl, Phenyl oder substituiertes Phenyl bedeuten, und wobei dieser (C5-C12)- Kohlenwasserstoffrest mit den möglichen vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) gegebenenfalls mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe(3) Y - Z together means a (C 5 -C 12 ) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 have been replaced by heteroatom groups such as O, NR 5 or SiR 6 R 7 where R 5 is (C r C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently of one another are (C 1 -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) - hydrocarbon radical with the possible above-mentioned variations (replacement by heteroatom radical (s)) optionally with one or more, preferably up to three identical or different radicals from the series
(CrC5)-Alkyl, Fluor, Chlor,(C r C 5 ) alkyl, fluorine, chlorine,
Halogen-(C1-C4)-alkyl und Halogen-(C1-C3)-alkoxy substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt,Halogen (C 1 -C 4 ) alkyl and halogen (C 1 -C 3 ) alkoxy is substituted; or, if not covered by the above definitions,
(4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren, vorzugsweise bis zu drei gleichen oder verschiedenen Resten aus der Reihe(4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, which is one or more, preferably up to three identical or different radicals from the series
(CrC5)-Alkyl, Fluor, Chlor,(C r C 5 ) alkyl, fluorine, chlorine,
Halogen-(C1-C3)-alkyl und Halogen-(C1-C3)-alkoxy, substituiert ist; undHalogen (C 1 -C 3 ) alkyl and halogen (C 1 -C 3 ) alkoxy is substituted; and
(5) Z(5) Z
(a) Aryl oder O-Aryl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu fünf, insbesondere bis zu drei gleichen oder verschiedenen Resten aus der Reihe(a) Aryl or O-aryl, where aryl is a phenyl group which may be one or more, preferably up to five, in particular up to three identical or different radicals from the series
Halogen,Halogen,
(C3-C6)-Cycloalkyl,(C 3 -C 6 ) cycloalkyl,
Phenoxy, substituiertes Phenoxy,Phenoxy, substituted phenoxy,
Phenyl, substitutiertes Phenyl,Phenyl, substituted phenyl,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
O-SiR9RloR1 1 ,O-SiR 9 R lo R 1 1 ,
(CrC6)-Alkyl und(C r C 6 ) alkyl and
(CrC7)-Alkoxy substituiert ist; und R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C1-C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten; wobei in (C-|-C6)-Alkyl und (C-,-C7)- Alkoxy gegebenenfalls eine oder mehrere, vorzugsweise bis zu 3 CH2-Gruppen durch Heteroatome/Gruppen, wie O, S, NR5 oder SiR6R7 ersetzt sind; R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (CrC6)-Alkylrest und der (C1-C7)-Alkoxyrest mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) außerdem mit einer oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur maximalen Anzahl an Resten gleichen oder verschiedenen der nachstehenden Resten aus der Reihe: Halogen, (C3-C6)-Cycloalkyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sein kann; Halogen Fluor oder Brom ist; oder(C r C 7 ) alkoxy is substituted; and R 9 , R 10 and R 1 1 are identical or different and independently of one another are (C 1 -C 4 ) -alkyl, phenyl and / or substituted phenyl; where in (C- | -C 6 ) alkyl and (C -, - C 7 ) - alkoxy optionally one or more, preferably up to 3 CH 2 groups by heteroatoms / groups such as O, S, NR 5 or SiR 6 R 7 are replaced; R 5 , R 6 and R 7 have the meaning as above under (3); the (C r C 6 ) -alkyl radical and the (C 1 -C 7 ) -alkoxy radical with or without the abovementioned variations (replacement by heteroatom radical (s)) also with one or more, preferably up to three, in the case of halogen bis for the maximum number of radicals identical or different of the following radicals from the series: halogen, (C 3 -C 6 ) -cycloalkyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl; Halogen is fluorine or bromine; or
(b) (C3-C6)-CycloaIkyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl- Rest gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe(b) denotes (C 3 -C 6 ) -cycloalkyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 is phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl radical optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series
(CrC12)-Alkyl,(C r C 12 ) alkyl,
(C2-C18)-Alkenyl,(C 2 -C 18 ) alkenyl,
(CrC12)-Alkoxy,(C r C 12 ) alkoxy,
(C2-C12)-Acyl, (C 2 -C 12 ) acyl,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
Hydroxyl,Hydroxyl,
Oxo,Oxo,
Halogen,Halogen,
Aryl,Aryl,
(Cj-C^-Alkandiyl,(C j -C ^ alkanediyl,
(C,-C18)-Alkandiyldioxy (C-,-C18)-Alkyl-oximino, Aryl-(C.|-C4)-alkyloximino und(C, -C 18 ) alkanediyl dioxy (C -, - C 18 ) alkyl oximino, aryl (C. | -C 4 ) alkyloximino and
(C2-C12)-Alkyliden substituiert ist und in den genannten (CrC12)-, (C2-C12)- und (CrC8)-Kohlenwasserstoff-Resten eine oder mehrere, vorzugsweise bis zu drei CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 6 C-Atome und/oder Heteroatomrest(e) dieser Kohlenwasserstoff-Reste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sind;(C 2 -C 12 ) alkylidene is substituted and in the (C r C 12 ), (C 2 -C 12 ) and (C r C 8 ) hydrocarbon radicals mentioned one or more, preferably up to three CH 2 groups can be replaced by heteroatoms / groups such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as under (3) and moreover 3 to 6 C atoms and / or heteroatom radical (s) of these hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the variations (replacement by heteroatom radical (s) and / or cycle formation) optionally with one or more, preferably up to three, in the case of Halogen are substituted up to the maximum number of identical or different radicals from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl;
R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben.R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
Die vorliegende Erfindung betrifft die Verbindungen der Formel 1 in Form der freien Base oder eines Säureadditionssalzes. Säuren, die zur Salzbildung herangezogen werden können, sind anorganische Säuren, wie Salzsäure, Bromwasserstoffsäure, Salpetersäure, Schwefelsäure, Phosphorsäure oder organische Säuren wie Ameisensäure, Essigsäure, Propionsäure, Malonsäure, Oxalsäure, Fumarsäure, Adipinsäure, Stearinsäure, Olsäure, Methansulfonsäure, Benzolsulfonsäure oder Toluolsulfonsäure.The present invention relates to the compounds of formula 1 in the form of the free base or an acid addition salt. Acids which can be used for salt formation are inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid or organic acids such as formic acid, acetic acid, propionic acid, malonic acid, oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid, benzenesulfonic acid or toluene .
Die Verbindungen der Formel 1 weisen zum Teil ein oder mehrere asymmetrische Kohlenstoffatome auf. Es können daher Racemate und Diastereomere auftreten. Die Erfindung umfaßt sowohl die reinen Isomeren als auch deren Gemische. Die Gemische von Diastereomeren können nach gebräuchlichen Methoden, z. B. durch selektive Kristallisation aus geeigneten Lösungsmitteln oder durch Chromatographie in die Komponenten aufgetrennt werden. Racemate können nach üblichen Methoden in die Enantiomeren aufgetrennt werden, so z. B. durch Salzbildung mit einer optisch aktiven Säure, Trennung der diastereomeren Salze und Freisetzung der reinen Enantiomeren mittels einer Base.Some of the compounds of formula 1 have one or more asymmetric carbon atoms. Racemates and diastereomers can therefore occur. The invention encompasses both the pure isomers and their mixtures. The mixtures of diastereomers can according to common methods, e.g. B. by selective crystallization from suitable solvents or by chromatography in the components. Racemates can be separated into the enantiomers by customary methods, for. B. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers by means of a base.
Die Erfindung betrifft weiterhin ein Verfahren zur Herstellung von Verbindungen der Formel 1 , das dadurch gekennzeichnet ist, daß man Verbindungen der Formel 2The invention further relates to a process for the preparation of compounds of formula 1, which is characterized in that compounds of formula 2
in der R1 , R2, R3 und R4 wie oben definiert sind und L eine Abgangsgruppe ist, mit den entsprechenden Aminen, Alkoholen, Phenolen oder Mercaptanen umsetzt, oder unter Bildung von Verbindungen der Formel 1 , worin Z wie unter (5b) definiert ist, solche Verbindungen der Formel 1 , worin R1 , R2, R3, R4, X und Y wie oben definiert sind und Z für einen ungesättigten carbocyclischen, wie Cycloalkyl oder Cycloalkenyl unter (5b) definiert substituierten Rest, vorzugsweise einen auf diese Weise substituierten Phenylrest steht, hydriert, und die so erhaltenen Verbindungen der Formel 1 gegebenenfalls in ihr Salz überführt.in which R 1 , R 2 , R 3 and R 4 are as defined above and L is a leaving group, with the corresponding amines, alcohols, phenols or mercaptans, or to form compounds of the formula 1, in which Z is as described in (5b ) is defined, such compounds of formula 1, wherein R 1 , R 2 , R 3 , R 4 , X and Y are as defined above and Z for an unsaturated carbocyclic, such as cycloalkyl or cycloalkenyl under (5b) defined substituted radical, preferably a phenyl radical substituted in this way is hydrogenated, and the compounds of formula 1 thus obtained are optionally converted into their salt.
Die oben beschriebene Substitutionsreaktion ist im Prinzip bekannt. Die Abgangsgruppe ist in weiten Grenzen variierbar und kann beispielsweise ein Halogenatom wie Fluor, Chlor, Brom oder Jod bedeuten oder Alkylthio wie Methyl- oder Ethylthio, oder Alkansulfonyloxy wie Methan-, Trifluormethan- oder Ethansulfonyloxy oder Arylsulfonyloxy, wie Benzolsulfonyloxy oder Toluolsulfonyloxy oder Alkylsulfonyl wie Methyl- oder Ethylsulfonyl oder Arylsulfonyl wie Phenyl- oder Toluolsulfonyl. Die Verbindungen der Formel 2 können nach bekannten Methoden hergestellt werden [z. B. J. Med., Chem. 32, 1970 (1989), J. Org. Chem. 2£ 776 (1964), J. Prakt. Chem. 331 . 369 (1989), J. Org. Chem. 1_4, 97 (1949), Chem. Ber. 74, 1 1 1 1 (1941 )]. Bevorzugt werden bei der Herstellung der Verbindungen 1 Verbindungen 2 eingesetzt, bei denen L = Cl Ist.The substitution reaction described above is known in principle. The leaving group can be varied within wide limits and can mean, for example, a halogen atom such as fluorine, chlorine, bromine or iodine or alkylthio such as methyl or ethylthio, or alkanesulfonyloxy such as methane, trifluoromethane or ethanesulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesulfonyloxy or alkylsulfonyl such as methyl - Or ethylsulfonyl or arylsulfonyl such as phenyl or toluenesulfonyl. The compounds of formula 2 can be prepared by known methods [e.g. BJ Med., Chem. 32, 1970 (1989), J. Org. Chem. 2 £ 776 (1964), J. Prakt. Chem. 331. 369 (1989), J. Org. Chem. 1_4, 97 (1949), Chem. Ber. 74, 1 1 1 1 (1941)]. Compounds 1 in which L = Cl are preferably used in the preparation of the compounds 1.
Die Umsetzungen mit Alkoholen und Mercaptanen werden in Gegenwart einer starken Base wie Natriumhydrid, Kaliumhydrid oder Kalium-tert.butylat in einem inerten aprotischen Lösungsmittel wie DMF, NMP, DMSO, THF, Dioxan oder Sulfolan bei einer Temperatur zwischen 0 und 80°C ausgeführt; bei der Umsetzung mit Alkoholaten kann es auch günstig sein, den dazugehörigen Alkohol als Lösungsmittel zu benutzen.The reactions with alcohols and mercaptans are carried out in the presence of a strong base such as sodium hydride, potassium hydride or potassium tert-butoxide in an inert aprotic solvent such as DMF, NMP, DMSO, THF, dioxane or sulfolane at a temperature between 0 and 80 ° C .; When reacting with alcoholates, it can also be advantageous to use the associated alcohol as a solvent.
Die Bedingungen für die Umsetzungen von 2 mit Aminen sind abhängig von den Substituenten R1 bis R4 in 2 und von der Struktur der eingesetzten Amine; sind die Reste R1 bis R4 in 2 inert, so kann 2 mit einem Überschuß Amin mit oder ohne Lösungsmittel bei Temperaturen zwischen 80 und 200°C zu 1 umgesetzt werden. Der Überschuß an Amin kann reduziert und die Temperatur erniedrigt werden, wenn saure Katalysatoren wie Phenol [J. Amer. Chem. Soc. 73, 2623 (1951 )] oder Salze wie Triethylammoniumchlorid oder Ammoniumchlorid verwendet werden. Als Lösungsmittel eignen sich z. B. DMF, N,N-Dimethylacetamid, DMSO, NMP, Dioxan, Diethylenglykoldimethylether, Triethylenglykol-dimethylether, Sulfolan, Toluol, Chlorbenzol oder Xylol. Es können auch Gemische der genannten Lösungsmittel verwendet werden.The conditions for the reaction of 2 with amines depend on the substituents R 1 to R 4 in 2 and on the structure of the amines used; if the radicals R 1 to R 4 in 2 are inert, 2 can be converted to 1 with an excess of amine with or without solvent at temperatures between 80 and 200 ° C. The excess of amine can be reduced and the temperature lowered if acidic catalysts such as phenol [J. Amer. Chem. Soc. 73, 2623 (1951)] or salts such as triethylammonium chloride or ammonium chloride. Suitable solvents are, for. B. DMF, N, N-dimethylacetamide, DMSO, NMP, dioxane, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, sulfolane, toluene, chlorobenzene or xylene. Mixtures of the solvents mentioned can also be used.
Ist oder sind einer oder mehrere Reste von R1 bis R4 in 2 eine RO-Funktion, so erhält man mit Aminen nach den oben genannten Methoden schlechte Ausbeuten an 1 oder andere nicht erwünschte Reaktionsprodukte; Ausnahmen sind die Reaktionen mit Anilinen und O-Alkyl- bzw. O-Aralkyl-hydroxylaminen, die zu den Produkten 3 und 4 führen (R' ist ein Substituent am Phenyl). If one or more radicals from R 1 to R 4 in 2 is an RO function, poor yields of 1 or other undesired reaction products are obtained with amines by the abovementioned methods; Exceptions are the reactions with anilines and O-alkyl- or O-aralkyl-hydroxylamines, which lead to products 3 and 4 (R 'is a substituent on the phenyl).
Die Verbindungen der Formel 3 lassen sich nach bekannten Methoden [z. B. F. Zymalkowski, Katalytische Hydrierungen, S. 191 , Enke Verlag, Stuttgart 1965] zu Verbindungen der Formel 1 katalytisch hydrieren (Schema 1 ).The compounds of formula 3 can by known methods [z. B. F. Zymalkowski, Catalytic hydrogenations, p. 191, Enke Verlag, Stuttgart 1965] to catalytically hydrogenate compounds of formula 1 (Scheme 1).
Schema 1Scheme 1
Die dabei anfallenden cis/trans-Gemische können durch Kristallisation oder Chromatographie getrennt werden.The resulting cis / trans mixtures can be separated by crystallization or chromatography.
Die Verbindungen der Formel 4 sind geeignete Zwischenprodukte, um eine breite Auswahl von Verbindungen der Formel 1 mit X = NH herzustellen (Schema 2) Schema 2:The compounds of formula 4 are suitable intermediates to prepare a wide range of compounds of formula 1 with X = NH (Scheme 2) Scheme 2:
1 ( X = N H )1 (X = N H)
Auf der Stufe 1 werden die Produkte der Formel 4 in Gegenwart von Basen wie Natriumhydrid oder Kalium-tert.butylat mit Alkylierungsmitteln der Formel L-Y-Z selektiv am Stickstoffsubstituenten in 4-Stellung des Pyridinringes zu 5 umgesetzt; in der Formel L-Y-Z bedeuten L Halogen oder R-SO3, Y wie oben definiert (außer Aryl) und Z wie oben angegeben. Bei der Verwendung von sterisch einheitlichen Alkylierungsmitteln sind auf diese Weise auch sterisch einheitliche Reaktionsprodukte zu erhalten. Eingesetzt werden bei dieser Reaktion Lösungsmittel wie z. B. DMF, DMSO, THF, Dimethoxyethan, Dioxan, Diethylenglykol-dimethylether, Sulfolan oder Toluol. Es können auch Gemische der genannten Lösungsmittel verwendet werden. Auf der Stufe 2 werden die Verbindungen der Formel 5 nach bekannten Methoden [R. Huisgen et al. B. 101 , 2559 (1968) C. H. Rayburn, W. R. Harlau, H. R. Haumer Am. Soc. 72, 1721 (1950)] reduktiv in die Verbindungen der Formel 1 umgewandelt.In stage 1, the products of the formula 4 are reacted selectively in the presence of bases such as sodium hydride or potassium tert-butoxide with alkylating agents of the formula LYZ on the nitrogen substituent in the 4-position of the pyridine ring to give 5; in the formula LYZ, L is halogen or R-SO 3 , Y is as defined above (except aryl) and Z is as indicated above. When using sterically uniform alkylating agents, sterically uniform reaction products can also be obtained in this way. Solvents such as z. B. DMF, DMSO, THF, dimethoxyethane, dioxane, diethylene glycol dimethyl ether, sulfolane or toluene. Mixtures of the solvents mentioned can also be used. At stage 2, the compounds of the formula 5 are prepared by known methods [R. Huisgen et al. B. 101, 2559 (1968) CH Rayburn, WR Harlau, HR Haumer Am. Soc. 72, 1721 (1950)] reductively converted into the compounds of formula 1.
Die eingesetzten Amine, Alkohole und Alkylierungsmittel sind nach literaturbekannten Methoden zugänglich. Die Alkohole können beispielsweise hergestellt werden durch Reduktion einer Carbonylgruppe mit einem geeigneten Reduktionsmittel, beispielsweise einem komplexen Metallhydrid oder im Falle eines Aldehyds oder Ketons auch mit Wasserstoff und einem Hydrierkatalysator. Weitere Möglichkeiten sind die Umsetzung einer metallorganischen Verbindung mit einer Carbonylgruppe oder einem Oxiran. Zur Darstellung von Cyclohexanol-Derivaten können auch geeignete substituierte Phenole mit Wasserstoff in Gegenwart eines Hydrierkatalysators umgesetzt werden.The amines, alcohols and alkylating agents used are accessible by methods known from the literature. The alcohols can be prepared, for example, by reducing a carbonyl group with a suitable reducing agent, for example a complex metal hydride or, in the case of an aldehyde or ketone, also with hydrogen and a hydrogenation catalyst. Other possibilities are the implementation of an organometallic compound with a carbonyl group or an oxirane. To prepare cyclohexanol derivatives, suitable substituted phenols can also be reacted with hydrogen in the presence of a hydrogenation catalyst.
Die Amine können beispielsweise hergestellt werden durch Reduktion eines Oxims oder eines Nitrils mit einem geeigneten Reduktionsmittel, beispielsweise einem komplexen Metallhydrid oder Wasserstoff in Gegenwart eines Hydrierkatalysators, reduktive Aminierung oder Leuckart-Wallach-Reaktion eines Aldehyds oder Ketons oder Gabriel-Reaktion eines Alkylhalogenids oder -Tosylats. Zur Darstellung von Cyclohexylamin-Derivaten können auch geeignete substituierte Aniline mit Wasserstoff in Gegenwart eines Hydrierkatalysators umgesetzt werden.The amines can be prepared, for example, by reducing an oxime or a nitrile with a suitable reducing agent, for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate . To prepare cyclohexylamine derivatives, suitable substituted anilines can also be reacted with hydrogen in the presence of a hydrogenation catalyst.
Die erfindungsgemäßen Verbindungen der Formel 1 zeichnen sich durch eine hervorragende fungizide Wirkung aus. Bereits in das pflanzliche Gewebe eingedrungene pilzliche Krankheitserreger lassen sich erfolgreich kurativ bekämpfen. Dies ist besonders wichtig und vorteilhaft bei solchen Pilzkrankheiten, die nach eingetretener Infektion mit den sonst üblichen Fungiziden nicht mehr wirksam bekämpft werden können. Das Wirkungsspektrum der beanspruchten Verbindungen erfaßt verschiedene wirtschaftlich bedeutende, phytopathogene Pilze, wie z. B. Phytophthora infestans, Plasmopara viticola, aber auch Erysiphe graminis und Pyrenophora teres. Die erfindungsgemäßen Verbindungen eignen sich daneben auch für den Einsatz in technischen Bereichen, beispielsweise als Holzschutzmittel, als Konservierungsmittel, in Dichtmassen, in Anstrichfarben, in Kühlschmiermittel für die Metallbearbeitung oder als Konservierungsmittel in Bohr- und Schneidölen.The compounds of formula 1 according to the invention are distinguished by an excellent fungicidal action. Fungal pathogens that have already penetrated into the plant tissue can be successfully combated curatively. This is particularly important and advantageous in the case of those fungal diseases which can no longer be effectively combated with the usual fungicides after infection has occurred. The spectrum of activity of the claimed compounds covers various economically important phytopathogenic fungi, such as. B. Phytophthora infestans, Plasmopara viticola, but also Erysiphe graminis and Pyrenophora teres. The compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives, in sealants, in paints, in cooling lubricants for metalworking or as preservatives in drilling and cutting oils.
Gegenstand der Erfindung sind auch Mittel, die die Verbindungen der Formel 1 neben geeigneten Formulierungshilfsmitteln enthalten. Die erfindungsgemäßen Mittel enthalten die Wirkstoffe der Formel 1 im allgemeinen zu 1 bis 95 Gew.-%.The invention also relates to compositions which contain the compounds of the formula 1 in addition to suitable formulation auxiliaries. The agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formula 1.
Sie können auf verschiedene Art formuliert werden, je nachdem wie es durch die biologischen und/oder chemisch-physikalischen Parameter vorgegeben ist. Als Formulierungsmöglichkeiten kommen daher in Frage: Spritzpulver (WP), emulgierbare Konzentrate (EC), wäßrige Dispersionen auf Öl- oder Wasserbasis (SC), Suspoemulsionen (SC), Stäubemittel (DP), Beizmittel, Granulate in Form von wasserdispergierbare Granulate (WG), ULV-Formulierungen, Mikrokapseln, Wachse oder Köder.They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options are therefore: wettable powder (WP), emulsifiable concentrates (EC), aqueous dispersions based on oil or water (SC), suspoemulsions (SC), dusts (DP), mordants, granules in the form of water-dispersible granules (WG) , ULV formulations, microcapsules, waxes or baits.
Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in: Winnacker-Küchler, "chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972 bis 73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.These individual formulation types are known in principle and are described, for example, in: Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972 to 73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben in: Watkins, "Handbook of Insecticide Dust Diluents and Carrier", 2nd Ed., Darland Books, caldwell N.J.; H. v. Olphen, "Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, N.Y.; Marschen, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's "Detergents and Emulsifiers Annual", MG Publ. Corp., Ridgewood N.Y.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflächenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carrier", 2nd Ed., Darland Books, caldwell NJ; H. v. Olphen, "Introduction to Clay Colloid Chemistry, 2nd Ed., J. Wiley & Sons, NY; Marschen," Solvents Guide ", 2nd Ed., Interscience, NY 1950; McCutcheon's" Detergents and Emulsifiers Annual ", MG Publ. Corp. , Ridgewood NY; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., NY 1964; Schönfeldt, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, Düngemitteln und/oder Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix.On the basis of these formulations, combinations with other pesticidally active substances, fertilizers and / or growth regulators can also be prepared, e.g. B. in the form of a finished formulation or as a tank mix.
Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdünnungs- oder Inertstoff noch Netzmittel, z. B. polyoxethylierte Alkylphenole, polyoxethyiierte Fettalkohole, Alkyl- oder Alkylphenol-sulfonate und Dispergiermittel, z. B. ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin- sulfonsaures Natrium oder auch oleylmethyltaurinsaures Natrium enthalten. Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel, z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen unter Zusatz von einem oder mehreren Emulgatoren hergestellt. Als Emulgatoren können beispielsweise verwendet werden:Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, are also a wetting agent, in addition to a diluent or inert substance. B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for. B. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleylmethyl tauric acid sodium. Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. The following can be used as emulsifiers:
Alkylarylsulfonsaure Calzium-Salze wie Ca- dodecylbenzolsulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester,Alkylarylsulfonic acid calcium salts such as cadodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters,
Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxld-Ethylenoxid- Sorbitanfettsäureester, Polyoxyethylensorbitan-Fettsäureester oder Polyoxethylensorbitester.Alkylaryl polyglycol ether, fatty alcohol polyglycol ether, propylene oxide-ethylene oxide-sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or polyoxethylene sorbitol ester.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z. B. Talkum, natürlichen Tonen wie Kaolin, Bentonit oder Pyropyllit oder Diatomeenerde. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite or pyropyllite or diatomaceous earth. Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates using adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten meistens 5 bis 20 Gew.-%. Bei Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden.In wettable powders, the active ingredient concentration is e.g. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20% by weight. In the case of granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which compound is liquid or solid and which granulation aids, fillers etc. are used.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Lösungsmittel, Füll- oder Trägerstoffe.In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers.
Zur Anwendung werden die in handelsüblicher Form vorliegenden Konzentrate gegebenenfalls in üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und teilweise auch bei Mikrogranulaten mittels Wasser.For use, the concentrates present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with microgranules using water.
Staubförmige und granulierte Zubereitungen sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt. Mit den äußeren Bedingen wie Temperatur, Feuchtigkeit u. a. variiert die erforderliche Aufwandmenge. Sie kann innerhalb weiter Grenzen schwanken, z. B. zwischen 0,005 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,01 und 5 kg/ha.Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use. The application rate required varies with the external conditions such as temperature, humidity and others. It can fluctuate within wide limits, e.g. B. between 0.005 and 10.0 kg / ha or more of active substance, but it is preferably between 0.01 and 5 kg / ha.
Die erfindungsgemäßen Wirkstoffe können in ihren handelsüblichen Formulierungen entweder allein oder in Kombination mit weiteren, literaturbekannten Fungiziden angewendet werden.The active compounds according to the invention can be used in their commercially available formulations either alone or in combination with other fungicides known from the literature.
Als literaturbekannte Fungizide, die erfindungsgemäß mit den Verbindungen der Formel 5 kombiniert werden können, sind z. B. folgende Produkte zu nennen: Aldimorph, Andoprim, Anilazine, BAS 480F, BAS 490F, Benalaxyl, Benodanil, Benomyl, Binapacryl, Bitertanol, Bromuconazol, Buthiobate, Captafol, Captan, Carbendazim, Carboxin, CGA 173506, Chlobenzthiazone, Chlorthalonil, Cymoxanil, Cyproconazole, Cyprofuram, Dichlofluanid, Dichlomezin, Diclobutrazol, Diethofencarb, Difenconazol (CGA 169374), Difluconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Dithianon, Dodemorph, Dodine, Edifenfos, Ethirimol, Etridiazol, Fenarimol, Fenfuram, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetate, Fentinhydroxide, Ferimzone (TF164), Fluazinam, Fluobenzimine, Fluquinconazole, Fluorimide, Flusilazole, FlutolaniH Flutriafol, Folpet, Fosetylaluminium, Fuberidazole, Fulsulfamide (MT-F651 ), Furalaxyl, Furconazol, Furmecyclox, Guazatine, Hexaconazole, ICI ASS 04, Imazalil, Imiben-Conazole, Iprobenfos, Iprodione, Isoprothiolane, KNF 317, Kupferverbindungen wie Cu-oxychlorid, Oxine-Cu, Cu-oxide, Mancozeb, Maneb, Mepanipyrim (KIF 3535), Metconazol, Mepronil, Metalaxyl, Methasulfocarb, Methfuroxam, MON 24000, Myclobutanil, Nabam, Nitrothalidopropyl, Nuarimol, Ofurace, Oxadixyl, Oxycarboxin, Penconazol, Pencycuron, PP 969, Probenazole, Propineb, Prochloraz, Procymidon, Propamocarb, Propiconazol, Prothiocarb, Pyracarbolid, Pyrazophos, Pyrifenox, Pyroquilon,' Rabenzazole, RH7592, Schwefel, Tebuconazole, TF 167, Thiabendazole, Thicyofen, Thiophanatemethyl, Thiram, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Tricyclazole, Tridemorph, Triflumizol, Triforine, Validamycin, Vinchlozolin, XRD 563, Zineb, Natriumdodecylsulfonate, Natriumdodecylsulfat, Natrium-C13/C15-alkoholethersulfonat, Natriumcetostearylphosphatester, Dioctyl-natrium-sulfosuccinat, Natrium- isopropylnaphthalenesulfonat, Natrium-methylenebisnaphthalenesulfonat, Cetyltrimethyl-ammoniumchlorid, Salze von langkettigen primären, sekundären oder tertiären Aminen, Alkyl-propyleneamine, Lauryl-pyrimidiniumbromid, ethoxilierte quarternierte Fettamine, Alkyl-dimethyl-benzyl-ammoniumchlorid und 1 -Hydroxyethyl-2-alkylimidazolin.As fungicides known in the literature, which can be combined according to the invention with the compounds of formula 5, z. B. to name the following products: Aldimorph, Andoprim, Anilazine, BAS 480F, BAS 490F, Benalaxyl, Benodanil, Benomyl, Binapacryl, Bitertanol, Bromuconazol, Buthiobate, Captafol, Captan, Carbendazim, Carboxin, CGA 173506, Chlobenzthiazone, Chlortoxanonilil cyproconazole, cyprofuram, dichlofluanid, Dichlomezin, diclobutrazol, diethofencarb, difenconazole (CGA 169374), Difluconazole, dimethirimol, dimethomorph, diniconazole, dinocap, dithianon, dodemorph, dodine, Edifenfos, ethirimol, etridiazole, fenarimol, fenfuram, fenpiclonil, fenpropidin, fenpropimorph, Fentin Acetate, Fentin Hydroxide, Ferimzone (TF164), Fluazinam, Fluobenzimine, Fluquinconazole, Fluorimide, Flusilazole, FlutolaniH Flutriafol, Folpet, Fosetylaluminium, Fuberidazole, Fulsulfamide (MT-F651), Furalaxazazazolazole, Furconazolonazole, Furconazoxololazole, Furconazoxololazole, Furconazoxololazole, Furconazoxololazole, Furconazoxololazole, Furconazoxalone, Furconazoxalone, Furconazoxalone, Furconazolone, Furconazoxalone, , Imiben-Conazole, Iprobefos, Iprodione, Isoprothiolane, KNF 317, copper compounds such as Cu oxychloride, Oxine-Cu, Cu-oxide, Mancozeb, Maneb, Mepa nipyrim (KIF 3535), metconazole, mepronil, metalaxyl, methasulfocarb, methfuroxam, MON 24000, myclobutanil, nabam, nitrothalidopropyl, nuarimol, ofurace, oxadixyl, oxycarboxin, penconazole, pencycuron, prop, 96am, prozamone, prozazolone, probazazole, prozazole propiconazole, Prothiocarb, Pyracarbolid, pyrazophos, pyrifenox, pyroquilon, 'Rabenzazole, RH7592, sulfur, tebuconazole, TF 167, thiabendazole, Thicyofen, thiophanate-methyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Tricyclazole, tridemorph, triflumizole, , Validamycin, vinchlozoline, XRD 563, isopropylnaphthalenesulfonat triforine zineb, sodium dodecylsulfonates, sodium dodecyl sulfate, sodium C13 / C15-alkoholethersulfonat, Natriumcetostearylphosphatester, dioctyl sodium sulfosuccinate, sodium, sodium methylenebisnaphthalenesulfonat, cetyl trimethyl ammonium chloride, salts of primary long-chain, secondary or tertiary amines, alkyl propylene amines, lauryl pyrimidinium bromide, ethoxylated quaternized fatty amines, alkyl dimethyl benzyl ammonium chloride and 1-hydroxyethyl-2-alkyl imidazoline.
Die oben genannten Kombinationspartner stellen bekannte Wirkstoffe dar, die zum großen Teil in Ch.R Worthing, U.S.B. Walker, The Pesticide Manual, 7. Auflage (1983), British Crop Protection Council beschrieben sind.The above-mentioned combination partners are known active ingredients, which are largely in Ch.R Worthing, U.S.B. Walker, The Pesticide Manual, 7th edition (1983), British Crop Protection Council.
Darüber hinaus kann der erfindungsgemäße Wirkstoff in seinen handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischung mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Akariziden, Nematiziden oder Herbiziden vorliegen. Zu den Insektiziden zählen beispielsweise Phosphorsäureester, Carbamate, Carbonsäureester, Formamidine, Zinnverbindungen, durch Mikroorganismen hergestellte Stoffe u. a. Bevorzugte Mischungspartner sind:In addition, the active ingredient according to the invention can be present in its commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, nematicides or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms and the like. a. Preferred mix partners are:
1 . Aus der Gruppe der Phosphorverbindungen1 . From the group of phosphorus compounds
Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, O,O-1 ,2,2,2-tetrachlorethylphosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isozophos, Isothioate, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidation, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion.Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfone, Dialifos, Diazinon, Dichlorvos, O. Dicrotoph , O-1, 2,2,2-tetrachloroethylphosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isozophos, Isioophos, Isio Isoxathion, Malathion, Methacrifos, Methamidophos, Methidation, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphosphos, Sulprofos, Temephos, Terblorososon, Trerblorosos, Terbufosos, T Vamidothione.
2. Aus der Gruppe der Carbamate2. From the group of carbamates
Aldicarb, 2-sec-Butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, Isoprocarb, Methomyl, 5-Methyl-m-cumenyl-butyryl- (methyl)carbamate, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Ethyl 4,6,9-triaza-4-benzyl-6,10-dimethyl-8-oxa-7-oxo-5, 1 1-dithia-9-dodecenoate (OK 135), 1 -Methylthio-(ethylideneamino)-N- methyl-N-(morpholinothio)-carbamate (UC 51717).Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cumenyl-butyryl- (methyl) carbamate, oxamyl, pirimicarb Thiodicarb, Thiofanox, ethyl 4,6,9-triaza-4-benzyl-6,10-dimethyl-8-oxa-7-oxo-5, 1 1-dithia-9-dodecenoate (OK 135), 1-methylthio- (ethylideneamino) -N-methyl-N- (morpholinothio) carbamate (UC 51717).
3. Aus der Gruppe der Carbonsäureester3. From the group of carboxylic acid esters
Allethrin, Alphametrin, 5-Benzyl-3-furylmethyl-(E)-(1 R)-cis- 2,2-di-methyl-3-(2-oxothiolan-3-ylidenemethyl)-cyclopropane-carboxylate, Bioallethrin, Bioallethrin((S)-cyclopentenylisomer), Bioresmethrin, Biphenate, (RS)-l-Cyano-1 -(6-phenoxy-2-pyridyl)-methyl-(1 RS)-trans-3- (4-tert. butylphenyl)-2,2-di-methylcyclopropanecarboxylate (NCI 85193), Cycloprothrin, Cyhalothrin, Cypermethrin, Cyphenothrin, Deltamethrin, Empenthrin, Esfenvalerate, Fenfluthrin, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (D-isomer), Permethrin, Pheothrin ((R)-Isomer), d-Prallethrin, Pyrethrine (natürliche Produkte), Resmethrin, Tefluthrin, Tetramethrin, Tralomethrin.Allethrin, alphametrin, 5-benzyl-3-furylmethyl- (E) - (1 R) -cis- 2,2-di-methyl-3- (2-oxothiolan-3-ylidenemethyl) -cyclopropane-carboxylate, bioallethrin, bioallethrin ((S) -cyclopentenyl isomer), bioresmethrin, biphenates, (RS) -l-cyano-1 - (6-phenoxy-2-pyridyl) -methyl- (1 RS) -trans-3- (4-tert.butylphenyl) -2,2-dimethylcyclopropane decarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin (ishrin, phrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin, (ishrin ) -Isomer), d-prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin.
4. Aus der Gruppe der Amidine Amitraz, Chlordimeform4. From the group of the amidines Amitraz, chlorodime form
5. Aus der Gruppe der Zinnverbindungen Cyhexatin, Fenbutatinoxide 6. Sonstige5. From the group of tin compounds cyhexatin, fenbutatin oxide 6. Other
Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2-(4- (Chlorphenyl)-4,5-diphenylthiophen (UBI-T 930), Chlorfentezine, Cyclopropancarbonsäure-(2-naphthylmethyl)ester (Ro12-0470), Cyromazin, N-(3,5-Dichlor-4-(1 ,1 ,2,3,3,3-hexafluor-1-propyloxy) phenyl)carbamoyl)-2-chlorbenzcarboximidsäureethylester, DDT, Dicofol, N-(N-(3,5-Di-chlor-4-(1 ,1 ,2,2-tetrafluorethoxy)phenylamino)carbonyl)-2,6- difluorbenzamid (XRD 473), Diflubenzuron, N-(2,3-Dihydro-3-methyl-1 ,3- thiazol-2-ylidene)-2,4-xylidine, Dinobuton, Dinocap, Endosulfan, Ethofenprox, (4-Ethoxyphenyl) (dimethyl) (3-(3-phenoxyphenyl)propyl)- silan, (4-Ethoxyphenyl) (3-(4-fluoro-3-phenoxyphenyl)propyl)dimethylsilan, Fenoxycarb, 2-Fluoro-5-(4-(4-ethoxyphenyl-4-methyl- 1-pentyl)diphenylether (MTI 800), Granulöse- und Kernpolyederviren, Fenthiocarb, Flubenzimine, Flucycloxuron, Flufenoxuron, Gamma-HCH, Hexythiazox, Hydramechylnon (AG 217300), Ivermectin, 2-Nitromethyl- 4,5-dihydro-6H-thiazin (SD 52618), 2-Nitromethyl-3,4-dihydrothiazol (SD 35651 ), 2-Nitromethylene-1 ,2-thiazinan-3-ylcarbamaldehyde (WL 108477), Propargite, Teflubenzuron, Tetradifon, Tetrasul, Thiocyclam, Triflumuron.Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) -4,5-diphenylthiophene (UBI-T 930), Chlorofentezine, Cyclopropancarbthylm- (2-naphthenyl ) ester (Ro12-0470), cyromazine, N- (3,5-dichloro-4- (1, 1, 2,3,3,3-hexafluoro-1-propyloxy) phenyl) carbamoyl) -2-chlorobenzcarboximidic acid ethyl ester, DDT , Dicofol, N- (N- (3,5-di-chloro-4- (1,1,2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron, N- ( 2,3-dihydro-3-methyl-1,3-thiazol-2-ylidenes) -2,4-xylidines, dinobutone, dinocap, endosulfan, ethofenprox, (4-ethoxyphenyl) (dimethyl) (3- (3-phenoxyphenyl ) propyl) silane, (4-ethoxyphenyl) (3- (4-fluoro-3-phenoxyphenyl) propyl) dimethylsilane, fenoxycarb, 2-fluoro-5- (4- (4-ethoxyphenyl-4-methyl-1-pentyl) ) diphenyl ether (MTI 800), granular and nuclear polyhedron viruses, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexythiazox, hydramechylnon (AG 217300), iverm ectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1, 2-thiazinan-3-ylcarbamaldehydes (WL 108477 ), Propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, triflumuron.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereitetenThe active substance content of those prepared from the commercially available formulations
Anwendungsformen kann in weiten Bereichen variieren, dieApplication forms can vary widely
Wirkstoffkonzentration der Anwendungsformen kann von 0,0001 bis zuDrug concentration of use forms can range from 0.0001 to
95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,001 und 1 Gew.-% liegen. Die95% by weight of active ingredient, preferably between 0.001 and 1% by weight. The
Anwendung geschieht in einer den Anwendungsformen angepaßten üblichenApplication takes place in a customary manner adapted to the application forms
Weise.Wise.
Die Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit und günstiger Warmblütertoxizität zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren, Helminthen und Mollusken, ganz besonders bevorzugt zur Bekämpfung von Insekten und Spinnentieren, die in der Landwirtschaft, bei der Tierzucht, in Forsten, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie sind gegen normal sensible und resistente Arten sowie alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören:With good plant tolerance and favorable toxicity to warm-blooded animals, the active substances are suitable for controlling animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids used in agriculture animal breeding, in forests, in the protection of stocks and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as all or individual stages of development. The pests mentioned above include:
Aus der Ordnung der Acarina z. B. Acarus siro, Agras spp., Omithodoros spp.,From the order of Acarina z. B. Acarus siro, Agras spp., Omithodoros spp.,
Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp.,
Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa,
Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp.,Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp.,
Eutetranychus spp.Eutetranychus spp.
Aus der Ordnung der Isopoda, z. B. Oniscus asellus, Armadillidium vulgäre,From the order of the Isopoda, e.g. B. Oniscus asellus, Armadillidium vulgare,
Porcellio scaber.Porcellio scaber.
Aus der Ordnung der Diplopoda z. B. Blaniulus guttulatus.From the order of the Diplopoda z. B. Blaniulus guttulatus.
Aus der Ordnung der Chilopoda z. B. Geophilus carpophagus, Scutigera spp.From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spp.
Aus der Ordnung der Symphyla z. B. Scutigerella immaculata.From the order of the Symphyla z. B. Scutigerella immaculata.
Aus der Ordung der Thysanura z. B. Lepisma saccharina.From the order of Thysanura z. B. Lepisma saccharina.
Aus der Ordnung der Collembola z. B. Onychiurus armatus.From the order of the Collembola z. B. Onychiurus armatus.
Aus der Ordnung der Orthoptera z. B. Blatta orientalis,From the order of Orthoptera z. B. Blatta orientalis,
Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis,
Schistocerca gregaria.Schistocerca gregaria.
Aus der Ordnung des Isoptera z. B. Reticulitermes spp..From the order of the Isoptera z. B. Reticulitermes spp ..
Aus der Ordnung der Anoplura z. B. Phylloxera vastatrix, Pemphigus spp.,From the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp.,
Pediculus humanus corporis, Haematopinus spp., Linognathus spp..Pediculus humanus corporis, Haematopinus spp., Linognathus spp ..
Aus der Ordnung der Mallophaga z. B. Trichodectes spp., Damalinea spp..From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp ..
Aus der Ordnung der Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.
Aus der Ordnung der Heteroptera z. B. Eurygaster spp., Dysdercus intermedius,From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius,
Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp..Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp ..
Aus der Ordnung der Homoptera z. B. Aleurodes brassicae, Bemisia tabaci,From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci,
Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. Aus der Ordnung der Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehnieila, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus sp aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp. From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppa, Fpp , Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehnieilana, Caulioacuaiaellaa, Galleria mellellaella Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.
Aus der Ordnung der Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonumus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica. Aus der Ordnung der Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp..From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Spp Psylloides chrysocephala, Epilachna varivestis, Atomaria., Oryzaephilus surinamensis spp, Anthonumus., Sitophilus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica. From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp ..
Aus der Ordnung der Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.
Aus der Ordnung der Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.. Aus der Ordnung der Arachnida z. B. Scorpio maurus, Latrodectus mactans. Aus der Klasse der Helminthen z. B. Haemonchus, Trichostrongulus, Ostertagia. Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris und Heterakis sowie Fasciola und pflanzenschädigende Nematoden z. B. solche der Gattungen Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus und Xiphinema.From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp .. From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans. From the class of the Helminth z. B. Haemonchus, Trichostrongulus, Ostertagia. Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola and plant-damaging nematodes z. B. those of the genera Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus and Xiphinema.
Aus der Klasse der Gastropoda z. B. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp.. Aus der Klasse der Bivalva z. B. Dreissena spp..From the class of the Gastropoda z. B. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp .. From the class of the Bivalva z. B. Dreissena spp ..
Die Erfindung betrifft auch insektizide und akarizide Mittel, die die Verbindungen der Formel I neben geeigneten Formulierungshilfsmitteln enthalten.The invention also relates to insecticidal and acaricidal compositions which comprise the compounds of the formula I in addition to suitable formulation auxiliaries.
Die erfindungsgemäßen Mittel enthalten die Wirkstoffe der Formeln I im allgemeinen zu 1 bis 95 Gew.-%.The agents according to the invention generally contain 1 to 95% by weight of the active compounds of the formulas I.
Sie können auf verschiedene Art formuliert werden, je nachdem wie es durch die biologischen und/oder chemisch-physikalischen Parameter vorgegeben ist. Als Formulierungsmöglichkeiten kommen daher infrage: Spritzpulver (WP), emulgierbare Konzentrate (EC), wäßrige Lösungen (SC), Emulsionen, versprühbare Lösungen, Dispersionen auf Öl- oder Wasserbasis (SC), Suspoemulsionen (SC), Stäubemittel (DP), Beizmittel, Granulate in Form von Mikro-, Sprüh-, Aufzugs- und Adsorptionsgranulaten, wasserdispergierbare Granulate (WG), ULV-Formulierungen, Mikrokapseln, Wachse oder Köder. Diese einzelnen Formulierungstypen sind im Prinzip bekannt und werden beispielsweise beschrieben in:They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulation options are therefore: wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SC), emulsions, sprayable solutions, dispersions based on oil or water (SC), suspoemulsions (SC), dusts (DP), mordants, Granules in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits. These individual types of formulation are known in principle and are described, for example, in:
Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker N.Y., 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.
Die notwendigen Formulierungshilfsmittel wie Inertmaterialien, Tenside, Lösungsmittel und weitere Zusatzstoffe sind ebenfalls bekannt und werden beispielsweise beschrieben 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.; Marschen, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; 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", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler, "Chemische Technologie", Band 7, C. Hauser Verlag München, 4. Aufl. 1986.The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also 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 .; March, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; 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, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1976; Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986.
Auf der Basis dieser Formulierungen lassen sich auch Kombinationen mit anderen pestizid wirksamen Stoffen, Düngemitteln und/oder Wachstumsregulatoren herstellen, z. B. in Form einer Fertigformulierung oder als Tankmix. Spritzpulver sind in Wasser gleichmäßig dispergierbare Präparate, die neben dem Wirkstoff außer einem Verdunnungs- oder Inertstoff noch Netzmittel, z. B. polyoxethylierte Alkylphenole, polyoxethylierte Fettalkohole, Alkyl- oder Alkylphenol-sulfonate und Dispergiermittel, z. B. ligninsulfonsaures Natrium, 2,2'-dinaphthylmethan-6,6'-disulfonsaures Natrium, dibutylnaphthalin- sulfonsaures Natrium oder auch oleylmethyltaurinsaures Natrium enthalten. Emulgierbare Konzentrate werden durch Auflösen des Wirkstoffes in einem organischen Lösungsmittel, z. B. Butanol, Cyclohexanon, Dimethylformamid, Xylol oder auch höhersiedenden Aromaten oder Kohlenwasserstoffen unter Zusatz von einem oder mehreren Emulgatoren hergestellt. Als Emulgatoren können beispielsweise verwendet werden: Alkylarylsulfonsaure Calcium-Salze wie Ca-dodecylbenzol-sulfonat oder nichtionische Emulgatoren wie Fettsäurepolyglykolester, Alkylarylpolyglykolether, Fettalkoholpolyglykolether, Propylenoxid-Ethylenoxid-Kondensationsprodukte, Alkylpoiyether, Sorbitanfettsäureester, Polyoxyethylensorbitan-Fettsäureester oder Polyoxethylensorbitester.On the basis of these formulations, combinations with other pesticidally active substances, fertilizers and / or growth regulators can also be prepared, e.g. B. in the form of a finished formulation or as a tank mix. Spray powders are preparations which are uniformly dispersible in water. B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, for. B. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonic acid sodium or oleylmethyl tauric acid sodium. Emulsifiable concentrates are obtained by dissolving the active ingredient in an organic solvent, e.g. B. butanol, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. As emulsifiers can be used, for example: alkylarylsulfonic acid calcium salts such as Ca-dodecylbenzene sulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl poiyethers, sorbitan fatty acid esters, polyoxyethylene ester or polyoxyethylene sorbitan polyethylenesorbitan-polyoxyethylene sorbitan or fatty acid polyoxyethylene sorbitan or fatty acid polyoxyethylene sorboxes.
Stäubemittel erhält man durch Vermählen des Wirkstoffes mit fein verteilten festen Stoffen, z. B. Talkum, natürlichen Tonen wie Kaolin, Bentonit, Pyrophyllit oder Diatomeenerde. Granulate können entweder durch Verdüsen des Wirkstoffes auf adsorptionsfähiges, granuliertes Inertmaterial hergestellt werden oder durch Aufbringen von Wirkstoffkonzentraten mittels Klebemitteln, z. B. Polyvinylalkohol, polyacrylsaurem Natrium oder auch Mineralölen, auf die Oberfläche von Trägerstoffen wie Sand, Kaolinite oder von granuliertem Inertmaterial. Auch können geeignete Wirkstoffe in der für die Herstellung von Düngemittelgranulaten üblichen Weise - gewünschtenfalls in Mischung mit Düngemitteln - granuliert werden.Dusts are obtained by grinding the active ingredient with finely divided solid substances, e.g. B. talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth. Granules can either be produced by spraying the active ingredient onto adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. As polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.
In Spritzpulvern beträgt die Wirkstoffkonzentration z. B. etwa 10 bis 90 Gew.-%, der Rest zu 100 Gew.-% besteht aus üblichen Formulierungsbestandteilen. Bei emulgierbaren Konzentraten kann die Wirkstoffkonzentration etwa 5 bis 80 Gew.-% betragen. Staubförmige Formulierungen enthalten meistens 5 bis 20 Gew.-% an Wirkstoff, versprühbare Lösungen etwa 2 bis 20 Gew.-%. Bei Granulaten hängt der Wirkstoffgehalt zum Teil davon ab, ob die wirksame Verbindung flüssig oder fest vorliegt und welche Granulierhilfsmittel, Füllstoffe usw. verwendet werden.In wettable powders, the active ingredient concentration is e.g. B. about 10 to 90 wt .-%, the rest of 100 wt .-% consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance concentration can be approximately 5 to 80% by weight. Dust-like formulations usually contain 5 to 20 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%. In the case of granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, fillers, etc. are used.
Daneben enthalten die genannten Wirkstofformulierungen gegebenenfalls die jeweils üblichen Haft-, Netz-, Dispergier-, Emulgier-, Penetrations-, Lösungsmittel, Füll- oder Trägerstoffe. Zur Anwendung werden die in handelsüblicher Form vorliegenden Konzentrate gegebenenfalls in üblicher Weise verdünnt, z. B. bei Spritzpulvern, emulgierbaren Konzentraten, Dispersionen und teilweise auch bei Mikrogranulaten mittels Wasser. Staubförmige und granulierte Zubereitungen sowie versprühbare Lösungen werden vor der Anwendung üblicherweise nicht mehr mit weiteren inerten Stoffen verdünnt.In addition, the active ingredient formulations mentioned may contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers or carriers. For use, the concentrates present in the commercial form are optionally diluted in the customary manner, for. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also with microgranules using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.
Mit den äußeren Bedingungen wie Temperatur, Feuchtigkeit u.a. variiert die erforderliche Aufwandmenge. Sie kann innerhalb weiter Grenzen schwanken, z. B. zwischen 0,001 und 10,0 kg/ha oder mehr Aktivsubstanz, vorzugsweise liegt sie jedoch zwischen 0,005 und 5 kg/ha.With the external conditions such as temperature, humidity, etc. the required application rate varies. It can fluctuate within wide limits, e.g. B. between 0.001 and 10.0 kg / ha or more of active substance, but is preferably between 0.005 and 5 kg / ha.
Die erfindungsgemäßen Wirkstoffe können in ihren handelsüblichen Formulierungen sowie in den aus diesen Formulierungen bereiteten Anwendungsformen in Mischungen mit anderen Wirkstoffen, wie Insektiziden, Lockstoffen, Sterilantien, Akariziden, Nematiziden, Fungiziden, wachstumsregulierenden Stoffen oder Herbiziden vorliegen.The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides.
Zu den Schädlingsbekämpfungsmitteln zählen beispielsweise Phosphorsäureester, Carbamate, Carbonsäureester, Formamidine, Zinnverbindungen, durch Mikroorganismen hergestellte Stoffe u.a.. Bevorzugte Mischungspartner sindThe pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds, substances produced by microorganisms, etc. Preferred mixing partners are
1. aus der Gruppe der Phosphorverbindungen1. from the group of phosphorus compounds
Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulphone, Dialifos, Diazinon, Dichlorvos, Dicrotophos, O,O-1 ,2,2,2-tetrachlorethylρhosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isazophos, Isothioate, Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion;Acephate, Azamethiphos, Azinphos-ethyl, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulphone, Dialifos, Diazinon, Dichlorvos, Dicrotoph O, O-1, 2,2,2-tetrachloroethylphosphorothioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isazophos, Isazophos, Isazophos , Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxos, Piroxim, Piroxim, Piroxim, Piroxim, Piroxim -methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion;
2. aus der Gruppe der Carbamate2. from the group of carbamates
Aldicarb, 2-sec-Butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, Isoprocarb, Methomyl, 5-Methyl-m-cu-menylbutyryl(methyl)carbamate, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Ethyl 4,6,9-triaza-4-benzyl-6, 10-dimethyl-8- oxa7-oxo-5,1 1 -dithia-9-dodecenoate (OK 135), I-Methylthio(ethylideneamino)- N-methyl-N-(morpholinothio)carbamate (UC 51717);Aldicarb, 2-sec-butylphenylmethylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, isoprocarb, methomyl, 5-methyl-m-cu-menylbutyryl (methyl) carbamate, oxamylarboxuricarboxicarboxir , Thiofanox, ethyl 4,6,9-triaza-4-benzyl-6, 10-dimethyl-8-oxa7-oxo-5.1 1 -dithia-9-dodecenoate (OK 135), I-methylthio (ethylideneamino) - N-methyl-N- (morpholinothio) carbamate (UC 51717);
3. aus der Gruppe der Carbonsäureester3. from the group of carboxylic acid esters
Allethrin, Alphametrin, 5-Benzyl-3-furylmethyl-(E)-(1 R)-cis-2,2-di-methyl- 3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, Bioallethrin, Bioallethrin((S)-cyclopentylisomer), Bioresmethrin, Biphenate, (RS)-1-Cyano-1-(6- phenoxy-2-pyridyl)methyl-(1 RS)-trans-3-(4-tert.-butylphenyl)-2,2- dimethylcyclopropanecarboxylate (NCI 85193), Cycloprothrin, Cyhalothrin, Cypermethrin, Cyphenothrin, Deltamethrin, Empenthrin, Esfenvalerate, Fenfluthrin, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, Fluvalinate (D-isomer), Permethrin, Pheothrin ((R)-Isomer), d-Pralethrin, Pyrethrine (natürliche Produkte), Resmethrin, Tefluthrin, Tetramethrin, Tralomethrin;Allethrin, alphametrin, 5-benzyl-3-furylmethyl- (E) - (1 R) -cis-2,2-di-methyl-3- (2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, bioallethrin, bioallethrin ((p ) -cyclopentyl isomer), bioresmethrin, biphenates, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1 RS) -trans-3- (4-tert-butylphenyl) -2, 2- dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, Esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, isomerin, (R) -phrinin (D) d-pralethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin;
4. aus der Gruppe der Amidine Amitraz, Chlordimeform; 5. aus der Gruppe der Zinnverbindungen Cyhexatin, Fenbutatinoxide;4. from the group of the amidines amitraz, chlorodime form; 5. from the group of tin compounds cyhexatin, fenbutatin oxide;
6. Sonstige6. Other
Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2-(4-(Chlorphenyl)-4,5-diphenylthiophen (UBI-T 930), Chlorfentezine, Cyclopropancarbonsäure-(2-naphthylmethyl)ester (Ro12-0470), Cyromazin, N-(3,5-Dichlor-4-( 1 , 1 , 2,3,3, 3-hexafluor-1 -propyloxy)phenyl)carbamoyl)-2- chlorbenzcarboximidsäureethylester, DDT, Dicofol, N-(N-(3,5-Di-chlor-4- (1 , 1 ,2,2-tetrafluorethoxy)phenylamino)carbonyl)-2,6-difluorbenzamid (XRD 473), Diflubenzuron, N-(2,3-Dihydro-3-methyl-1 ,3-thiazol-2-ylidene)-2,4-xylidine, Dinobuton, Dinocap, Endosulfan, Ethofenprox, (4-Ethoxyphenyl)(dimethyl)(3-(3- phenoxyphenyl)propyl)silan, (4-Ethoxyphenyl) (3-(4-fluoro- 3-phenoxyphenyl)propyl)dimethylsilan, Fenoxycarb, 2-Fluoro-5-(4- (4-ethoxyphenyl)-4-methyl-1 -pentyl)diphenylether (MTI 800), Granulöse- und Kernpolyederviren, Fenthiocarb, Flubenzimine, Flucycloxuron, Flufenoxuron, Gamma-HCH, Hexythiazox, Hydramechylnon (AC 217300), Ivermectin, 2-Nitromethyl-4,5-dihydro-6H-thiazin (SD 52618),Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4- (Chlorphenyl) -4,5-diphenylthiophene (UBI-T 930), Chlorofentezine, Cyclopropancarbthylm- (2-naphthenyl ) ester (Ro12-0470), cyromazine, N- (3,5-dichloro-4- (1, 1, 2,3,3, 3-hexafluoro-1-propyloxy) phenyl) carbamoyl) -2-chlorobenzcarboximidic acid ethyl ester, DDT , Dicofol, N- (N- (3,5-di-chloro-4- (1, 1, 2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron, N- ( 2,3-dihydro-3-methyl-1,3-thiazol-2-ylidenes) -2,4-xylidines, dinobutone, dinocap, endosulfan, ethofenprox, (4-ethoxyphenyl) (dimethyl) (3- (3-phenoxyphenyl ) propyl) silane, (4-ethoxyphenyl) (3- (4-fluoro-3-phenoxyphenyl) propyl) dimethylsilane, fenoxycarb, 2-fluoro-5- (4- (4-ethoxyphenyl) -4-methyl-1-pentyl ) diphenyl ether (MTI 800), granular and nuclear polyhedron viruses, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexythiazox, hydramechylnon (AC 217300), I vermectin, 2-nitromethyl-4,5-dihydro-6H-thiazine (SD 52618),
2-Nitromethyl-3,4-dihydrothiazol (SD 35651 ), 2-Nitromethylene-1 ,2-thiazinan-3- ylcarbamaldehyde (WL 108477), Propargite, Teflubenzuron, Tetradifon, Tetrasul, Thiocyclam, Triflumuron.2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1, 2-thiazinan-3-ylcarbamaldehyde (WL 108477), propargite, teflubenzuron, tetradifone, tetrasul, thiocyclam, triflumuron.
Der Wirkstoffgehalt der aus den handelsüblichen Formulierungen bereiteten Anwendungsformen kann von 0,00000001 bis zu 95 Gew.-% Wirkstoff, vorzugsweise zwischen 0,00001 und 1 Gew.-% liegen.The active substance content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise. Die erfindungsgemäßen Wirkstoffe eignen sich auch zur Bekämpfung von Endo- und Ektoparasiten auf dem veterinärmedizinischen Gebiet bzw. auf dem Gebiet der Tierhaltung.The application takes place in a customary manner adapted to the application forms. The active compounds according to the invention are also suitable for combating endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry.
Die Anwendung der erfindungsgemäßen Wirkstoffe geschieht hier in bekannter Weise wie durch orale Anwendung in Form von beispielsweise Tabletten, Kapseln, Tränken, Granulaten, durch dermale Anwendung in Form beispielsweise des Tauchens (Dippen), Sprühens (Sprayen), Aufgießen (pour-on and spot-on) und des Einpuderns sowie durch parenterale Anwendung in Form beispielsweise der Injektion.The active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form of, for example, dipping (dipping), spraying (spraying), pouring on (pour-on and spot) -on) and powdering and by parenteral use in the form of, for example, injection.
Die erfindungsgemäßen neuen Verbindungen der Formel I können demgemäß auch besonders vorteilhaft in der Viehhaltung (z. B. Rinder, Schafe, Schweine und Geflügel wie Hühner, Gänse usw.) eingesetzt werden. In einer bevorzugten Ausführungsform der Erfindung werden den Tieren die neuen Verbindungen, gegebenenfalls in geeigneten Formulierungen (vgl. oben) und gegebenenfalls mit dem Trinkwasser oder Futter oral verabreicht. Da eine Ausscheidung im Kot in wirksamer Weise erfolgt, läßt sich auf diese Weise sehr einfach die Entwicklung von Insekten im Kot der Tiere verhindern. Die jeweils geeigneten Dosierungen und Formulierungen sind insbesondere von der Art und dem Entwicklungsstadium der Nutztiere und auch vom Befallsdruck abhängig und lassen sich nach den üblichen Methoden leicht ermitteln und festlegen. Die neuen Verbindungen können bei Rindern z. B. in Dosierungen von 0,01 bis 1 mg/kg Körpergewicht eingesetzt werden.The novel compounds of the formula I according to the invention can accordingly also be used particularly advantageously in animal husbandry (for example cattle, sheep, pigs and poultry such as chickens, geese, etc.). In a preferred embodiment of the invention, the animals are given the new compounds, if appropriate in suitable formulations (see above) and if appropriate with the drinking water or feed orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way. The appropriate dosages and formulations depend in particular on the type and stage of development of the livestock and also on the infestation pressure and can be easily determined and determined using the usual methods. The new compounds in cattle z. B. in doses of 0.01 to 1 mg / kg body weight.
Die folgenden Beispiele dienen zur Erläuterung der Erfindung, ohne daß diese darauf beschränkt wäre. A. Chemische Beispiele:The following examples serve to illustrate the invention without being restricted thereto. A. Chemical examples:
Beispiel 1 4-O-Benzylhydroxylamino-3-methoxy-2-methoxymethylpyridinExample 1 4-O-Benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine
13 g 4-Chlor-3-methoxy-2-methoxymethylpyridin, 50 g Phenol und 30 g O-Benzylhydroxylamin werden 4 Stunden unter Stickstoff auf 1 15 bis 120°C erhitzt. Nach dem Abkühlen wird der Ansatz in eine Lösung von 32 g NaOH in 200 ml Wasser gegossen. Das Produkt wird mit Methylenchlorid extrahiert. Der nach dem Abdestillieren des Methylenchlorids und des überschüssigen O-Benzylhydroxylamins verbleibende Rückstand wird durch Säulenchromatographie an Kieselgel mit Ethylacetat gereinigt. 14 g = 74 %13 g of 4-chloro-3-methoxy-2-methoxymethylpyridine, 50 g of phenol and 30 g of O-benzylhydroxylamine are heated at 115 to 120 ° C. for 4 hours under nitrogen. After cooling, the mixture is poured into a solution of 32 g NaOH in 200 ml water. The product is extracted with methylene chloride. The residue remaining after distilling off the methylene chloride and the excess O-benzylhydroxylamine is purified by column chromatography on silica gel with ethyl acetate. 14 g = 74%
1H-HMR (100 MHz, CDCI3) = 8,2 (d, 1 H), 7,4 (s, 5H), 7,0 (d, 2H), 4,9 (s, 2H), 1 H-HMR (100 MHz, CDCI 3 ) = 8.2 (d, 1H), 7.4 (s, 5H), 7.0 (d, 2H), 4.9 (s, 2H),
4.5 (s, 2H), 3,7 (s, 3H), 3,4 (s, 3H) ppm4.5 (s, 2H), 3.7 (s, 3H), 3.4 (s, 3H) ppm
Beispiel 2Example 2
4-[O-Benzyl-N-(4-cis-tert.-butylcyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethylpyridin4- [O-benzyl-N- (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine
Zu 2,8 g Kalium-tert.-butylat in 10 ml absolutem DMSO tropft man unter Stickstoff die Lösung von 5,4 g 4-O-Benzylhydroxylamino- 3-methoxy-2-methoxymethylpyridin in 10 ml absolutes Tetrahydrofuran. Anschließend tropft man die Lösung von 8,2 g 4-trans-tert.-Butyl-O- tosylcyclohexanol in 15 ml absolutes THF zu und rührt sie 14 Stunden bei 50°C. Danach wird das THF im Vakuum abdestilliert und der Rückstand mit Wasser und Methylenchlorid aufgearbeitet. Die Methylenchloridphase wird über Kieselgel gereinigt. Ausbeute: 3,5 g = 43 %.The solution of 5.4 g of 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine in 10 ml of absolute tetrahydrofuran is added dropwise under nitrogen to 2.8 g of potassium tert-butoxide in 10 ml of absolute DMSO. The solution of 8.2 g of 4-trans-tert-butyl-o-tosylcyclohexanol in 15 ml of absolute THF is then added dropwise and the mixture is stirred at 50 ° C. for 14 hours. The THF is then distilled off in vacuo and the residue is worked up with water and methylene chloride. The methylene chloride phase is purified over silica gel. Yield: 3.5 g = 43%.
1H-NMR (100 MHz, CDCI3) = 8,3 (d, 1 H), 7,3 (d, 1 H), 7,3 (s, 5H), 4,7 (s, 2H), 1 H-NMR (100 MHz, CDCI 3 ) = 8.3 (d, 1 H), 7.3 (d, 1 H), 7.3 (s, 5H), 4.7 (s, 2H),
4.6 (s, 2H), 3,9 (s, 3H), 3,7 (m, 1 H), 3,5 (s, 3H), 0,9 bis 2,1 (m, 9H), 0,8 (s, 9H) ppm Beispiel 34.6 (s, 2H), 3.9 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 0.9 to 2.1 (m, 9H), 0, 8 (s, 9H) ppm Example 3
4-[O-Benzyl-N-(4-cis-( 1 ,1 ,3, 3-tetramethylbutyl)-cyclohexyl]-hydroxylamino-3- methoxy-2-methoxymethylpyridin4- [O-benzyl-N- (4-cis- (1, 1, 3, 3-tetramethylbutyl) cyclohexyl] hydroxylamino-3-methoxy-2-methoxymethylpyridine
wurde dargestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- methoxymethylpyridin und trans-4-( 1 ,1 ,3, 3-TetramethylbutyD- O-tosylcyclohexanol. Ausbeute: 26 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine and trans-4- (1, 1, 3, 3-tetramethylbutyD-O-tosylcyclohexanol. Yield: 26%
1H-NMR (100 MHz, CDCI3) = 8,3 (d, 1 H), 7,4 (d, 1 H), 7,3 (s, 5H), 4,7 (s, 2H), 4,6 (s, 2H), 3,9 (s, 3H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,4 bis 2,1 (m, 9H), 0,9 und 1 ,0 (2s, 15H) ppm 1 H-NMR (100 MHz, CDCI 3 ) = 8.3 (d, 1 H), 7.4 (d, 1 H), 7.3 (s, 5H), 4.7 (s, 2H), 4.6 (s, 2H), 3.9 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 1.4 to 2.1 (m, 9H), 0.9 and 1.0 (2s, 15H) ppm
Beispiel 4Example 4
4-[O-Benzyl-N-(4-cis-tert.-amylcyclohexyl)]-hydroxylamino-3-methoxy-2- methoxy-methylpyridin-Hydrochlorid4- [O-benzyl-N- (4-cis-tert-amylcyclohexyl)] - hydroxylamino-3-methoxy-2-methoxy-methylpyridine hydrochloride
wurde dargestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy- 2-methoxymethylpyridin und trans-4-tert.-amyl-O-tosylcyclohexan. Ausbeute: 35 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine and trans-4-tert-amyl-O-tosylcyclohexane. Yield: 35%
1H-NMR (100 MHz, CDCI3) = 8,3 (t, 1 H), 7,6 (d, 1 H), 7,4 (s, 5H), 5,4 (m, 1 H), 4,8 (s, 4H), 4,4 (m, 1 H), 3,8 (s, 3H), 3,6 (s, 3H), 1 ,0 bis 2,1 (m, 9H), 0,8 (s, t, 9H) ppm 1 H NMR (100 MHz, CDCI 3 ) = 8.3 (t, 1 H), 7.6 (d, 1 H), 7.4 (s, 5H), 5.4 (m, 1 H) , 4.8 (s, 4H), 4.4 (m, 1H), 3.8 (s, 3H), 3.6 (s, 3H), 1.0 to 2.1 (m, 9H) , 0.8 (s, t, 9H) ppm
Beispiel 5Example 5
4-[4-cis-( 1 , 1 ,3, 3-Tetramethylbutyl)-cyclohexylamino]-3-methoxy-2-methoxy- methylpyridin-Hydrochlorid4- [4-cis- (1, 1, 3, 3-tetramethylbutyl) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine hydrochloride
1 ,2 g 4-[O-Benzyl-N-(4-cis-(1 ,1 ,3,3-Tetramethylbutyl))-cyciohexyl]- hydroxylamino-3-methoxy-2-methoxymethylpyridin werden in 20 ml Methanol mit 0,5 g Raney-Nickel bei Normaldruck bis zum Ende der Wasserstoffaufnahme hydriert. Die filtrierte Lösung wird eingeengt im Vakuum und der Rückstand in Hexan gelöst. Auf Zugabe von etherischer HCI fällt das Hydrochlorid aus. Es wird abgesaugt, mit Ether gewaschen und getrocknet. 0,8 g = 85 %1.2 g of 4- [O-benzyl-N- (4-cis- (1,1,3,3-tetramethylbutyl)) - cyciohexyl] - hydroxylamino-3-methoxy-2-methoxymethylpyridine are dissolved in 20 ml of methanol with 0 , 5 g of Raney nickel are hydrogenated at normal pressure until the end of the hydrogen uptake. The filtered solution is concentrated in vacuo and the residue in Hexane dissolved. The hydrochloride precipitates on addition of ethereal HCl. It is filtered off, washed with ether and dried. 0.8 g = 85%
1H-NMR (100 MHz, CDCI3) = 8, 1 (t, 1 H), 6,7 (d, 1 H), 5,9 (m, 1 H), 4,9 (s, 2H), 3,9 (s, 3H), 3,9 (m, 1 H), 3,6 (s, 3H), 1 ,0 bis 2,1 (m, 9H), 1 ,0 (2s, 15H) ppm 1 H NMR (100 MHz, CDCI 3 ) = 8.1, (t, 1 H), 6.7 (d, 1 H), 5.9 (m, 1 H), 4.9 (s, 2H) , 3.9 (s, 3H), 3.9 (m, 1H), 3.6 (s, 3H), 1.0 to 2.1 (m, 9H), 1.0 (2s, 15H) ppm
Beispiel 6 4-(4-cis-tert.-Butylcyclohexylamino)-3-methoxy-2-methoxymethylpyridinExample 6 4- (4-cis-tert-Butylcyclohexylamino) -3-methoxy-2-methoxymethylpyridine
wurde analog Beispiel 5 hergestellt aus 4-[O-Benzyl-N-(4-cis- tert.-butylcyclohexyl)-hydroxylamino]-3-methoxy-2-methoxy-methylpyridin (Beispiel 2) Ausbeute: 90 %was prepared analogously to Example 5 from 4- [O-benzyl-N- (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-methoxy-methylpyridine (Example 2) Yield: 90%
1H-NMR (100 MHz, CDCI3) = 8,2 (t, 1 H), 6,8 (d, 1 H), 5,9 (m, 1 H), 4,8 (s, 2H), 3,9 (s, 3H), 3,9 (m, 1 H), 3,6 (s, 3H), 1 ,0 bis 2,1 (m, 9H), 0,9 (s, 9H) ppm 1 H NMR (100 MHz, CDCI 3 ) = 8.2 (t, 1 H), 6.8 (d, 1 H), 5.9 (m, 1 H), 4.8 (s, 2H) , 3.9 (s, 3H), 3.9 (m, 1H), 3.6 (s, 3H), 1.0 to 2.1 (m, 9H), 0.9 (s, 9H) ppm
Beispiel 7Example 7
4-[4-cis-( 1 , 1 -Dimethy lprop-( 1 )-yl)-cyclohexylamino]-3-methoxy-2- methoxymethylpyridin4- [4-cis- (1,1-dimethyl prop- (1) -yl) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine
wurde analog Beispiel 5 hergestellt aus 4-[O-Benzyl-N-(4-cis-tert.- amylcyclohexyl)]-hydroxylamino-3-methoxy-2-methoxymethylpyridin (Beispiel 4).was prepared analogously to Example 5 from 4- [O-benzyl-N- (4-cis-tert.-amylcyclohexyl)] - hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 4).
Die freie Base wurde aus der Lösung des Hydrochlorids in Methylenchlorid durch Schütteln mit Natriumhydrogencarbonatlösung in Freiheit gesetzt.The free base was released from the solution of the hydrochloride in methylene chloride by shaking with sodium bicarbonate solution.
1H-NMR (100 MHz, CDCI3) = 8,0 (d, 1 H), 6,5 (d, 1 H), 5,8 (d, 1 H), 4,5 (s, 2H), 3,8 (s, 3H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 , 1 bis 2,1 (m, 9H), 0,8 (s, t, 9H) ppm Beispiel 8 1 H NMR (100 MHz, CDCI 3 ) = 8.0 (d, 1 H), 6.5 (d, 1 H), 5.8 (d, 1 H), 4.5 (s, 2H) , 3.8 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 1.1, 2.1 to 2.1 (m, 9H), 0.8 (s, t, 9H) ppm Example 8
Ethyl -2,6-dimethyl-4-(cis-4-tert.-butyl-cyclohexylamino)-nicotinatEthyl -2,6-dimethyl-4- (cis-4-tert-butyl-cyclohexylamino) nicotinate
2, 1 g Ethyl-4-chlor-2,6-dimethylnicotinat werden unter Stickstoff mit 4,7 g 4-cis-tert.-Butylcyclohexylamin 3 Stunden auf 170 bis 180°C erhitzt. Nach dem Abkühlen wird die sirupöse Masse mit Wasser und Methylenchlorid ausgeschüttelt, die organische Phase über CaCI2 getrocknet und das Produkt durch Säulenchromatographie isoliert (Kieselgel/Toluol : Ethylacetat 3 : 1 ). Ausbeute: 1 ,8 g2.1 g of ethyl 4-chloro-2,6-dimethylnicotinate are heated under nitrogen with 4.7 g of 4-cis-tert-butylcyclohexylamine at 170 to 180 ° C. for 3 hours. After cooling, the syrupy mass is shaken out with water and methylene chloride, the organic phase is dried over CaCl 2 and the product is isolated by column chromatography (silica gel / toluene: ethyl acetate 3: 1). Yield: 1.8 g
1 H-NMR (100 MHz, CDCI3) = 0,85 (s, 9H), 1 ,37 (t, 3H), 2,37 und 2,60 (2s, 6H), 3,70 (m, 1 H), 4,33 (q, 2H) ppm 1 H NMR (100 MHz, CDCI 3 ) = 0.85 (s, 9H), 1.37 (t, 3H), 2.37 and 2.60 (2s, 6H), 3.70 (m, 1 H), 4.33 (q, 2H) ppm
Beispiel 9 Ethyl-2-methyl-4-(cis-4-tert.-amyl-cyclohexylamino)-nicotinatExample 9 Ethyl 2-methyl-4- (cis-4-tert-amyl-cyclohexylamino) nicotinate
2,0 g 4-Chlor-2-methyl-3-ethoxycarbonyl-pyridin und 1 ,7 g cis-4-tert.-Amylcyclohexan sowie katalytische Mengen Ammoniumchlorid werden 10 Stunden auf 100°C erhitzt. Nach dem Abkühlen wird in 20 ml Methanol aufgenommen und mit 2N Natronlauge neutralisiert. Die so erhaltene Reaktionsmischung wird im Vakuum zur Trockene gebracht und die freie Base mit Dichlormethan extrahiert. Nach dem Trocknen mit Na2SO4, Filtration und Entfernen des Lösungsmittels verbleiben 3,0 g Sirup.2.0 g of 4-chloro-2-methyl-3-ethoxycarbonyl-pyridine and 1.7 g of cis-4-tert-amylcyclohexane as well as catalytic amounts of ammonium chloride are heated at 100 ° C. for 10 hours. After cooling, it is taken up in 20 ml of methanol and neutralized with 2N sodium hydroxide solution. The reaction mixture thus obtained is brought to dryness in vacuo and the free base is extracted with dichloromethane. After drying with Na 2 SO 4 , filtration and removal of the solvent, 3.0 g of syrup remain.
1H-NMR (100 MHz, CDCI3) = 8,2 (d, 1 H), 7,2 (d, 1 H), 4,4 (q, 2H), 3,6 (m, 1 H), 1 ,4 (t, 3H) ppm 1 H NMR (100 MHz, CDCI 3 ) = 8.2 (d, 1 H), 7.2 (d, 1 H), 4.4 (q, 2H), 3.6 (m, 1 H) , 1, 4 (t, 3H) ppm
Beispiel 10 Ethyl-2-methyl-4-(cis-4-phenyl-cyclohexylamino)-nicotinatExample 10 Ethyl 2-methyl-4- (cis-4-phenylcyclohexylamino) nicotinate
Die Darstellung erfolgte analog Beispiel 9 aus 4-Chlor-2-methyl-3- ethoxycarbonylpyridin und 4-cis-Phenylcyclohexylamin Fp.: 191 °C Beispiel 1 1 2-Methoxymethyl-3-methoxy-4-(4-cis-tert.-butyl-cyclohexyloxy)-pyridinThe preparation was carried out analogously to Example 9 from 4-chloro-2-methyl-3-ethoxycarbonylpyridine and 4-cis-phenylcyclohexylamine, mp: 191 ° C. Example 1 1 2-methoxymethyl-3-methoxy-4- (4-cis-tert-butyl-cyclohexyloxy) pyridine
Zu 0,36 g (12 mMol) NaH (80 %ig) In 25 ml DMSO wird bei 25°C eine Mischung aus 1 ,88 g (10 mMol) 2-Methoxymethyl-3-methoxy-4-chlor-pyridin, 2,03 g (13 mMol) 4-cis-tert.-Butyl-cyclohexanol und 15 ml DMSO getropft. Anschließend wird 6 Stunden bei 60°C gerührt. Zur Aufarbeitung wird bei 20 bis 25 °C gesättigte Ammoniumchloridlösung zugegeben und mit Ethylacetat extrahiert. Das Reaktionsprodukt wird chromatographisch (SiO2; zunächst EtOAc/CH2CI2 [1 : 3] dann EtOAc) gereinigt. Ausbeute: 1 ,23 g (40 %)To 0.36 g (12 mmol) NaH (80%) in 25 ml DMSO at 25 ° C a mixture of 1.88 g (10 mmol) 2-methoxymethyl-3-methoxy-4-chloropyridine, 2nd , 03 g (13 mmol) of 4-cis-tert-butyl-cyclohexanol and 15 ml of DMSO were added dropwise. The mixture is then stirred at 60 ° C for 6 hours. For working up, saturated ammonium chloride solution is added at 20 to 25 ° C. and extracted with ethyl acetate. The reaction product is purified by chromatography (SiO 2 ; first EtOAc / CH 2 CI 2 [1: 3] then EtOAc). Yield: 1.23 g (40%)
1H-NMR (CDCI3) = 8,2 (d, 1 H), 6,8 (d, 1 H), 4,6 (s, 2H), 4,2 (m, 1 H), 3,8 (s, 3H), 3,5 (s, 1 H), 0,9 - 2,3 (m, 9H), 0,9 (s, 9H) 1 H-NMR (CDCI 3 ) = 8.2 (d, 1 H), 6.8 (d, 1 H), 4.6 (s, 2H), 4.2 (m, 1 H), 3, 8 (s, 3H), 3.5 (s, 1H), 0.9 - 2.3 (m, 9H), 0.9 (s, 9H)
Beispiel 12 Ethyl-2,6-dimethyl-4-[2-(2,4-dimethyiphenoxy)-ethylamino]-nicotinatExample 12 Ethyl 2,6-dimethyl-4- [2- (2,4-dimethyiphenoxy) ethylamino] nicotinate
wurde dargestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnicotinat und 2-(2,4-Dimethylphenoxy)-ethylamin.was prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 2- (2,4-dimethylphenoxy) ethylamine.
Beispiel 13 Ethyl-2,6-dimethyl-4-(2,2,6,6-tetramethylpiperidin-(4)-ylamino)-nicotinatExample 13 Ethyl 2,6-dimethyl-4- (2,2,6,6-tetramethylpiperidine- (4) -ylamino) nicotinate
wurde dargestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnicotinat und 2,2,6,6-Tetramethyl-4-aminopiperidin. Fp.: 89 bis 90°Cwas prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 2,2,6,6-tetramethyl-4-aminopiperidine. Mp .: 89 to 90 ° C
Beispiel 14 Ethyl-2,6-dimethyl-4-[2-methyl-3-(4-tert.-butylcyclohexyl)-propylamino]-nicotinatExample 14 Ethyl 2,6-dimethyl-4- [2-methyl-3- (4-tert-butylcyclohexyl) propylamino] nicotinate
wurde dargestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnicotinat und 2-Methyl-3-(4-tert.-butylcyclohexyl)-propylamin. n^3: 1 ,4738 Beispiel 15 Ethyl-2,6-dimethyl-4-(dec(2)ylamino)-nicotinatwas prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 2-methyl-3- (4-tert-butylcyclohexyl) propylamine. n ^ 3 : 1, 4738 Example 15 Ethyl 2,6-dimethyl 4- (dec (2) ylamino) nicotinate
wurde dargestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnlcotinat und 2-Aminodecan. n^3: 1 ,4700was prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnlcotinat and 2-aminodecane. n ^ 3 : 1, 4700
Beispiel 16 Ethyl-2,6-dimethyl-4-(4-phenylcyclohexylamino)-nicotinatExample 16 Ethyl 2,6-dimethyl 4- (4-phenylcyclohexylamino) nicotinate
wurde hergestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnicotinat und 4-Phenylcyclohexylamin. n^3: 1 ,5389was prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 4-phenylcyclohexylamine. n ^ 3 : 1, 5389
Beispiel 17 Ethyl-2,6-dimethyl-4-[N-(4-butylphenyl)-piperidin(4)ylamino]-nicotinatExample 17 Ethyl 2,6-dimethyl-4- [N- (4-butylphenyl) piperidine (4) ylamino] nicotinate
wurde hergestellt analog Beispiel 8 aus Ethyl-4-chlor-2,6-dimethylnicotinat und 4-Amino-N-(4-butylphenyl)-piperidin. n^3: 1 ,5400was prepared analogously to Example 8 from ethyl 4-chloro-2,6-dimethylnicotinate and 4-amino-N- (4-butylphenyl) piperidine. n ^ 3 : 1, 5400
Beispiel 18 2-Acetoxymethyl-3-methoxy-4-(4-cis-tert.-butyl-cyclohexyloxy)-piperidinExample 18 2-acetoxymethyl-3-methoxy-4- (4-cis-tert-butyl-cyclohexyloxy) piperidine
4,16 g (15 mMol) 2-Methyl-3-methoxy-4-(4-cis-tert.-butylcyclohexyloxy)-pyridin werden in 100 ml CH2CI2 bei 25°C mit 7,45 g (23,75 Mmol) m-Chlorperbenzoesäure (55 %ig) versetzt und bei dieser Temperatur 28 Stunden gerührt. Nach dem Waschen mit gesättigter NaHCO3-Lösung, dem Abdampfen des Lösungsmittel und der chromatographischen Reinigung [SiO2; EtOAc/AcOH (5 : 1 )] erhält man 4,19 g (95,2 %) 2-Methyl-3-methoxy-4-(4-cis-tert.-butyl- cyclohexyloxy)-pyridin-N-oxid, die mit 20 ml Acetanhydrid 1 Stunde auf 120°C erwärmt werden. Die Reaktionsmischung wird Im Vakuum eingedampft und der Rückstand chromatographisch (SiO2; EtOAc) gereinigt. Ausbeute: 4,95 g (99 %) 1H-NMR (CDCI3) = 8,2 (d, 1 H), 6,8 (d, 1 H), 5,2 (s, 2H), 4,6 (m, 1 H), 3,9 (s, 3H), 2,1 (s, 3H), 0,9 bis 2,3 (m, 9H), O,9(s, 9H), ppm4.16 g (15 mmol) of 2-methyl-3-methoxy-4- (4-cis-tert-butylcyclohexyloxy) pyridine are dissolved in 100 ml of CH2Cl 2 at 25 ° C with 7.45 g (23.75 mmol ) m-Chloroperbenzoic acid (55%) added and stirred at this temperature for 28 hours. After washing with saturated NaHCO 3 solution, evaporation of the solvent and chromatographic purification [SiO 2 ; EtOAc / AcOH (5: 1)] 4.19 g (95.2%) of 2-methyl-3-methoxy-4- (4-cis-tert-butylcyclohexyloxy) pyridine-N-oxide are obtained, which are heated to 120 ° C. for 1 hour with 20 ml of acetic anhydride. The reaction mixture is evaporated in vacuo and the residue is purified by chromatography (SiO 2 ; EtOAc). Yield: 4.95 g (99%) 1 H NMR (CDCI3) = 8.2 (d, 1 H), 6.8 (d, 1 H), 5.2 (s, 2H), 4.6 (m, 1 H), 3.9 (s, 3H), 2.1 (s, 3H), 0.9 to 2.3 (m, 9H), O.9 (s, 9H), ppm
Beispiel 19 4-O-Benzylhydroxylamino-3-ethoxy-2-ethoxymethyl-pyridinExample 19 4-O-Benzylhydroxylamino-3-ethoxy-2-ethoxymethyl-pyridine
Die Darstellung geschah analog Beispiel 1 aus 4-Chlor-3-ethoxy-2- ethoxymethylpyridin und O-Benzylhydroxylamin. Ausbeute: 90 %The illustration was carried out analogously to Example 1 from 4-chloro-3-ethoxy-2-ethoxymethylpyridine and O-benzylhydroxylamine. Yield: 90%
1H-NMR (100 MHz, CDCI3): 8,2 (d, 1 H), 7,5 (s, 1 H), 7,4 (s, 5H), 7,0 (d, 1 H), 4,9 (s, 2H), 4,6 (s, 2H), 3,9 (q, 2H), 3,6 (9,2H), 1 ,3 (t, 3H), 1 ,2 (t, 3H) ppm. 1 H NMR (100 MHz, CDCI 3 ): 8.2 (d, 1 H), 7.5 (s, 1 H), 7.4 (s, 5H), 7.0 (d, 1 H) , 4.9 (s, 2H), 4.6 (s, 2H), 3.9 (q, 2H), 3.6 (9.2H), 1, 3 (t, 3H), 1, 2 ( t, 3H) ppm.
Beispiel 20 4-O-Benzylhydroxylamino-3-brom-2-methoxymethyl-pyridinExample 20 4-O-Benzylhydroxylamino-3-bromo-2-methoxymethyl-pyridine
Die Darstellung geschah analog Beispiel 1 aus 4-Chlor-3-brom-2- methoxymethylpyridin und O-Benzylhydroxylamin. Ausbeute: 95 %The illustration was carried out analogously to Example 1 from 4-chloro-3-bromo-2-methoxymethylpyridine and O-benzylhydroxylamine. Yield: 95%
1H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 7,7 (s, 1 H), 7,4 (m, 1 H), 6,9 (d, 1 H), 4,9 (s, 2H), 4,6 (s, 2H), 3,5 (s, 3H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 7.7 (s, 1 H), 7.4 (m, 1 H), 6.9 (d, 1 H), 4.9 (s, 2H), 4.6 (s, 2H), 3.5 (s, 3H) ppm.
Beispiel 21 4-O-Benzylhydroxylamino-3-methoxy-2-allyloxy-pyridinExample 21 4-O-Benzylhydroxylamino-3-methoxy-2-allyloxypyridine
Die Darstellung geschah analog Beispiel 1 aus 4-Chlor-3-methoxy-2- allyloxypyridin und O-Benzylhydroxylamin. Ausbeute: 46,9 %The presentation was carried out analogously to Example 1 from 4-chloro-3-methoxy-2-allyloxypyridine and O-benzylhydroxylamine. Yield: 46.9%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,5 (s, 1 H), 7,4 (s, 5H), 5,8-6,1 (m, 1 H), 5, 1 -5,4 (m, 2H), 4,9 (s, 2H), 4,1-4,2 (m, 2H), 3,8 (s, 3H) ppm. Beispiel 22 4-O-Benzylhydroxylamino-3-chlor-2-methoxymethyl-pyridin 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.5 (s, 1 H), 7.4 (s, 5H), 5.8-6.1 (m, 1 H), 5, 1 -5.4 (m, 2H), 4.9 (s, 2H), 4.1-4.2 (m, 2H), 3.8 (s, 3H) ppm. Example 22 4-O-Benzylhydroxylamino-3-chloro-2-methoxymethyl-pyridine
Die Darstellung geschah analog Beispiel 1 aus 3,4-Dichlor-2- methoxymethylpyridin und O-Benzylhydroxylamin. Ausbeute: 52,8 %The illustration was carried out analogously to Example 1 from 3,4-dichloro-2-methoxymethylpyridine and O-benzylhydroxylamine. Yield: 52.8%
1H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 7,6 (s, 1 H), 7,3-7,5 (m, 5H), 7,0 (s, 1 H), 4,9 (s, 2H), 4,6 (s, 2H), 3,5 (s, 3H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 7.6 (s, 1 H), 7.3-7.5 (m, 5H), 7.0 (s, 1H), 4.9 (s, 2H), 4.6 (s, 2H), 3.5 (s, 3H) ppm.
Beispiel 23Example 23
4-[O-Benzyl-N(4-cis-phenylcyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethyl-pyridin4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4-Phenyl-1 -tosyloxycyclohexan. Ausbeute: 39 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4-phenyl-1-tosyloxycyclohexane. Yield: 39%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,3 (m, 6H), 4,7 (s, 2H), 4,6 (s, 2H), 3,9 (s, 3H), 3,8 (m, 1 H), 3,5 (s, 3H), 2,8 (m, 1 H), 1 ,5-2,4 (m, 8H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.3 (m, 6H), 4.7 (s, 2H), 4.6 (s, 2H) , 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.8 (m, 1H), 1.5-2.4 (m, 8H) ) ppm.
Beispiel 24Example 24
4-[O-Benzyl-N(4-cis-(4-ethoxyphenyl)cyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethylpyridin4- [O-benzyl-N (4-cis- (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4-(4-Ethoxyphenyl)-1 -tosyloxy- cyclohexan. Ausbeute: 46 % 1H-NMR (CDCI3. 100 MHz): δ: 8,2 (d, 1 H), 7,3 (m, 6H), 7,0 (m, 4H), 4,7 (s, 2H), 4,6 (s, 2H), 4,0 (q, 2H), 3,9 (s, 3H), 3,8 (m, 1 H), 3,5 (s, 3H), 2,8 (m, 1 H), 1 ,4 (t, 3H), 1 ,4-2,3 (m, 8H) ppm.was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-ethoxyphenyl) -1-tosyloxycyclohexane. Yield: 46% 1 H-NMR (CDCI3. 100 MHz): δ: 8.2 (d, 1 H), 7.3 (m, 6H), 7.0 (m, 4H), 4.7 (s, 2H), 4.6 (s, 2H), 4.0 (q, 2H), 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.8 ( m, 1H), 1.4 (t, 3H), 1.4-2.3 (m, 8H) ppm.
Beispiel 25 4-(O-Benzyl-N-decyl-hydroxylamino)-3-methoxy-2-methoxymethylpyridinExample 25 4- (O-Benzyl-N-decyl-hydroxylamino) -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- methylpyridin (Beispiel 1 ) und Dodecylbromid. Ausbeute: 80 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methylpyridine (Example 1) and dodecyl bromide. Yield: 80%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,3 (s, 5H), 7,3 (d, 1 H), 4,7 (s, 2H), 4,6 (s, 2H), 3,8 (s, 3H), 3,5 (s, 3H), 3,3 (t, 2H), 1 ,1 -1 ,8 (m, 16H), 0,9 (t, 3H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.3 (s, 5H), 7.3 (d, 1 H), 4.7 (s, 2H) ), 4.6 (s, 2H), 3.8 (s, 3H), 3.5 (s, 3H), 3.3 (t, 2H), 1, 1 -1, 8 (m, 16H) , 0.9 (t, 3H) ppm.
Beispiel 26 4-(4-cis-Phenylcyclohexylamino)-3-methoxy-2-methoxymethylpyridinExample 26 4- (4-cis-Phenylcyclohexylamino) -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 aus 4-[O-Benzyl-N(4-cis-phenylcyclohexyl)- hydroxylamino]-3-methoxy-2-methoxymethyl-pyridin (Beispiel 23) Ausbeute: 100 %was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine (Example 23) Yield: 100%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 7,2 (m, 5H), 6,5 (d, 1 H), 4,9 (d, 1 H), 4,5 (s, 2H), 4,9 (s, 3H), 4,8 (m, 1 H), 3,5 (s, 3H), 2 (m, 1 H), 1 ,6-2,2 (m, 9H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.2 (m, 5H), 6.5 (d, 1 H), 4.9 (d, 1 H), 4.5 (s, 2H), 4.9 (s, 3H), 4.8 (m, 1H), 3.5 (s, 3H), 2 (m, 1H), 1, 6-2.2 (m, 9H) ppm.
Beispiel 27 4-t4-cis(4-Ethoxyphenyl)-cyclohexylamino)-3-methoxy-2-methoxymethylpyridinExample 27 4-t4-cis (4-ethoxyphenyl) cyclohexylamino) -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 aus 4-[O-Benzyl-N(4-cis-(4- ethoxyphenyl)cyclohexyl)-hydroxylamino]-3-methoxy-2-methoxymethylpyridin (Beispiel 24). Ausbeute: 74 % 1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1H), 6,9 (m, 4H), 6,5 (d, 1H), 4,9was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis- (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 24). Yield: 74% 1H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1H), 6.9 (m, 4H), 6.5 (d, 1H), 4.9
(d, 1H), 4,6 (s, 2H), 4,0 (q, 2H), 3,9 (s, 3H), 3,8 (m, 1H), 2,5 (m, 1H), 1,6-2,1(d, 1H), 4.6 (s, 2H), 4.0 (q, 2H), 3.9 (s, 3H), 3.8 (m, 1H), 2.5 (m, 1H) , 1.6-2.1
(m, 8H), 1,4 (t, 3H) ppm.(m, 8H), 1.4 (t, 3H) ppm.
Beispiel 28 4-Decylamino-3-methoxy-2-methoxymethyl-pyridinExample 28 4-Decylamino-3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 5 aus 4-(O-Benzyl-N-decylhydroxylamino)-3- methoxy-2-methoxymethylpyridin (Beispiel 25). Ausbeute: 84 %was prepared analogously to Example 5 from 4- (O-benzyl-N-decylhydroxylamino) -3-methoxy-2-methoxymethylpyridine (Example 25). Yield: 84%
1H-NMR (100 MHz, CDCI3): δ: 8,0 (d, 1H), 6,4 (d, 1H), 4,6 (t, 1H), 4,5 (s, 2H), 3,0 (s, 3H), 2,0 (s, 3H), 3,1 (q, 2H), 1,2-1,6 ( , 16H), 0,9 (t, 3H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.0 (d, 1H), 6.4 (d, 1H), 4.6 (t, 1H), 4.5 (s, 2H), 3.0 (s, 3H), 2.0 (s, 3H), 3.1 (q, 2H), 1.2-1.6 (, 16H), 0.9 (t, 3H) ppm.
Beispiel 29Example 29
4-[O-Benzyl-N(1,4-dioxa-spiro[4,5]-dec-8-yl)hydroxylamino]-3-methoxy-2- methoxymethylpyridin4- [O-benzyl-N (1,4-dioxa-spiro [4,5] dec-8-yl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine
Die Darstellung erfolgte analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3- methoxy-2-methoxymethylpyridin (Beispiel 1) und 8-Tosyloxy-1,4-dioxa- spiro[4,5]-decan. Ausbeute: 78 %The preparation was carried out analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and 8-tosyloxy-1,4-dioxaspiro [4,5] -decane. Yield: 78%
1H-NMR (100 MHz, CDCI3): 8,2 (d, 1H), 7,4 (s, 5H), 7,3 (d, 1H), 4,7 (s, 2H), 4,6 (s, 2H), 3,9 (s, 3H), 3,8 (s, 3H), 3,7 (m, 1H), 3,5 (s, 4H), 1,4-2,3 (m, 8H) ppm. Beispiel 30 1 H-NMR (100 MHz, CDCI 3 ): 8.2 (d, 1H), 7.4 (s, 5H), 7.3 (d, 1H), 4.7 (s, 2H), 4, 6 (s, 2H), 3.9 (s, 3H), 3.8 (s, 3H), 3.7 (m, 1H), 3.5 (s, 4H), 1.4-2.3 (m, 8H) ppm. Example 30
4-[O-Benzyl-N(3,3-dimethyl-1 ,5-dioxa-spiro[5,5]undecan(9)yl)hydroxylamino]-3- methoxy-2-methoxymethyl-pyridin4- [O-benzyl-N (3,3-dimethyl-1,5-dioxa-spiro [5,5] undecan (9) yl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-0-Benzylhydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und 3,3-Dimethyl-9-tosyloxy-1 ,5-dioxa- spiro[5,5]undecan. Ausbeute: 68 %was prepared analogously to Example 2 from 4-0-benzylhydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and 3,3-dimethyl-9-tosyloxy-1, 5-dioxaspiro [5.5] undecane. Yield: 68%
1H-NMR (100 MHz, CDCI3): δ\ 8,2 (d, 1 H), 7,3 (m, 5H), 7,2 (d, 1 H), 4,7 (s, 2H), 4,6 (s, 2H), 9,8 (s, 3H), 3,7 (m, 1 H), 3,5 (m, 7H), 1 ,2-2,4 (m, 12H), 1 ,0 (s, 6H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ \ 8.2 (d, 1 H), 7.3 (m, 5H), 7.2 (d, 1 H), 4.7 (s, 2H) ), 4.6 (s, 2H), 9.8 (s, 3H), 3.7 (m, 1H), 3.5 (m, 7H), 1, 2-2.4 (m, 12H) ), 1.0 (s, 6H) ppm.
Beispiel 31Example 31
4-[O-Benzyl-N(4-cis-tert.-butylcyclohexyl)-hydroxylaminoJ-3-brom-2- methoxymethyl-pyridin4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylaminoJ-3-bromo-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-brom-2- methoxymethylpyridin (Beispiel 20) und 4-trans-tert.-Butyl-1-tosyloxy- cyclohexan. Ausbeute: 56,4 %was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-bromo-2-methoxymethylpyridine (Example 20) and 4-trans-tert-butyl-1-tosyloxycyclohexane. Yield: 56.4%
1 H-NMR (100 MHz, CDCI3): δ: 8,4 (s, 1 H), 7,2-7,4 (m, 6H), 4,6 (s, 2H), 4,7 (s, 2H), 3,5 (s, 3H), 3,5 (m, 1 H), 1 ,0-2,0 (m, 9H), 0,8 (s, 9H) Beispiel 32 1 H NMR (100 MHz, CDCI 3 ): δ: 8.4 (s, 1 H), 7.2-7.4 (m, 6H), 4.6 (s, 2H), 4.7 ( s, 2H), 3.5 (s, 3H), 3.5 (m, 1H), 1, 0-2.0 (m, 9H), 0.8 (s, 9H) Example 32
4-[O-Benzyl-N(4-cis-phenylcyclohexyl)-hydroxylamino]-3-brom-2- methoxymethylpyridin4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-brom-2- methoxymethyl-pyridin (Beispiel 20) und trans-4-Phenyl-1 -tosyloxy-cyclohexan. Ausbeute: 29,9 %was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-bromo-2-methoxymethyl-pyridine (Example 20) and trans-4-phenyl-1-tosyloxy-cyclohexane. Yield: 29.9%
1H-NMR (100 MHz, CDCI3): δ 8,4 (d, 1 H), 7,2-7,4 (m, 1 1 H), 4,7 (s, 2H), 4,6 (s, 2H), 3,5 (s, 3H), 3,6 (m, 1 H), 2,9 (m, 1 H), 1 ,3-2,3 (m, 8H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ 8.4 (d, 1 H), 7.2-7.4 (m, 1 1 H), 4.7 (s, 2H), 4.6 (s, 2H), 3.5 (s, 3H), 3.6 (m, 1H), 2.9 (m, 1H), 1, 3-2.3 (m, 8H) ppm.
Beispiel 33Example 33
4-[O-Benzyl-N(spiro[5,5]undecan(3)yl)hydroxylamino]-3-methoxy-2- methoxymethyl-pyridin4- [O-benzyl-N (spiro [5,5] undecan (3) yl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und 3-Tosyloxy-spiro[5,5]undecan. Ausbeute: 81 % was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and 3-tosyloxy-spiro [5.5] undecane. Yield: 81%
1H-NMR (CDCI3, 100 MHz): δ: 8,2 (d,1 H), 7,4 (m,5H), 7,2 (d, 1 H), 4,6 (s,2H), 4,7 (s,2H), 3,8(s,3H), 3,7 (m,1 H) 3,5 (s,3H), 1 ,0-2,0 (m,18H) ppm. Beispiel 34 1 H NMR (CDCI 3 , 100 MHz): δ: 8.2 (d, 1 H), 7.4 (m, 5H), 7.2 (d, 1 H), 4.6 (s, 2H) ), 4.7 (s, 2H), 3.8 (s, 3H), 3.7 (m, 1H) 3.5 (s, 3H), 1, 0-2.0 (m, 18H) ppm. Example 34
4-[O-Benzyl-N(spiro[5,5]undecan(3)yl)hydroxylamino]-3-chlor-2-methoxymethyl- pyridin4- [O-benzyl-N (spiro [5,5] undecan (3) yl) hydroxylamino] -3-chloro-2-methoxymethylpyridine
OO
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-chlor-2- methoxymethylpyridin (Beispiel 22) und 3-Tosyloxy-spiro[5,5]undecan. Ausbeute: 77 %was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-chloro-2-methoxymethylpyridine (Example 22) and 3-tosyloxy-spiro [5.5] undecane. Yield: 77%
1H-NMR (CDCI3, 100 MHz): δ: 8,3 (d,1 H), 7,3 (m,5H), 7,3 (d, 1 H), 4,6 (s,2H), 4,7 (s,2H), 4,6 (s,2H), 3,5 (s,3H) 3,3 (m,1 H), 0,9-2,0 (m, 18H) ppm. 1 H NMR (CDCI 3 , 100 MHz): δ: 8.3 (d, 1 H), 7.3 (m, 5H), 7.3 (d, 1 H), 4.6 (s, 2H) ), 4.7 (s, 2H), 4.6 (s, 2H), 3.5 (s, 3H) 3.3 (m, 1H), 0.9-2.0 (m, 18H) ppm.
Beispiel 35Example 35
4-[O-Benzyl-N-(4-cis(4(2(2,5,5-trimethyl-1 ,5-dioxan-2-yl)- ethoxy)phenyl)cyclohexyl)-hydroxylamino]-3-methoxy-2-methoxymethyl-pyridin4- [O-benzyl-N- (4-cis (4 (2 (2,5,5-trimethyl-1,5-dioxan-2-yl) ethoxy) phenyl) cyclohexyl) hydroxylamino] -3-methoxy -2-methoxymethyl pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4(4(2(2,5,5-Trimethyl-1 ,5-dioxan-2- yl)-ethoxy)phenyl)-1-tosyloxy-cyclohexan. was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4 (2 (2,5,5-trimethyl-1,5-dioxane-2- yl) -ethoxy) phenyl) -1-tosyloxy-cyclohexane.
Ausbeute: 34 %Yield: 34%
1 H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7, 1-7,4 (m,9H), 6,8 (d,1 H), 4,7 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7, 1-7.4 (m, 9H), 6.8 (d, 1 H), 4.7
(s,2H), 4,6 (s,2H), 4,2-4,1 (m,4H), 3,9 (m,1 H) 3,9 (s,3H), 3,5 (q,4H), 3,5(s, 2H), 4.6 (s, 2H), 4.2-4.1 (m, 4H), 3.9 (m, 1H) 3.9 (s, 3H), 3.5 ( q, 4H), 3.5
(s,3H), 2,8 (m, 1 H), 1 ,5-2,4 (m,4H), 1 ,5 (s,3H), 1 ,0 (s,3H), 0,9 (s,3H) ppm. Beispiel 36(s, 3H), 2.8 (m, 1H), 1, 5-2.4 (m, 4H), 1, 5 (s, 3H), 1, 0 (s, 3H), 0.9 (s, 3H) ppm. Example 36
4-[O-Benzyl-N-4-cis < (4-tetrahydrof ur(2)yl-methoxy)phenyl > -cyclohexylamino]-4- [O-benzyl-N-4-cis <(4-tetrahydrof ur (2) yl-methoxy) phenyl> -cyclohexylamino] -
3-methoxy-2-methoxymethyl-pyridin3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4<4(Tetrahydrofur(2)yl- methoxyjphenyl > -1 -tosyloxy-cyclohexan.was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 <4 (tetrahydrofur (2) yl-methoxyjphenyl> -1-tosyloxy-cyclohexane.
Ausbeute: 51 ,4 %Yield: 51.4%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,2-7,4 (m,9H), 6,8 (d, 1 H), 4,6 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2-7.4 (m, 9H), 6.8 (d, 1 H), 4.6
(s,2H), 4,7 (s,2H), 4,3 (m,1 H), 3,9 (s,1 H) 3,8-4,1 (m,5H), 3,5 (s,3H), 2,8(s, 2H), 4.7 (s, 2H), 4.3 (m, 1H), 3.9 (s, 1H) 3.8-4.1 (m, 5H), 3.5 (s, 3H), 2.8
(m,1 H), 1 ,5-2,2 (m, 12H).(m, 1H), 1.5-2.2 (m, 12H).
Beispiel 37Example 37
4-[O-Benzyl-N(4-cis(4(dimethyl-tert.-butylsilyloxy)phenyl)-cyclohexyl)- hydroxylamino-3-methoxy-2-methoxymethyl-pyridin4- [O-benzyl-N (4-cis (4 (dimethyl-tert-butylsilyloxy) phenyl) cyclohexyl) hydroxylamino-3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4(4(Dimethyl-tert.-butyl- silyloxy)phenyl)-1 -tosyloxy-cyclohexan.was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4 (dimethyl-tert-butylsilyloxy) phenyl) -1-tosyloxy-cyclohexane.
Ausbeute: 23 %Yield: 23%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,1 -7,4 (m,9H), ..,8 (d,1 H), 4,7 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.1 -7.4 (m, 9H), .., 8 (d, 1 H), 4, 7
(s,2H), 4,6 (s,2H), 3,9 (s,3H), 3,9 (m,1 H), 3,4 (s,3H), 2,8 (m,1 H), 1 ,5-2,2(s, 2H), 4.6 (s, 2H), 3.9 (s, 3H), 3.9 (m, 1H), 3.4 (s, 3H), 2.8 (m, 1 H), 1, 5-2.2
(m, 8H), 1 ,0 (s,9H), 0,2 (s,6H) ppm.(m, 8H), 1.0 (s, 9H), 0.2 (s, 6H) ppm.
Beispiel 38Example 38
4-[O-Benzyl-N(4-cis(4(2,2-dimethoxyethoxy)phenyl)-cyclohexyl)-hydroxylamino]-4- [O-benzyl-N (4-cis (4 (2,2-dimethoxyethoxy) phenyl) cyclohexyl) hydroxylamino] -
3-methoxy-2-methoxymethyl-pyridin3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- methoxymethyl-pyridin (Beispiel 1 ) und trans-4(4(2,2-Dimethoxyethoxy)phenyl)- 1 -tosyloxy-cyclohexan. Ausbeute: 66,2 % 1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,2 (m,9H), 7,2-7,4 (m,9H), 6,8 (d, 1 H), 5,3 (s,1 H), 4,8 (t,1 H), 4,7 (s,2H), 4,6 (s,2H), 4,0 (d,2H), 3,9 (m,1 H), 3,9 (s,3H), 3,5 (s,3H), 3,4 (s,6H), 2,8 (m,1 H), 1 ,5-2,1 (m,8H) ppm.was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4 (4 (2,2-dimethoxyethoxy) phenyl) -1-tosyloxy-cyclohexane. Yield: 66.2% 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2 (m, 9H), 7.2-7.4 (m, 9H), 6.8 ( d, 1 H), 5.3 (s, 1 H), 4.8 (t, 1 H), 4.7 (s, 2H), 4.6 (s, 2H), 4.0 (d, 2H), 3.9 (m, 1H), 3.9 (s, 3H), 3.5 (s, 3H), 3.4 (s, 6H), 2.8 (m, 1H), 1.5-2.1 (m, 8H) ppm.
Beispiel 39Example 39
4-[O-Benzyl-N(4-cis(4-but-2-oxy-phenyl)cyclohexyl)-hydroxylamino]-3-methoxy-4- [O-benzyl-N (4-cis (4-but-2-oxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-
2-methoxymethyl-pyridin2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4(4-But-2-oxy-phenyl)-1-tosyloxy- cyclohexanwas prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 (4-but-2-oxy-phenyl) -1-tosyloxy-cyclohexane
Ausbeute: 49,0 %Yield: 49.0%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,1-7,4 (m,9H), 6,8 (d,2H), 4,7 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.1-7.4 (m, 9H), 6.8 (d, 2H), 4.7
(s,2H), 4,6 (s,2H), 4,3 (m,1 H),3,9 (s,3H), 3,8 (m,1 H), 3,5 (s,3H), 2,8 (m,1 H),(s, 2H), 4.6 (s, 2H), 4.3 (m, 1H), 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.8 (m, 1H),
1 ,5-2,3 (m, 10H), 1 ,3 (d,3H), 1 ,0 (t,3H) ppm.1.5-2.3 (m, 10H), 1.3 (d, 3H), 1.0 (t, 3H) ppm.
Beispiel 40Example 40
4-[O-Benzyl-N(4-cis-4-(2-ethoxyethoxy)phenyl)cyclohexyl)-hydroxylamino]-3- methoxy-2-methoxymethyl-pyridin4- [O-benzyl-N (4-cis-4- (2-ethoxyethoxy) phenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4[4(2-ethoxyethoxy)phenyl]-1- tosyloxy-cyclohexan.was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4 [4 (2-ethoxyethoxy) phenyl] -1-tosyloxy-cyclohexane.
Ausbeute: 56,4 %Yield: 56.4%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,2-7,4 (m,9H), 6,8 (d,1 H), 4,6 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2-7.4 (m, 9H), 6.8 (d, 1 H), 4.6
(s,2H), 4,7 (s,2H), 4,2 (t,2H), 3,9 (s,3H), 3,9 (m,1 H), 3,8 (t,2H), 3,6 (q,2H),(s, 2H), 4.7 (s, 2H), 4.2 (t, 2H), 3.9 (s, 3H), 3.9 (m, 1H), 3.8 (t, 2H) ), 3.6 (q, 2H),
3,5 (s,3H), 2,8 (m, 1 H), 1 ,5-2,2 (m,8H), 1 ,2 (t,3H) ppm. Beispiel 413.5 (s, 3H), 2.8 (m, 1H), 1.5-2.2 (m, 8H), 1, 2 (t, 3H) ppm. Example 41
O-Benzyl-N-(4-cis{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-cyclohexyl)-N-(3- methoxy-2-methoxymethyl-pyridin-4-yl)-hydroxylamineO-benzyl-N- (4-cis {4- [2- (2-methoxyethoxy) ethoxy] phenyl} cyclohexyl) -N- (3-methoxy-2-methoxymethyl-pyridin-4-yl) -hydroxylamines
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethyl-pyridin (Beispiel 1 ) und trans-4-[4(2(2-methoxyethoxy)- ethoxy)phenyl]-1 -tosyloxy-cyclohexan.was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4- [4 (2 (2-methoxyethoxy) ethoxy) phenyl] -1-tosyloxy -cyclohexane.
Ausbeute: 42,4 %Yield: 42.4%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,2 (m,9H), 6,8 (d,1 H),4,7 (s,2H), 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2 (m, 9H), 6.8 (d, 1 H), 4.7 (s, 2H) ),
4,6 (s,2H), 4, 1 (m,2H), 3,9 (m,2H, 3,9 (s,3H), 3,9-3,8 (m,1 H), 3,8 (m,2H), 3,64.6 (s, 2H), 4.1 (m, 2H), 3.9 (m, 2H, 3.9 (s, 3H), 3.9-3.8 (m, 1H), 3 , 8 (m, 2H), 3.6
(m,2H), 3,5 (s,3H), 3,4 (s,3H), 2,8 (m,1 H), 1 ,5-2,2 (m,8H) ppm(m, 2H), 3.5 (s, 3H), 3.4 (s, 3H), 2.8 (m, 1H), 1.5-2.2 (m, 8H) ppm
Beispiel 42Example 42
4-[O-Benzyl-N(4-cis-(4-propoxyphenyl)-cyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethyl-pyridin4- [O-benzyl-N (4-cis- (4-propoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4-(4-Propoxyphenyl)-1 -tosyloxy- cyclohexan. Ausbeute: 50,3 %was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-propoxyphenyl) -1-tosyloxy-cyclohexane. Yield: 50.3%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,1-7,4 (m,9H), 6,8 (d,1 H), 4,7 (s,2H), 4,6 (s,2H), 3,9 (t,2H), 3,9 (s,3H), 3,8 (m,1 H), 3,5 (s,3H) 2,8 (m,1 H), 1 ,5-2,3 (m,10H), 1 ,1 (t,3H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.1-7.4 (m, 9H), 6.8 (d, 1 H), 4.7 (s, 2H), 4.6 (s, 2H), 3.9 (t, 2H), 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H) ) 2.8 (m, 1H), 1.5-2.3 (m, 10H), 1.1, (t, 3H) ppm.
Beispiel 43Example 43
4-[O-Benzyl-N(4-cis(4-isopropoxyphenyl)-cyclohexyl)-hydroxylamino]-3-methoxy-4- [O-benzyl-N (4-cis (4-isopropoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-
2-methoxymethyl-pyridin2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethylpyridin (Beispiel 1 ) und trans-4-(4-lsopropoxyphenyl)-1 -tosyloxy- cyclohexan Ausbeute: 54,6 % 1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1H), 7,1-7,4 (m,9H), 6,8 (d,1H), 4,7 (s,2H), 4,6 (s,2H), 4,5 (m,1H), 3,9 (s,3H), 3,5 (s,3H), 2,8 (m,1H), 1,5-2,2 (m,8H), 1,3-1,4 (d,6H) ppm.was prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethylpyridine (Example 1) and trans-4- (4-isopropoxyphenyl) -1-tosyloxycyclohexane Yield: 54.6% 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1H), 7.1-7.4 (m, 9H), 6.8 (d, 1H), 4.7 (s , 2H), 4.6 (s, 2H), 4.5 (m, 1H), 3.9 (s, 3H), 3.5 (s, 3H), 2.8 (m, 1H), 1 , 5-2.2 (m, 8H), 1.3-1.4 (d, 6H) ppm.
Beispiel 44Example 44
4-[O-Benzyl-N(4-cis-(4-butoxyphenyl)cyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethyl-pyridin4- [O-benzyl-N (4-cis- (4-butoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzyl-hydroxylamino-3-methoxy-2- methoxymethyl-pyridin (Beispiel 1) und trans-4-(4-Butoxyphenyl)-1- tosyloxycyclohexanwas prepared analogously to Example 2 from 4-O-benzyl-hydroxylamino-3-methoxy-2-methoxymethyl-pyridine (Example 1) and trans-4- (4-butoxyphenyl) -1-tosyloxycyclohexane
Ausbeute: 55,6 %Yield: 55.6%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d,1H), 7,2-7,4 (m,9H), 6,8 (d,1H), 4,6 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1H), 7.2-7.4 (m, 9H), 6.8 (d, 1H), 4.6
(s,2H), 4,7 (s,2H), 3,9 (m,2H), 3,8 (s,3H),3,9 (m,1H), 3,5 (s,3H), 2,8 (m,1H),(s, 2H), 4.7 (s, 2H), 3.9 (m, 2H), 3.8 (s, 3H), 3.9 (m, 1H), 3.5 (s, 3H) , 2.8 (m, 1H),
1,5-2,3 (m,12H), 1,0 (t,3H) ppm.1.5-2.3 (m, 12H), 1.0 (t, 3H) ppm.
Beispiel 45Example 45
4-[O-Benzyl-N-(4-cis-tert.-amylcyclohexyl)hydroxylamino]-3-brom-2- methoxymethyl-pyridin4- [O-benzyl-N- (4-cis-tert-amylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-brom-2- methoxymethylpyridin (Beispiel 20) und trans-4( 1,1,3, 3-Tetramethylbutyl)-1- tosy loxy-cyclohexan .was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-bromo-2-methoxymethylpyridine (Example 20) and trans-4 (1,1,3, 3-tetramethylbutyl) -1-tosyloxy-cyclohexane.
Ausbeute: 31 % H-NMR (100 MHz, CDCI3): δ 8,5 (d,1H), 7,4 (q,1H), 7,3 (m,5H), 4,7 (s,2H),Yield: 31% H-NMR (100 MHz, CDCI 3 ): δ 8.5 (d, 1H), 7.4 (q, 1H), 7.3 (m, 5H), 4.7 (s, 2H) ),
4,6 (s,2H), 3,5 (s,3H),3,5 (m,1H), 1,1-2,0 (m,10H), 0,8 (s,6H), 0,8 (t,3H) ppm. Beispiel 464.6 (s, 2H), 3.5 (s, 3H), 3.5 (m, 1H), 1.1-2.0 (m, 10H), 0.8 (s, 6H), 0 .8 (t, 3H) ppm. Example 46
4-[O-Benzyl-N(4-cis-tert.-butylcyclohexyl)-hydroxylamino]-3-ethoxy-2- ethoxymethylpyridin4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-ethoxy-2- ethoxymethylpyridin und 4-trans-tert.-Butyl-1 -tosyloxy-cyclohexan. Ausbeute: 18,7 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-ethoxy-2-ethoxymethylpyridine and 4-trans-tert-butyl-1-tosyloxy-cyclohexane. Yield: 18.7%
^-NMR (100 MHz, CDCI3): δ: 8,2 (d,1 H), 7,3 (m,6H), 4,6 (d,2H), 4,1 (q,2H), 3,7 (q,2H), 3,8 (m,1 H), 1 ,2-2,1 (m,15H), 0,8 (s,9H) ppm.^ -NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1H), 7.3 (m, 6H), 4.6 (d, 2H), 4.1 (q, 2H), 3.7 (q, 2H), 3.8 (m, 1H), 1, 2-2.1 (m, 15H), 0.8 (s, 9H) ppm.
Beispiel 47Example 47
4-[O-Benzyl-N(4-cis-phenylcyclohexyl)-hydroxyiamino]-3-ethoxy-2- ethoxymethylpyridin4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxyiamino] -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-ethoxy-2- ethoxymethylpyridin (Beispiel 19) und trans-4-Phenyl-1 -tosyloxycyclohexan. Ausbeute: 43 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-ethoxy-2-ethoxymethylpyridine (Example 19) and trans-4-phenyl-1-tosyloxycyclohexane. Yield: 43%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,3 (m, 6H), 4,7 (m, 4H), 4,1 (q, 2H), 3,9 (m, 1 H), 3,7 (q, 2H), 2,9 (m, 1 H), 1 ,1-2,3 (m, 14H) 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.3 (m, 6H), 4.7 (m, 4H), 4.1 (q, 2H) , 3.9 (m, 1H), 3.7 (q, 2H), 2.9 (m, 1H), 1, 1-2.3 (m, 14H)
Beispiel 48Example 48
4-[O-Benzyl-N(4-cis(4-ethoxyphenyl)cyclohexyl)-hydroxylamino]-3-ethoxy-2- ethoxymethylpyridin4- [O-benzyl-N (4-cis (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-ethoxy-2- ethoxymethylpyridin (Beispiel 19) und trans-4(4-Ethoxyphenyl)-1 -tosyloxy- cyclohexan Ausbeute: 15,9 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-ethoxy-2-ethoxymethylpyridine (Example 19) and trans-4 (4-ethoxyphenyl) -1-tosyloxycyclohexane Yield: 15.9%
^-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 6,8-7,4 (m, 10H), 4,7 (m, 4H), 3,9- 4,2 (m, 5H), 3,7 (q, 2H), 2,9 (m, 1 H), 1 ,2-2,5 (m, 17 H) ppm. Beispiel 49^ -NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1H), 6.8-7.4 (m, 10H), 4.7 (m, 4H), 3.9-4 , 2 (m, 5H), 3.7 (q, 2H), 2.9 (m, 1H), 1, 2-2.5 (m, 17H) ppm. Example 49
4-[O-Benzyl-N(4-cis-tert.-amylcyclohexyl)-hydroxylamino]-3-ethoxy-2- ethoxymethyl-pyridin4- [O-benzyl-N (4-cis-tert-amylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethyl-pyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-ethoxy-2- ethoxymethylpyridin (Beispiel 19) und trans-4-tert.-amyl-1-tosyloxycyclohexan. Ausbeute: 24 %was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-ethoxy-2-ethoxymethylpyridine (Example 19) and trans-4-tert-amyl-1-tosyloxycyclohexane. Yield: 24%
1H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 7,3 (m, 6H), 4,7 (d, 4H), 4,1 (q, 2H), 3,8 (m, 1 H), 3,7 (q, 2H), 0,7-2,1 (m, 26 H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 7.3 (m, 6H), 4.7 (d, 4H), 4.1 (q, 2H) , 3.8 (m, 1H), 3.7 (q, 2H), 0.7-2.1 (m, 26H) ppm.
Beispiel 50Example 50
4-[O-Benzyl-N(4-butylidencyclohexyl-)]hydroxylamino-3-methoxy-2- methoxymethylpyridin4- [O-benzyl-N (4-butylidene cyclohexyl -)] hydroxylamino-3-methoxy-2-methoxymethylpyridine
5 g Butyltriphenylphosphoniumchlorid in 25 ml Dimethoxyethan werden bei 0°C mit der äquimolaren Menge Butyllithium in Hexan versetzt. Nach 2 Stunden bei 25 °C gibt man 5,3 g 4[O-Benzyl-N(4-oxocyclohexyl)hydroxylamino]-3-methoxy- 2-methoxymethylpyridin (Beispiel 56) dazu und rührt 6 Stunden. Dann wird eingeengt und der Rückstand mit H2O und CH2CI2 ausgeschüttelt. Säulenreinigung mit Ethylacetat/Aceton an Kieselgel ergibt 3 g = 52,1 % Sirup. 1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,2-7,4 (m, 6H), 5,1 (t, 1 H), 4,7 (s, 2H), 4,6 (s, 2H), 3,8 (s, 3H), 3,7 (m, 1 H), 3,4 (s, 3H), 1 ,1-2,7 (m, 12H), 0,9 (t, 3H) ppm.5 g of butyltriphenylphosphonium chloride in 25 ml of dimethoxyethane are mixed with the equimolar amount of butyllithium in hexane at 0 ° C. After 2 hours at 25 ° C., 5.3 g of 4 [O-benzyl-N (4-oxocyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 56) are added and the mixture is stirred for 6 hours. The mixture is then concentrated and the residue is shaken out with H 2 O and CH 2 CI 2 . Column cleaning with ethyl acetate / acetone on silica gel gives 3 g = 52.1% syrup. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2-7.4 (m, 6H), 5.1 (t, 1 H), 4.7 (s, 2H), 4.6 (s, 2H), 3.8 (s, 3H), 3.7 (m, 1H), 3.4 (s, 3H), 1, 1-2.7 (m, 12H), 0.9 (t, 3H) ppm.
Beispiel 51 4-(4-Butylidencyclohexyl)amino-3-methoxy-2-methoxymethylpyridin H ,Example 51 4- (4-butylidene cyclohexyl) amino-3-methoxy-2-methoxymethylpyridine H,
3g 4[O-Benzyl-N(4-butylidencyclohexyl-)]hydroxyIamino-3-methoxy-2- methoxymethylpyridin (Beispiel 50) werden in 20 ml Methanol/2 ml Wasser gelöst. Dazu gibt man 3 g Zinkstaub und 12 ml Eisessig. Nach 17 stündigem Rühren wird filtriert und eingeengt. Der Rückstand wird mit 2N Natronlauge und Methylenchlorid ausgeschüttelt. Säulenreinigung der Methylenchloridphase mit Ethylacetat/Methanol 5/1 an Kieselgel ergibt 1 ,8 g = 82,2 % Öl. ^-NMR (100 MHz, CDCI3): δ: 8,0 (d, 1 H), 6,5 (d, 1 H), 5,0-5,3 (m, 1 H), 4,6 (m, 1 H), 4,5 (s, 2H), 3,8 (s, 3H), 3,7 (s, 3H), 3,4 (m, 1 H), 0,8-2,8 (m, 15H) ppm. 3 g of 4 [O-benzyl-N (4-butylidene-cyclohexyl -)] hydroxyIamino-3-methoxy-2-methoxymethylpyridine (Example 50) are dissolved in 20 ml of methanol / 2 ml of water. Add 3 g of zinc dust and 12 ml of glacial acetic acid. After stirring for 17 hours, the mixture is filtered and concentrated. The residue is extracted with 2N sodium hydroxide solution and methylene chloride. Column cleaning of the methylene chloride phase with ethyl acetate / methanol 5/1 on silica gel gives 1.8 g = 82.2% oil. ^ -NMR (100 MHz, CDCI 3 ): δ: 8.0 (d, 1 H), 6.5 (d, 1 H), 5.0-5.3 (m, 1 H), 4.6 (m, 1 H), 4.5 (s, 2H), 3.8 (s, 3H), 3.7 (s, 3H), 3.4 (m, 1H), 0.8-2, 8 (m, 15H) ppm.
Beispiel 52Example 52
4-[O-Benzyl-N(4-cis-tert.-butylcyclohexyl)-hydroxylamino]-3-methoxy-2- allyloxymethylpyridin4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- allyloxymethylpyridin (Beispiel 21 ) und 4-trans-tert.-butyl-1-tosyloxy-cyclohexan. 1 H-NMR (100 MHz, CDCI3): δ: 8,3 (s, 1 H), 7,3 (s, 5H), 7,4 (d, 1 H), 5,8-6,2 (m, 1 H), 5,1 -5,4 (m, 2H), 4,7 (d, 2H), 4,1 (m, 2H), 3,9 (s, 3H), 3,8 m (1 H), 1 ,0-2, 1 (m, 9H), 0,9, (s, 9H) ppm.was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-allyloxymethylpyridine (Example 21) and 4-trans-tert-butyl-1-tosyloxy-cyclohexane. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.3 (s, 1 H), 7.3 (s, 5H), 7.4 (d, 1 H), 5.8-6.2 (m, 1H), 5.1 -5.4 (m, 2H), 4.7 (d, 2H), 4.1 (m, 2H), 3.9 (s, 3H), 3.8 m (1H), 1, 0-2, 1 (m, 9H), 0.9, (s, 9H) ppm.
Beispiel 53Example 53
4-[O-Benzyl-N(4-cis-phenylcyclohexyl)-hydroxylamino]-3-methoxy-2- allyloxymethylpyridin4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine
wurde hergestellt analog Beispiel 2 aus 4-O-Benzylhydroxylamino-3-methoxy-2- allyloxymethylpyridin (Beispiel 21 ) und 4-Phenyl-1 -tosyloxy-cyclohexan. Ausbeute: 33,7 % H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,2 (m, 6H), 5,8-6,2 (m, 1 H), 5,1 -5,4 (m, 2H), 4,7 (d, 2H), 4,1-4,2 (m, 2H), 3,9 (s, 3H), 3,9 (m, 1 H), 2,9 (m, 1 H), 1 ,4-2,3 (m, 8H) ppm. Beispiel 54was prepared analogously to Example 2 from 4-O-benzylhydroxylamino-3-methoxy-2-allyloxymethylpyridine (Example 21) and 4-phenyl-1-tosyloxy-cyclohexane. Yield: 33.7% H-NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2 (m, 6H), 5.8-6.2 (m, 1 H) ), 5.1 -5.4 (m, 2H), 4.7 (d, 2H), 4.1-4.2 (m, 2H), 3.9 (s, 3H), 3.9 ( m, 1H), 2.9 (m, 1H), 1.4-2.3 (m, 8H) ppm. Example 54
4-[O-Benzyl-N(4-oxo-cyclohexyl)hydroxylamino]-3-methoxy-2- methoxymethylpyridin4- [O-benzyl-N (4-oxo-cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine
6g 4fO-Benzyl-N(1 ,4-dioxa-spiro[4,5]-dec-8-yl)hydroxylamino]-3-methoxy-2- methoxymethylpyridin (Beispiel 29) läßt man 5 Stunden mit 98 %iger Ameisensäure stehen. Dann wird im Vakuum eingeengt und der Rückstand mit 2N NaOH und Methylenchlorid ausgeschüttelt. Die Methylenchloridphase wird eingeengt. 5,3 g = 98,6 % Ausbeute.6 g of 4fO-benzyl-N (1,4-dioxa-spiro [4,5] -dec-8-yl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 29) are left for 5 hours with 98% formic acid . The mixture is then concentrated in vacuo and the residue is extracted with 2N NaOH and methylene chloride. The methylene chloride phase is concentrated. 5.3 g = 98.6% yield.
1H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 7,3 (m, 5H), 7,2 (d, 1 H), 4,6 (s, 4H), 4,2 (m, 1 H), 3,7 (s, 3H), 3,4 (s, 3H), 1 ,8-2,5 (m, 8H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 7.3 (m, 5H), 7.2 (d, 1 H), 4.6 (s, 4H) ), 4.2 (m, 1H), 3.7 (s, 3H), 3.4 (s, 3H), 1.8-2.5 (m, 8H) ppm.
Beispiel 55Example 55
4-[4-(-O-tert.-Butylhydroxylamino)-cyclohexylamino]-3-methoxy-2- methoxymethylpyridin4- [4 - (- O-tert-butylhydroxylamino) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine
Zu 1 ,8 g 4[4-(O-Benzyloximino)-cyclohexylamino]-3-methoxy-2- methoxymethylpyridin (Beispiel 57) in 20 ml Methanol werden 0,6 g NaBH3CN gegeben und 1 Spatelspitze Methylorange zugegeben. Dann wird etherische HCI wird in dem Maße zugetropft, daß die Lösung immer rot bleibt, wobei die Temperatur auf 40°C steigt. Nach dem Ende der Reaktion wird eingeengt und der Rückstand mit 2N NaOH und CH2CI2 ausgeschüttelt. Die CH2CI2-Phase wird über Kieselgel gereinigt. 1 ,9 g = 100 % Ausbeute. ηH-NMR (100 MHz, CDCI3): δ: 8,0 (d, 1 H), 6,5 (d, 1 H), 4,7 (d, 1 H), 4,5 (s, 2H), 3,7 (s, 3H), 3,4 (s, 3H), 2,6-2,9 (m, 2H), 1 ,3-2,1 (m, 8H), 1 ,2 (m, 9H)To 1.8 g of 4 [4- (O-benzyloximino) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine (Example 57) in 20 ml of methanol are added 0.6 g of NaBH 3 CN and 1 spatula tip of methyl orange is added. Then ethereal HCI is added dropwise to such an extent that the solution always remains red, the temperature rising to 40 ° C. After the end of the reaction, the mixture is concentrated and the residue is extracted with 2N NaOH and CH 2 Cl 2 . The CH 2 CI 2 phase is purified over silica gel. 1.9 g = 100% yield. η H-NMR (100 MHz, CDCI 3 ): δ: 8.0 (d, 1 H), 6.5 (d, 1 H), 4.7 (d, 1 H), 4.5 (s, 2H), 3.7 (s, 3H), 3.4 (s, 3H), 2.6-2.9 (m, 2H), 1, 3-2.1 (m, 8H), 1, 2 (m, 9H)
Beispiel 56 4(4-Oxocyclohexylamino)-3-methoxy-2-methoxymethylpyridinExample 56 4 (4-Oxocyclohexylamino) -3-methoxy-2-methoxymethylpyridine
4,4 g 4(1 ,4-Dioxa-spiro[4,5]-dec-8-yl)amino-3-methoxy-2-methoxymethylpyridin (Beispiel 59) läßt man in 100 ml 98 %iger Ameisensäure 17 Stunden stehen. Dann wird eingeengt und der Rückstand mit 2N NaOH und CH2CI2 ausgeschüttelt. Nach dem Einengen der organischen Phase erhält man 3,4 g = 89,9 % Kristalle.4.4 g of 4 (1,4-dioxa-spiro [4,5] -dec-8-yl) amino-3-methoxy-2-methoxymethylpyridine (Example 59) are left to stand in 100 ml of 98% formic acid for 17 hours . The mixture is then concentrated and the residue is extracted with 2N NaOH and CH 2 CI 2 . After concentrating the organic phase, 3.4 g = 89.9% crystals are obtained.
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 4,6 (d, 1 H), 4,5 (s, 2H), 4,1 (m, 1 H), 3,8 (s, 3H), 3,5 (s, 3H), 1 ,8-2,5 (m, 8H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 4.6 (d, 1 H), 4.5 (s, 2H), 4.1 (m, 1H), 3.8 (s, 3H), 3.5 (s, 3H), 1.8-2.5 (m, 8H) ppm.
Beispiel 57Example 57
4-[4-(O-tert.-Butyloximino)-cyclohexylamino]-3-methoxy-2- methoxymethylpyridin4- [4- (O-tert-butyloximino) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine
3.4 g 4-(4-Oxocyclohexylamino)-3-methoxy-2-methoxymethylpyridin (Beispiel 56) und 5 g O-tert-Butylhydroxylamin*Hydrochlorid werden in 25 ml Methanol gelöst. Nach dem Zutropfen von 8 ml 30 %iger Natriummethylatlösung läßt man ausreagieren und engt die Lösung dann ein. Der Rückstand wird mit H2O und CH2CI2 geschüttelt. Beim Einengen der CH2CI2-Phase erhält man 4, 1 g =3.4 g of 4- (4-oxocyclohexylamino) -3-methoxy-2-methoxymethylpyridine (Example 56) and 5 g of O-tert-butylhydroxylamine * hydrochloride are dissolved in 25 ml of methanol. After the dropwise addition of 8 ml of 30% sodium methylate solution, the mixture is left to react and the solution is then concentrated. The residue is shaken with H 2 O and CH 2 CI 2 . Concentrating the CH 2 CI 2 phase gives 4.1 g =
94,7 % Kristalle.94.7% crystals.
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 4,6 (d, 1 H), 4,5 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 4.6 (d, 1 H), 4.5 (s,
2H), 3,8 (s, 3H), 3,5, (s, 3H), 3, 1 (m, 1 H), 1 ,3-2,5 (m, 8H), 1 ,3 (s, 9H) ppm.2H), 3.8 (s, 3H), 3.5, (s, 3H), 3, 1 (m, 1 H), 1, 3-2.5 (m, 8H), 1, 3 (s , 9H) ppm.
Beispiel 58 4-[4-(O-Benzyloximino)-cyclohexylamino]-3-methoxy-2-methoxymethylpyridinExample 58 4- [4- (O-Benzyloximino) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine
Die Darstellung erfolgte analog Beispiel 57 aus 4-(4-Oxocyclohexylamino)-3- methoxy-2-methoxymethylpyridin (Beispiel 56) und O-Benzylhydroxylamin.The preparation was carried out analogously to Example 57 from 4- (4-oxocyclohexylamino) -3-methoxy-2-methoxymethylpyridine (Example 56) and O-benzylhydroxylamine.
Ausbeute: 100 %, SirupYield: 100%, syrup
1H-NMR (CDCI3, 100 MHz): δ: 8, 1 (d, 2H), 7,4 (m, 5H), 6,5 (d, 2H), 5,1 (s, 1 H-NMR (CDCI 3 , 100 MHz): δ: 8, 1 (d, 2H), 7.4 (m, 5H), 6.5 (d, 2H), 5.1 (s,
2H),2H),
4,6 (d, 1 H), 4,5 (s, 2H), 3,8 (s, 3H), 3,5 (m, 1 H), 3,4 (s, 3H), 2,0-2,5 (m, 8H),4.6 (d, 1H), 4.5 (s, 2H), 3.8 (s, 3H), 3.5 (m, 1H), 3.4 (s, 3H), 2.0 -2.5 (m, 8H),
1.5 (m, 2H) ppm. verbraucht ist wird filtriert und eingeengt. Säulenreinigung mit Ethylacetat/Methanol 5/1 an Kieselgel ergibt 3,9 g = 98,3 % Kristalle. ^-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 4,6 (d, 1 H), 4,5 (s, 2H), 3,8 (s, 3H), 3,5 (s, 3H), 3,5 (s, 4H), 3,4 (m, 1 H), 1 ,5-2,3 (m, 8H) ppm1.5 (m, 2H) ppm. is used is filtered and concentrated. Column cleaning with ethyl acetate / methanol 5/1 on silica gel gives 3.9 g = 98.3% crystals. ^ -NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 4.6 (d, 1 H), 4.5 (s, 2H) ), 3.8 (s, 3H), 3.5 (s, 3H), 3.5 (s, 4H), 3.4 (m, 1H), 1, 5-2.3 (m, 8H) ) ppm
Beispiel 60Example 60
4-(3,3-Dimethyl-1 ,5-dioxa[5,5]-undecan(9)yl-)amino-3-methoxy-2- methoxymethylpyridin4- (3,3-dimethyl-1,5-dioxa [5,5] -undecan (9) yl-) amino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog (Beispiel 59) aus 4[O-Benzyl-N(3,3-dimethyl-1 ,5-dioxa- spiro[5,5]undecan(9)yl)hydroxylamino]-3-methoxy-2-methoxymethyl-pyridin was prepared analogously (Example 59) from 4 [O-benzyl-N (3,3-dimethyl-1,5-dioxastiro [5,5] undecan (9) yl) hydroxylamino] -3-methoxy-2-methoxymethyl -pyridine
(Beispiel 30).(Example 30).
Ausbeute 81 ,9 % H-NMR (100 MHz, CDCI3): δ 8, 1 (d, 1 H), 6,5 (d, 1 H), 4,6 (d, 1 H), 4,5 (s,Yield 81.9% H-NMR (100 MHz, CDCI 3 ): δ 8, 1 (d, 1 H), 6.5 (d, 1 H), 4.6 (d, 1 H), 4.5 (s,
2H), 3,8 (s, 3H), 3,5 (s, 3H), 3,5 (m, 4H), 3,4 (m, 1 H), 1 ,5-2,3 (m, 8H), 1 ,02H), 3.8 (s, 3H), 3.5 (s, 3H), 3.5 (m, 4H), 3.4 (m, 1H), 1, 5-2.3 (m, 8H), 1, 0
(s, 6H) ppm. Beispiel 61 4-[4-cis(4-Propoxyphenyl)-cyclohexylamino)-3-methoxy-2-methoxymethylpyridin(s, 6H) ppm. Example 61 4- [4-cis (4-Propoxyphenyl) cyclohexylamino) -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 aus 4-[O-Benzyl-N(4-cis-(4-propoxyphenyl)- cyclohexyl)-hydroxyamino]-3-methoxy-2-methoxymethyl-pyridin (Beispiel 42). Ausbeute: 75 %was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis- (4-propoxyphenyl) cyclohexyl) hydroxyamino] -3-methoxy-2-methoxymethyl-pyridine (Example 42). Yield: 75%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 7,0 (m,4H), 6,5 (d,2H), 4,9 (d,2H), 4,5 (s,2H), 3,9 (t,2H), 3,8 (s,3H), 3,8 (m,1 H), 3,5 (s,3H), 2,6 (m,1 H), 1 ,6-2,1 (m,10H), 1 ,0 (t,3H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 7.0 (m, 4H), 6.5 (d, 2H), 4.9 (d, 2H), 4.5 (s, 2H), 3.9 (t, 2H), 3.8 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.6 ( m, 1H), 1.6-2.1 (m, 10H), 1.0 (t, 3H) ppm.
Beispiel 62Example 62
4-[4-cis(4-lsopropoxyphenyl)-cyclohexylamino)3-methoxy-2- methoxymethylpyridin4- [4-cis (4-isopropoxyphenyl) cyclohexylamino) 3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4[O-Benzyl-N(4-cis-(4-isopropoxyphenyl)-cyclohexyl)-hydroxylamino]-3-methoxy-4 [O-benzyl-N (4-cis- (4-isopropoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-
2-methoxymethylpyridin (Beispiel 43)2-methoxymethylpyridine (Example 43)
Ausbeute: 90 %Yield: 90%
1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d,1 H), 7,0 (m,4H), 6,5 (d, 1 H), 4,9 (d,1 H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1, (d, 1 H), 7.0 (m, 4H), 6.5 (d, 1 H), 4.9 (d, 1 H),
4,5 (s,2H), 4,5 (m,1 H), 3,8 (s,3H), 3,7 (m,1 H), 3,5 (s,3H), 2,6 (m,1 H), 1 ,6-2,14.5 (s, 2H), 4.5 (m, 1H), 3.8 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 2.6 (m, 1H), 1, 6-2.1
(m,8H), 1 ,3 (s,3H), 1 ,3 (s,3H) ppm.(m, 8H), 1, 3 (s, 3H), 1, 3 (s, 3H) ppm.
Beispiel 63Example 63
4-[4-cis(4-Butoxyphenyl)-phenyl-cyclohexylamino)-3-methoxy-2- methoxymethylpyridin4- [4-cis (4-butoxyphenyl) phenyl cyclohexylamino) -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4[O-Benzyl-N(4-cis-(4-butoxyphenyl)-cyclohexyl)-hydroxylamino]-3-methoxy-2- methoxymethyl-pyridin (Beispiel 44). Ausbeute: 89 % 1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d,2H), 7,0 (m,4H), 6,5 (d,2H), 4,9 (d,1 H), 4,5 (s,2H), 3,9 (t,2H), 3,8 (s,3H), 3,7 (m,1 H), 3,5 (s,3H), 2,6 (m,1 H), 1 ,6-2,1 (m, 12H), 1 ,0 (t,3H) ppm.4 [O-benzyl-N (4-cis- (4-butoxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl-pyridine (Example 44). Yield: 89% 1 H-NMR (100 MHz, CDCI 3 ): δ: 8, 1 (d, 2H), 7.0 (m, 4H), 6.5 (d, 2H), 4.9 (d, 1 H) , 4.5 (s, 2H), 3.9 (t, 2H), 3.8 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 2.6 (m, 1H), 1.6-2.1 (m, 12H), 1.0 (t, 3H) ppm.
Beispiel 64Example 64
4-[4-cis(4-But-2-oxyphenyl)-cyclohexylamino]-3-methoxy-2- methoxymethylpyridin4- [4-cis (4-but-2-oxyphenyl) cyclohexylamino] -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[0-Benzyl-N(4-cis(4-but-2-oxyphenyl)-cyclohexyl)-hydroxylamino]-3-methoxy-4- [0-benzyl-N (4-cis (4-but-2-oxyphenyl) cyclohexyl) hydroxylamino] -3-methoxy-
2-methoxymethyl-pyridin (Beispiel 39)2-methoxymethyl-pyridine (Example 39)
Ausbeute: 84 %Yield: 84%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 7,0 (m,4H), 6,5 (d,1 H), 4,9 (d,2H), 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 7.0 (m, 4H), 6.5 (d, 1H), 4.9 (d, 2H) ,
4,5 (s,2H), 4,3 (m,1 H), 3,8 (s,3H), 3,8 (m,1 H), 2,6 (m,1 H), 1 ,5-2,1 (m,10H),4.5 (s, 2H), 4.3 (m, 1H), 3.8 (s, 3H), 3.8 (m, 1H), 2.6 (m, 1H), 1, 5-2.1 (m, 10H),
1 ,3 (d,3H), 1 ,0 (t,3H) ppm.1, 3 (d, 3H), 1, 0 (t, 3H) ppm.
Beispiel 65Example 65
4-[4-cis(4-(2-Ethoxyethoxy)phenyl]cyclohexyl-amino-3-methoxy-2- methoxymethylpyridin4- [4-cis (4- (2-ethoxyethoxy) phenyl] cyclohexylamino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N(4-cis-4(2-ethoxyethoxy)phenyl)cyclohexyl)hydroxylamino]-3- methoxy-2-methoxymethylpyridin (Beispiel 40)4- [O-benzyl-N (4-cis-4 (2-ethoxyethoxy) phenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 40)
Ausbeute: 68 %Yield: 68%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 7,0 (q,4H), 6,5 (d,2H), 4,9 (d,1 H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 7.0 (q, 4H), 6.5 (d, 2H), 4.9 (d, 1 H) ,
4,5 (s,2H), 4,0 (m,4H), 3,9 (m,1 H), 3,8 (s,3H), 3,6 (q,2H), 3,5 (s,3H), 2,64.5 (s, 2H), 4.0 (m, 4H), 3.9 (m, 1H), 3.8 (s, 3H), 3.6 (q, 2H), 3.5 ( s, 3H), 2.6
(m,1 H), 1 ,6-2,1 (m,8H), 1 ,3 (t,3H) ppm. Beispiel 66(m, 1H), 1, 6-2.1 (m, 8H), 1, 3 (t, 3H) ppm. Example 66
(4-cis-{4-[2-(2-Methoxy-ethoxy)-ethoxy]-phenyl}-cyclohexyl)-(3-methoxy-2- methoxymethyl-pyridin-4-yl)-amin(4-cis- {4- [2- (2-methoxyethoxy) ethoxy] phenyl} cyclohexyl) - (3-methoxy-2-methoxymethyl-pyridin-4-yl) amine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
O-Benzyl-N-(4-cis{4-[2-(2-methoxy-ethoxy)-ethoxy]-phenyl}-cyclohexyl)-N-(3- methoxy-2-methoxymethyl-pyridin-4-yl)-hydroxylamin (Beispiel 41 )O-benzyl-N- (4-cis {4- [2- (2-methoxyethoxy) ethoxy] phenyl} cyclohexyl) -N- (3-methoxy-2-methoxymethyl-pyridin-4-yl) -hydroxylamine (Example 41)
Ausbeute: 81 %Yield: 81%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d,1 H), 7,0 (m,4H), 6,5 (d,1 H), 4,9 (m,1 H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.0 (m, 4H), 6.5 (d, 1 H), 4.9 (m, 1 H),
4.6 (s,2H), 3,8 (s,3H), 4,0 (m,4H), 3,6 (m,4H), 3,7 (m,1 H), 3,5 (s,3H), 3,4 (s,3H), 2,6 (s,1 H), 1 ,6-2, 1 (m,8H) ppm.4.6 (s, 2H), 3.8 (s, 3H), 4.0 (m, 4H), 3.6 (m, 4H), 3.7 (m, 1H), 3.5 (s, 3H), 3.4 (s, 3H), 2.6 (s, 1H), 1, 6-2, 1 (m, 8H) ppm.
Beispiel 67Example 67
4- <4-cis[4-(2,2-Dimethoxyethoxy)-phenyl]-cyclohexylamino >-3-methoxy-2- methoxymethylpyridin4- <4-cis [4- (2,2-dimethoxyethoxy) phenyl] cyclohexylamino> -3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N(4-cis(4(2,2-dimethoxyethoxy)phenyl)cyclohexyl)-hydroxylamino]-4- [O-benzyl-N (4-cis (4 (2,2-dimethoxyethoxy) phenyl) cyclohexyl) hydroxylamino] -
3-methoxy-2-methoxymethylpyridin (Beispiel 38).3-methoxy-2-methoxymethylpyridine (Example 38).
Ausbeute: 51 %Yield: 51%
^-NMR (100 MHz, CDCI3): δ: 8, 1 (d,1 H), 7,0 (m,4H), 6,5 (d, 1 H), 4,9 (d,1 H),^ -NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1H), 7.0 (m, 4H), 6.5 (d, 1H), 4.9 (d, 1H) ),
4.7 (t,1 H), 4,5 (s,2H), 4,0 (d,2H), 3,8 (s,3H), 3,7 (m,1 H), 3,5 (s,3H), 3,5 (s,6H), 2,6 (m, 1 H), 1 ,6-2, 1 (m,8H) ppm.4.7 (t, 1H), 4.5 (s, 2H), 4.0 (d, 2H), 3.8 (s, 3H), 3.7 (m, 1H), 3.5 (s , 3H), 3.5 (s, 6H), 2.6 (m, 1H), 1, 6-2, 1 (m, 8H) ppm.
Beispiel 68Example 68
4-[4-cis-(4-Dimethyl-tert.-butyl-silyloxy)phenyl]cyclohexylamino-3-methoxy-2- methoxymethylpyridin4- [4-cis- (4-dimethyl-tert-butylsilyloxy) phenyl] cyclohexylamino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N(4-cis(4(dimethyl-tert.-butyl-silyloxy)phenyl)cyclohexyl)- hydroxyamino-3-methoxy-2-methoxymethylpyridin (Beispiel 37) Ausbeute: 90,0 %4- [O-benzyl-N (4-cis (4 (dimethyl-tert-butylsilyloxy) phenyl) cyclohexyl) hydroxyamino-3-methoxy-2-methoxymethylpyridine (Example 37) Yield: 90.0%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 6,9 (m,4H), 6,5 (d,2H), 5,0 (d,2H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 6.9 (m, 4H), 6.5 (d, 2H), 5.0 (d, 2H),
4.5 (s,2H), 3,9 (s,3H), 3,7 (m,1H), 3,5 (s,3H), 2,6 (m,1H), 1,6-2,1 (m,8H), 1,0 (s,9H), 0,2 (s,6H) ppm.4.5 (s, 2H), 3.9 (s, 3H), 3.7 (m, 1H), 3.5 (s, 3H), 2.6 (m, 1H), 1.6-2.1 (m, 8H), 1.0 (s, 9H), 0.2 (s, 6H) ppm.
Beispiel 69Example 69
4-[4-cis(4-Tetrahydrofur(2)ylmethoxy)phenyl]cyclohexylamino-3-methoxy-2- methoxymethylpyridin4- [4-cis (4-tetrahydrofur (2) ylmethoxy) phenyl] cyclohexylamino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N-4-cis < (4-tetrahydrof ur(2)yl-methoxy)phenyl > -cyclohexylamino]-4- [O-benzyl-N-4-cis <(4-tetrahydrof ur (2) yl-methoxy) phenyl> -cyclohexylamino] -
3-methoxy-2-methoxymethylpyridin (Beispiel 36)3-methoxy-2-methoxymethylpyridine (Example 36)
Ausbeute: 89 %Yield: 89%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 7,0 (m,4H), 6,5 (d,1H), 4,9 (d,1H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 7.0 (m, 4H), 6.5 (d, 1H), 4.9 (d, 1H),
4.6 (s,2H), 4,3 (m,1H), 3,8 (s,3H), 3,8-4,0 (m,4H), 3,7 (m,1H), 3,5 (s,3H), 2,6 (m,1H), 1,6-2,1 (m,12H) ppm.4.6 (s, 2H), 4.3 (m, 1H), 3.8 (s, 3H), 3.8-4.0 (m, 4H), 3.7 (m, 1H), 3.5 (s, 3H), 2.6 (m, 1H), 1.6-2.1 (m, 12H) ppm.
Beispiel 70 4-(Spiro[5,5]undecan(3)yl)amino-3-chlor-2-methoxymethyl-pyridinExample 70 4- (Spiro [5,5] undecan (3) yl) amino-3-chloro-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 51 auswas produced analogously to Example 51
4-[O-Benzyl-N(Spiro[5,5]undecan(3)yl-hydroxylamino]-3-chlor-2- methoxymethylpyridin (Beispiel 34).4- [O-Benzyl-N (Spiro [5,5] undecan (3) yl-hydroxylamino] -3-chloro-2-methoxymethylpyridine (Example 34).
Ausbeute: 84 %Yield: 84%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d,2H), 6,5 (d,2H), 4,8 (d,2H), 4,6 (s,3H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 2H), 6.5 (d, 2H), 4.8 (d, 2H), 4.6 (s, 3H),
3,5 (s,3H), 3,4 (m,1H), 1,2-1,9 (m,18H) ppm. Beispiel 71 4-(Spiro[5,5]undecan(3)yl)amino-3-methoxy-2-methoxymethyl-pyridin3.5 (s, 3H), 3.4 (m, 1H), 1.2-1.9 (m, 18H) ppm. Example 71 4- (Spiro [5,5] undecan (3) yl) amino-3-methoxy-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-tO-Benzyl-N(spiro[5,5]undecan(3)yl)hydroxylamino]-3-methoxy-2- methoxymethylpyridin (Beispiel 33)4-tO-benzyl-N (spiro [5,5] undecan (3) yl) hydroxylamino] -3-methoxy-2-methoxymethylpyridine (Example 33)
Ausbeute: 50,5 %Yield: 50.5%
1 H-NMR (CDCI3, 100 MHz): δ: 8, 1 (d,2H), 6,5 (d,2H), 4,6 (m,1 H), 4,5 (s,2H), 1 H-NMR (CDCI 3 , 100 MHz): δ: 8, 1 (d, 2H), 6.5 (d, 2H), 4.6 (m, 1 H), 4.5 (s, 2H) ,
3,8 (s,3H), 3,5 (s,3H), 3,3 (m, 1 H), 1 ,2-2,0 (m,18H) ppm.3.8 (s, 3H), 3.5 (s, 3H), 3.3 (m, 1H), 1, 2-2.0 (m, 18H) ppm.
Beispiel 72Example 72
4-[cis(4(2(2,5,5-Trimethyl-1 ,5-dioxan-2-yl)ethoxy)phenyl)cyclohexyl]amino-3- methoxy-2-methoxymethylpyridin4- [cis (4 (2 (2,5,5-trimethyl-1,5-dioxan-2-yl) ethoxy) phenyl) cyclohexyl] amino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N-(4-cis(4(2(2,5,5-trimethyl-1 ,5-dioxan-2- yl)ethoxy)phenyl)cyclohexyl)-hydroxylamino]-3-methoxy-2-methoxymethyl- pyridin (Beispiel 35)4- [O-benzyl-N- (4-cis (4 (2 (2,5,5-trimethyl-1,5-dioxan-2-yl) ethoxy) phenyl) cyclohexyl) hydroxylamino] -3-methoxy- 2-methoxymethylpyridine (Example 35)
Ausbeute: 100 %Yield: 100%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d,1 H), 7,0 (m,4H), 6,5 (d,2H), 4,9 (d,1 H), 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.0 (m, 4H), 6.5 (d, 2H), 4.9 (d, 1 H) ),
4,5 (s,2H), 4, 1 (t,2H), 3,8 (s,3H), 3,8 (m,1 H), 3,5 (m,4H), 3,5 (s,3H), 2,64.5 (s, 2H), 4, 1 (t, 2H), 3.8 (s, 3H), 3.8 (m, 1H), 3.5 (m, 4H), 3.5 ( s, 3H), 2.6
(m, 1 H), 1 ,6-2,4 (m,10H), 1 ,4 (s,3H), 1 ,0 (s,3H), 0,9 (s,3H) ppm. Beispiel 73(m, 1H), 1.6-2.4 (m, 10H), 1.4 (s, 3H), 1.0 (s, 3H), 0.9 (s, 3H) ppm. Example 73
4-[4-cis(4(2-oxoethoxy)phenyl)cyclohexyl]-amino-3-methoxy-2-methoxy- methylpyridin4- [4-cis (4 (2-oxoethoxy) phenyl) cyclohexyl] amino-3-methoxy-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 56 auswas produced from Example 56
4-[O-Benzyl-N(4-cis(4(2,2-dimethoxy)phenyl)cyclohexyl)-hydroxylamino]-3- methoxy-2-methoxymethγlpyridin (Beispiel 67).4- [O-benzyl-N (4-cis (4 (2,2-dimethoxy) phenyl) cyclohexyl) hydroxylamino] -3-methoxy-2-methoxymethyl pyridine (Example 67).
Ausbeute: 90,4 %Yield: 90.4%
1H-NMR (100 MHz, CDCI3): δ: 9,9 (s,1 H), 8,1 (d, 1 H), 7,0 (m,4H), 6,5 (d,1 H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 9.9 (s, 1 H), 8.1 (d, 1 H), 7.0 (m, 4H), 6.5 (d, 1 H),
4,9 (d,1 H), 4,5 (d,2H), 3,9 (s,3H), 3,8 (m,1 H), 3,5 (s,3H), 2,6 (m,1 H), 1 ,6-2,14.9 (d, 1H), 4.5 (d, 2H), 3.9 (s, 3H), 3.8 (m, 1H), 3.5 (s, 3H), 2.6 (m, 1H), 1, 6-2.1
(m,8H) ppm.(m, 8H) ppm.
Beispiel 74 4-(4-cis-tert.-Butylcyclohexylamino)-3-ethoxy-2-ethoxymethylpyridinExample 74 4- (4-cis-tert-Butylcyclohexylamino) -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N(4-cis-tert.-butylcyclohexyl)-hydroxylamino]-3-ethoxy-2- ethoxymethylpyridin (Beispiel 46)4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 46)
Ausbeute: 80 %Yield: 80%
^-NM (100 MHz, CDCI3): δ 8,1 (d,1 H), 6,4 (d,1 H), 4,9 (d, 1 H), 4,5 (s,1 H),^ -NM (100 MHz, CDCI 3 ): δ 8.1 (d, 1 H), 6.4 (d, 1 H), 4.9 (d, 1 H), 4.5 (s, 1 H) ),
4,0 (q,2H), 3,8 (q,2H), 3,7 (m,1 H), 1 ,1 -2,1 (m,15H), 0,9 (s,3H)4.0 (q, 2H), 3.8 (q, 2H), 3.7 (m, 1H), 1, 1 -2.1 (m, 15H), 0.9 (s, 3H)
Beispiel 75 4-(4-cis-tert.-Amylcyclohexylamino)-3-ethoxy-2-ethoxymethylpyridinExample 75 4- (4-cis-tert-Amylcyclohexylamino) -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 5 auswas produced analogously to Example 5
4-[O-Benzyl-N(4-cis-tert.-amylcyclohexyl)-hydroxylamino]-3-ethoxy-2- ethoxymethylpyridin (Beispiel 49)4- [O-benzyl-N (4-cis-tert-amylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 49)
Ausbeute: 81 %Yield: 81%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d,1 H), 6,4 (d,1 H), 4,8 (d,1 H), 4,5 (s,2H), 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.4 (d, 1 H), 4.8 (d, 1 H), 4.5 (s, 2H),
3,9 (q,2H), 3,7 (m, 1 H), 3,7 (q,2H), 1 ,1 -2,0 (m,18H), 0,8 (s,6H), 0,8 (t,3H) Beispiel 76 4-(4-cis-Phenylcyclohexyl)amino-3-ethoxy-2-ethoxymethylpyridin3.9 (q, 2H), 3.7 (m, 1H), 3.7 (q, 2H), 1, 1 -2.0 (m, 18H), 0.8 (s, 6H), 0.8 (t, 3H) Example 76 4- (4-cis-Phenylcyclohexyl) amino-3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 5 aus 4-[O-Benzyl-N(4-cis-Phenylcyclohexyl)- hydroxyl-amino]-3-ethoxy-2-ethoxymethylpyridin (Beispiel 47)was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 47)
Ausbeute: 53 %Yield: 53%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 7,1-7,4 (m, 5H), 6,4 (d, 1 H), 5,0 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.1-7.4 (m, 5H), 6.4 (d, 1 H), 5.0
(d, 1 H), 4,5 (s, 2H), 4,0 (q, 2H), 3,8 (m, 1 H), 3,7 (q, 2H), 2,7 (m, 1H), 1 ,5-2,1(d, 1H), 4.5 (s, 2H), 4.0 (q, 2H), 3.8 (m, 1H), 3.7 (q, 2H), 2.7 (m, 1H), 1, 5-2.1
(m, 8H), 1 ,2 (t, 3H)ppm, 1 ,5 (t, 3H) ppm.(m, 8H), 1, 2 (t, 3H) ppm, 1, 5 (t, 3H) ppm.
Beispiel 77 4-[4-cis(4-Ethoxyphenyl)cyclohexylamino]-3-ethoxy-2-ethoxymethylpyridinExample 77 4- [4-cis (4-Ethoxyphenyl) cyclohexylamino] -3-ethoxy-2-ethoxymethylpyridine
wurde hergestellt analog Beispiel 5 aus 4-[O-Benzyl-N(4-cis(4-ethoxyphenyl) cyclohexyl)-hydroxylamino]-3-ethoxy-2-ethoxymethylpyridin (Beispiel 48) Ausbeute: 76,3 %was prepared analogously to Example 5 from 4- [O-benzyl-N (4-cis (4-ethoxyphenyl) cyclohexyl) hydroxylamino] -3-ethoxy-2-ethoxymethylpyridine (Example 48). Yield: 76.3%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,7-7,2 (m, 4H), 6,5 (d, 1 H), 5,0 (d, 1 H), 4,6 (s, 2H), 4,0 (q, 2H), 3,8 (m, 1 H), 3,7 (q, 2H), 2,5 (m, 1 H), 1 ,2-2,1 (m, 17H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.7-7.2 (m, 4H), 6.5 (d, 1 H), 5.0 (d, 1H), 4.6 (s, 2H), 4.0 (q, 2H), 3.8 (m, 1H), 3.7 (q, 2H), 2.5 (m, 1 H), 1, 2-2.1 (m, 17H) ppm.
Beispiel 78 4-(4-cis-Phenylcyclohexylamino)-2-allyloxymethyl-3-methoxy-pyridinExample 78 4- (4-cis-Phenylcyclohexylamino) -2-allyloxymethyl-3-methoxy-pyridine
wurde hergestellt analog Beispiel 50 aus 4-[O-Benzyl-N(4-cis-phenylcyclohexyl)- hydroxylamino]-3-methoxy-2-allyloxymethylpyridin (Beispiel 53)was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine (Example 53)
Ausbeute: 99,0 %Yield: 99.0%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 7,2 (m, 6H), 6,5 (d, 1 H), 5,8-6,2 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.2 (m, 6H), 6.5 (d, 1 H), 5.8-6.2
(m, 1 H), 5, 1-5,4 (m, 2H), 4,9 (d, 1 H), 4,6 (s, 2H), 4,1 -4,2 (m, 2H), 3,8 (s, 3H),(m, 1H), 5, 1-5.4 (m, 2H), 4.9 (d, 1H), 4.6 (s, 2H), 4.1 -4.2 (m, 2H) ), 3.8 (s, 3H),
3,7 (m, 1 H), 2,5-2,8 (m, 1 H), 1 ,5-2,1 (m, 8H)ppm. Beispiel 79 4-(4-cis-tert.-Butylcyclohexyiamino)-2-allyloxymethyl-3-methoxy-pyridin3.7 (m, 1H), 2.5-2.8 (m, 1H), 1.5-2.1 (m, 8H) ppm. Example 79 4- (4-cis-tert-Butylcyclohexyiamino) -2-allyloxymethyl-3-methoxy-pyridine
wurde hergestellt analog Beispiel 50 aus 4-[O-Benzyl-N(4-cis-tert.- butylcyclohexyl)-hydroxylamino]-3-methoxy-2-allyloxymethylpyridin (Beispiel 52) Ausbeute: 79,1 %was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-methoxy-2-allyloxymethylpyridine (Example 52) Yield: 79.1%
^-NMR (100 MHz, CDCI3): δ: 8, 1 (d, 1 H), 7,2 (m, 6H), 6,5 (d, 1 H), 5,8-6,2 (m, 1 H), 5,1-5,4 (m, 2H), 4,9 (d, 1 H), 4,6 (s, 2H), 4,1-4,2 (m, 2H), 3,8 (s, 3H), 3,7 (m, 1 H), 2,5-2,8 (m, 1 H), 1 ,5-2,1 (m, 8H) ppm.^ -NMR (100 MHz, CDCI 3 ): δ: 8, 1 (d, 1 H), 7.2 (m, 6H), 6.5 (d, 1 H), 5.8-6.2 ( m, 1H), 5.1-5.4 (m, 2H), 4.9 (d, 1H), 4.6 (s, 2H), 4.1-4.2 (m, 2H) , 3.8 (s, 3H), 3.7 (m, 1H), 2.5-2.8 (m, 1H), 1.5-2.1 (m, 8H) ppm.
Beispiel 80 4-(4-cis-tert.-Butylcyclohexyl)amino-2-methoxymethylpyridinExample 80 4- (4-cis-tert-Butylcyclohexyl) amino-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 50 aus 4-[O-Benzyl-N(4-cis-tert.- butylcyclohexyl)-hydroxylamino]-3-brom-2-methoxymethylpyridin (Beispiel 31 ) Ausbeute: 36 %was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 31). Yield: 36%
1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d, 1 H), 6,6 (d, 2H), 6,4 (q, 1 H), 4,5 (s, 2H), 4,4 (d, 1 H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,0-2,0 (m, 8H), 0,8 (s, 9H) ppm. 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1, (d, 1H), 6.6 (d, 2H), 6.4 (q, 1H), 4.5 (s, 2H) ), 4.4 (d, 1 H), 3.7 (m, 1 H), 3.5 (s, 3H), 1, 0-2.0 (m, 8H), 0.8 (s, 9H) ppm.
Beispiel 81 4-(4-cis-Phenylcyclohexylamino)-2-methoxymethylpyridinExample 81 4- (4-cis-Phenylcyclohexylamino) -2-methoxymethylpyridine
wurde hergestellt analog Beispiel 50 aus 4-[O-Benzyl-N(4-cis-phenylcyclohexyl)- hydroxylamino]-3-brom-2-methoxymethylpyridin (Beispiel 32)was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-phenylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 32)
Ausbeute: 38 %Yield: 38%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 7,2 (m, 5H), 6,6 (d, 1 H), 6,4 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 7.2 (m, 5H), 6.6 (d, 1 H), 6.4
(q, 1 H), 4,5 (s, 2H), 4,5 (m, 1 H), 3,8 (m, 1 H), 3,5 (s, 3H), 2,6 (m, 1 H), 1 ,6-2,1(q, 1H), 4.5 (s, 2H), 4.5 (m, 1H), 3.8 (m, 1H), 3.5 (s, 3H), 2.6 (m , 1 H), 1, 6-2.1
(m, 8H) ppm. Beispiel 82 4-[4-cis-(2,2-Diemethylpropyl)-cyclohexylamino]-2-methoxypyridin(m, 8H) ppm. Example 82 4- [4-cis- (2,2-dimethylpropyl) cyclohexylamino] -2-methoxypyridine
wurde hergestellt analog Beispiel 50 aus 4-[O-Benzyl-N(4-cis-tert.- amylcyclohexyl)-hydroxylamino]-3-brom-2-methoxymethylpyridin (Beispiel 45) Ausbeute: 52,3 %was prepared analogously to Example 50 from 4- [O-benzyl-N (4-cis-tert.-amylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 45) Yield: 52.3%
1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d, 1 H), 6,6 (d, 1 H), 6,3 (q, 1 H), 4,5 (s, 2H), 4,4 (d, 1 H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,1 -1 ,6 (m, 1 1 H), 0,8 (t, 3H), 0,8 (s, 6H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8, 1 (d, 1 H), 6.6 (d, 1 H), 6.3 (q, 1 H), 4.5 (s, 2H), 4.4 (d, 1 H), 3.7 (m, 1 H), 3.5 (s, 3H), 1, 1 -1, 6 (m, 1 1 H), 0.8 (t, 3H), 0.8 (s, 6H) ppm.
Beispiel 83 3-Brom-4(4-cis-tert.-butyl-cyclohexylamino)-2-methoxymethylpyridinExample 83 3-Bromo-4 (4-cis-tert-butyl-cyclohexylamino) -2-methoxymethylpyridine
wurde hergestellt durch Umsetzung von 4-[O-Benzyl-N(4-cis-tert.- butylcyclohexyl)-hydroxylamino]-3-brom-2-methoxymethylpyridin (Beispiel 31 ) mit einer Ti(O)-Lösung analog M. Malinowski und L. Kaczmarek, Journal f. prakt. Chemie 330 (1988) 154.was prepared by reacting 4- [O-benzyl-N (4-cis-tert-butylcyclohexyl) hydroxylamino] -3-bromo-2-methoxymethylpyridine (Example 31) with a Ti (O) solution analogous to M. Malinowski and L. Kaczmarek, Journal f. Practical Chemistry 330 (1988) 154.
Ausbeute: 30 %Yield: 30%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 6,4 (d, 1 H), 5,2 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 6.4 (d, 1 H), 5.2 (d, 1 H), 4.6 (s,
2H), 3,6 (s, 3H), 3,8 (m, 1 H), 1 ,1-2,0 (m, 9H), 0,8 (s, 3H) ppm.2H), 3.6 (s, 3H), 3.8 (m, 1H), 1, 1-2.0 (m, 9H), 0.8 (s, 3H) ppm.
Beispiel 84 3-Chlor-4-[cis-(4-tert.-butyl)cyclohexylamino]-2-methoxymethyl-pyridinExample 84 3-Chloro-4- [cis- (4-tert-butyl) cyclohexylamino] -2-methoxymethyl-pyridine
1 g 2-Methoxymethyl-3,4-dichlorpyridin und 1 g cis-4-tert.-Butylcyclohexylamin werden zusammen mit 4,3 mg Ammoniumchlorid in 4 ml N-Methylpyrrolidon 3,5 Stunden auf 180°C erhitzt. Dann gießt man den Ansatz auf gesättigte Bicarbonatlösung und versetzt das Produkt mit Ethylacetat. Die Ethylacetatphase wird 3 mal mit Wasser gewaschen und anschließend über Kieselgel chromatographiert mit Ethylacetat/Hexan 1 /1 als Eluent. Ausbeute: 47 %. Öl. 1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d, 1 H), 6,5 (d, 1 H), 5, 1 (d, 1 H), 4,6 (s, 2H), 3,5 (s, 3H), 3,7 (m, 1 H), 1 ,0-2,0 (m, 9H), 0,9 (s, 9H) ppm.1 g of 2-methoxymethyl-3,4-dichloropyridine and 1 g of cis-4-tert-butylcyclohexylamine are heated together with 4.3 mg of ammonium chloride in 4 ml of N-methylpyrrolidone at 180 ° C. for 3.5 hours. Then the mixture is poured onto saturated bicarbonate solution and the product is mixed with ethyl acetate. The ethyl acetate phase is washed 3 times with water and then chromatographed on silica gel using ethyl acetate / hexane 1/1 as the eluent. Yield: 47%. Oil. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8, 1 (d, 1 H), 6.5 (d, 1 H), 5, 1 (d, 1 H), 4.6 (s, 2H), 3.5 (s, 3H), 3.7 (m, 1H), 1.0, 2.0-2.0 (m, 9H), 0.9 (s, 9H) ppm.
Beispiel 85 3-Chlor-4-[4-cis-but(2)yl-cyclohexylamino]-2-methoxymethylpyridinExample 85 3-Chloro-4- [4-cis-but (2) yl-cyclohexylamino] -2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-cis-but(2)yl-cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis-but (2) yl-cyclohexylamine.
Ausbeute: 40 %Yield: 40%
1H-NMR (100 MHz, CDCI3): δ 8,1 (d, 1 H), 6,5 (d, 1 H), 5,1 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ 8.1 (d, 1 H), 6.5 (d, 1 H), 5.1 (d, 1 H), 4.6 (s,
2H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,0-2,0 (m, 12H), 0,9 (t, 3H), 0,9 (d, 3H) ppm.2H), 3.7 (m, 1H), 3.5 (s, 3H), 1, 0-2.0 (m, 12H), 0.9 (t, 3H), 0.9 (d, 3H) ppm.
Beispiel 86 3-Chlor-4-[4-trans-but(2)yl-cyclohexylamino]-2-methoxymethylpyridinExample 86 3-Chloro-4- [4-trans-but (2) yl-cyclohexylamino] -2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-trans-but(2)-yl-cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-trans-but (2) -yl-cyclohexylamine.
Ausbeute: 38 %Yield: 38%
1 H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 5,0 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 5.0 (d, 1 H), 4.6 (s,
2H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,0-2,0 (m, 12H), 0,9 (t, 3H), 0,9 (d, 3H) ppm.2H), 3.7 (m, 1H), 3.5 (s, 3H), 1, 0-2.0 (m, 12H), 0.9 (t, 3H), 0.9 (d, 3H) ppm.
Beispiel 87 3-Chlor-4-[4-cis-cyclohexyl-cyclohexylamino]-2-methoxymethylpyridinExample 87 3-Chloro-4- [4-cis-cyclohexyl-cyclohexylamino] -2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-cis-cyclohexyl-cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis-cyclohexyl-cyclohexylamine.
Ausbeute: 35 %Yield: 35%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 5,1 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 5.1 (d, 1 H), 4.6 (s,
2H), 3,7 (m, 1 H), 3,5 (s, 3H), 0,9-2,0 (m, 20H) ppm. Beispiel 88 3-Chlor-4-[4-trans-cyclohexyl-cyclohexylamino]-2-methoxymethylpyridin2H), 3.7 (m, 1H), 3.5 (s, 3H), 0.9-2.0 (m, 20H) ppm. Example 88 3-Chloro-4- [4-trans-cyclohexyl-cyclohexylamino] -2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-trans-Cyclohexyl-cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4-trans-cyclohexyl-cyclohexylamine.
Ausbeute: 17 %Yield: 17%
^-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1H), 6,5 (d, 1H), 4,7 (d, 1H), 4,6 (s,^ -NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1H), 6.5 (d, 1H), 4.7 (d, 1H), 4.6 (s,
2H), 3,5 (s, 3H), 3,2 (m, 1H), 0,9-2,2 (m, 20H) ppm.2H), 3.5 (s, 3H), 3.2 (m, 1H), 0.9-2.2 (m, 20H) ppm.
Beispiel 89Example 89
3-Chlor-4-[4-cis( 1,1,3, 3-tetramethylbutyl)cyclohexylamino]-2-methoxymethyl- pyridin3-chloro-4- [4-cis (1,1,3, 3-tetramethylbutyl) cyclohexylamino] -2-methoxymethylpyridine
undand
Beispiel 90Example 90
3-Chlor-4-[4-trans( 1,1,3, 3-tetramethylbutyl)-cyclohexylamino]-2- methoxymethylpyridin3-chloro-4- [4-trans (1,1,3, 3-tetramethylbutyl) cyclohexylamino] -2-methoxymethylpyridine
wurden hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und Cis/trans-4-Tetramethylbutyl)cyclohexylamin und anschließende Isomerentrennung an Sephadex mit Methanol. Ausbeute (trans-lsomer): 17 % Ausbeute (cis-lsomer): 17 %were prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and cis / trans-4-tetramethylbutyl) cyclohexylamine and subsequent isomer separation on Sephadex with methanol. Yield (trans-isomer): 17% Yield (cis-isomer): 17%
1H-NMR (100 MHz, CDCI3) (trans-lsomer): δ 8,1 (d, 1H), 6,5 (d, 1H), 4,7 (d, 1H), 4,6 (s, 2H), 3,5 (s, 3H), 3,2 (m, 1H), 1,1-2,2 (m, 11H), 1,0 (s, 6H), 1,0 (s, 9H) ppm. 1 H-NMR (100 MHz, CDCI 3 ) (trans-isomer): δ 8.1 (d, 1H), 6.5 (d, 1H), 4.7 (d, 1H), 4.6 (s , 2H), 3.5 (s, 3H), 3.2 (m, 1H), 1.1-2.2 (m, 11H), 1.0 (s, 6H), 1.0 (s, 9H) ppm.
^-NMR (100 MHz, CDCI3) (cis-lsomer): δ: 8,1 (d, 1H), 6,5 (d, 1H), 5,1 (d, 1H), 4,6 (s, 2H), 3,8 (m, 1H), 3,5 (s, 3H), 1,2-2,0 (m, 11H), 1,0 (s, 9H), 0,9 (s, 6H) ppm. Beispiel 91 3-Chlor-4-(3-cis-isoamyl-cyclopentyl)amino-2-methoxymethyl-pyridin^ -NMR (100 MHz, CDCI 3 ) (cis-isomer): δ: 8.1 (d, 1H), 6.5 (d, 1H), 5.1 (d, 1H), 4.6 (s , 2H), 3.8 (m, 1H), 3.5 (s, 3H), 1.2-2.0 (m, 11H), 1.0 (s, 9H), 0.9 (s, 6H) ppm. Example 91 3-Chloro-4- (3-cis-isoamyl-cyclopentyl) amino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 89 aus 2-Methoxymethyl-3,4-dichlorpyridin und 3-lsoamyl-cyclopentylamin.was prepared analogously to Example 89 from 2-methoxymethyl-3,4-dichloropyridine and 3-isoamyl-cyclopentylamine.
Ausbeute: 39 %Yield: 39%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,5 (d, 1 H), 4,8 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.5 (d, 1 H), 4.8 (d, 1 H), 4.6 (s,
2H), 3,8 (m, 1 H), 3,4 (s, 3H), 1 ,0-2,2 (m, 9H), 0,8 (t, 3H), 0,8 (s, 6H) ppm.2H), 3.8 (m, 1H), 3.4 (s, 3H), 1, 0-2.2 (m, 9H), 0.8 (t, 3H), 0.8 (s, 6H) ppm.
Beispiel 92Example 92
3-Chlor-4-[4-(4-(2-ethoxyethoxy)ethoxy)phenyl]cyclohexylamino-2- methoxymethyl-pyridin3-chloro-4- [4- (4- (2-ethoxyethoxy) ethoxy) phenyl] cyclohexylamino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-[4-(2-Ethoxyethoxy)ethoxy]phenyl-cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4- [4- (2-ethoxyethoxy) ethoxy] phenyl-cyclohexylamine.
Ausbeute: 40 %Yield: 40%
1 H-NMR: 8,2 (d, 1 H), 7,0 (m, 4H), 6,5 (d, 1 H), 5, 1 (d, 1 H), 4,6 (s, 2H), 3,4-4,2 1 H NMR: 8.2 (d, 1 H), 7.0 (m, 4H), 6.5 (d, 1 H), 5, 1 (d, 1 H), 4.6 (s, 2H), 3.4-4.2
(m, 14H), 1 , 1 -2,6 (m, 9H), 1 ,2 (t, 3H) ppm.(m, 14H), 1.1-2.6 (m, 9H), 1.2 (t, 3H) ppm.
Beispiel 93 3-Chlor-4-[2-(2,4-dimethyl)phenoxy]propylamino-2-methoxymethyl-pyridinExample 93 3-Chloro-4- [2- (2,4-dimethyl) phenoxy] propylamino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 2-(2,4-Dimethyl)phenoxy-propylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2- (2,4-dimethyl) phenoxypropylamine.
Ausbeute: 34 %Yield: 34%
1H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 6,6-7,0 (m, 4H), 6,5 (d, 1 H), 5,3 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 6.6-7.0 (m, 4H), 6.5 (d, 1 H), 5.3
(m, 1 H), 4,6 (s, 2H), 4,4-4,6 (m, 14H), 3,5 (s, 3H), 3,3-3,5 (m, 2H), 2,2(m, 1H), 4.6 (s, 2H), 4.4-4.6 (m, 14H), 3.5 (s, 3H), 3.3-3.5 (m, 2H) , 2.2
(d, 6H), 1 ,4 (d, 3H) ppm. Beispiel 94 3-Chlor-4-[1 -(4-difluormethoxyphenyl)]-propylamino-2-methoxymethylpyridin(d, 6H), 1.4 (d, 3H) ppm. Example 94 3-Chloro-4- [1 - (4-difluoromethoxyphenyl)] propylamino-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 1-(4-Difluormethoxyphenyl)-propylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 1- (4-difluoromethoxyphenyl) propylamine.
Ausbeute: 27 %Yield: 27%
1H-NMR (100 MHz, CDCI3): δ: 8,0 (d, 1 H), 7,2 (q, 4H), 6,5 (t, 1 H), 6,2 (d, 1 H), 1 H NMR (100 MHz, CDCI 3 ): δ: 8.0 (d, 1 H), 7.2 (q, 4H), 6.5 (t, 1 H), 6.2 (d, 1 H),
5.2 (d, 1 H), 4,6 (s, 2H), 4,3 (m, 1 H), 3,5 (s, 3H), 1 ,9 (m, 2H), 1 ,0 (t, 3H) ppm.5.2 (d, 1H), 4.6 (s, 2H), 4.3 (m, 1H), 3.5 (s, 3H), 1, 9 (m, 2H), 1, 0 (t , 3H) ppm.
Beispiel 95Example 95
3-Chlor-4-[2-methyl-3-(4-tert.-butylphenyl)]-propylamino-2-methoxymethyl- pyridin3-chloro-4- [2-methyl-3- (4-tert-butylphenyl)] propylamino-2-methoxymethylpyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 2-Methyl-3-(4-tert.-Butylphenyl)-propylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2-methyl-3- (4-tert-butylphenyl) propylamine.
Ausbeute: 54 %Yield: 54%
1H-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 7,2 (m, 4H), 6,3 (d, 1 H), 4,9 (m, 1 H NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.2 (m, 4H), 6.3 (d, 1 H), 4.9 (m,
1 H), 4,6 (s, 2H), 3,5 (s, 3H), 3,1 (m, 2H), 2,5-2,7 (m, 2H), 1 ,9-2,2 (m, 1 H),1 H), 4.6 (s, 2H), 3.5 (s, 3H), 3.1 (m, 2H), 2.5-2.7 (m, 2H), 1, 9-2, 2 (m, 1 H),
1.3 (s, 9H), 1 ,0 (d, 3H) ppm.1.3 (s, 9H), 1.0 (d, 3H) ppm.
Beispiel 96Example 96
3-Chlor-4-[2-(2,3-dimethyl-4-ethoxyethylphenoxy)]-ethylamino-2- methoxymethyl-pyridin3-chloro-4- [2- (2,3-dimethyl-4-ethoxyethylphenoxy)] ethylamino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 2(2,3-Dimethyl-4-ethoxyethyl)phenoxy-ethylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2 (2,3-dimethyl-4-ethoxyethyl) phenoxyethylamine.
Ausbeute: 13 %Yield: 13%
1 H-NMR (100 MHz, CDCI3): δ: 8,2 (d, 1 H), 6,8 (q, 2H), 6,3 (d, 1 H), 5,4 1 H NMR (100 MHz, CDCI 3 ): δ: 8.2 (d, 1 H), 6.8 (q, 2H), 6.3 (d, 1 H), 5.4
(m, 1 H), 4,6 (s, 2H), 4,2 (t, 2H), 3,4-3,7 (m, 8H), 3,5 (s, 3H), 2,8-3,0 (m, 2H),(m, 1H), 4.6 (s, 2H), 4.2 (t, 2H), 3.4-3.7 (m, 8H), 3.5 (s, 3H), 2.8 -3.0 (m, 2H),
2,2 (s, 3H), 2,2 (s, 3H), 1 ,2 (t, 3H) ppm. Beispiel 97 3-Chlor-4-[cis-4-butyl-cyclohexyl]amino-2-methoxymethylpyridin2.2 (s, 3H), 2.2 (s, 3H), 1, 2 (t, 3H) ppm. Example 97 3-Chloro-4- [cis-4-butylcyclohexyl] amino-2-methoxymethylpyridine
undand
Beispiel 98 3-Chlor-4-[trans-4-butyl-cyclohexyl]amino-2-methoxymethyl-pyridinExample 98 3-Chloro-4- [trans-4-butylcyclohexyl] amino-2-methoxymethylpyridine
wurden hergestellt analog Beispiel 89/90 aus 2-Methoxymethyl-3,4-dichlor- pyridin und 4-cis/trans-Butyl-cyclohexylamin.were prepared analogously to Example 89/90 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis / trans-butyl-cyclohexylamine.
Ausbeute: 12 % (cis-lsomer)Yield: 12% (cis isomer)
^-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 6,4 (d, 1 H), 5,0 (d, 1 H), 4,6 (s,^ -NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 6.4 (d, 1 H), 5.0 (d, 1 H), 4.6 (s,
2H), 3,7 (m, 1 H), 3,5 (s, 3H), 1 ,0-1 ,9 (m, 15H), 0,9 (t, 3H) ppm und2H), 3.7 (m, 1H), 3.5 (s, 3H), 1, 0-1, 9 (m, 15H), 0.9 (t, 3H) ppm and
Ausbeute: 9 % (trans-lsomer)Yield: 9% (trans isomer)
1H-NMR (100 MHz, CDCI3): δ 8,1 (d, 1 H), 6,5 (d, 1 H), 4,7 (d, 1 H), 4,6 (s, 1 H-NMR (100 MHz, CDCI 3 ): δ 8.1 (d, 1 H), 6.5 (d, 1 H), 4.7 (d, 1 H), 4.6 (s,
2H),3,5 (s, 3H), 3,2 (m, 1 H), 1 ,0-2,2 (m, 15H), 0,9 (t, 3H) ppm.2H), 3.5 (s, 3H), 3.2 (m, 1H), 1, 0-2.2 (m, 15H), 0.9 (t, 3H) ppm.
Beispiel 99 3-Chlor-4-[2-methyl-3(4-isopropylphenyl)]propylamino-2-methoxymethyl-pyridinExample 99 3-Chloro-4- [2-methyl-3 (4-isopropylphenyl)] propylamino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 2-Methyl-3(4-isopropylphenyl)propylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 2-methyl-3 (4-isopropylphenyl) propylamine.
Ausbeute: 33 %Yield: 33%
1H-NMR (100 MHz, CDCI3): δ: 8, 1 (d, 2H), 7,1 (m, 4H), 6,3 (d, 1 H), 4,9 (m, 1 H-NMR (100 MHz, CDCI 3 ): δ: 8, 1 (d, 2H), 7.1 (m, 4H), 6.3 (d, 1 H), 4.9 (m,
1 H), 4,6 (s, 2H), 3,5 (s, 3H), 2,0-3,2 (m, 6H), 1 ,2 (d, 6H), 1 ,0 (d, 3H) ppm. Beispiel 100 3-Chlor-4-[4-(4-fluorbenzyliden)cyclohexyl]amino-2-methoxymethyl-pyridin1 H), 4.6 (s, 2H), 3.5 (s, 3H), 2.0-3.2 (m, 6H), 1, 2 (d, 6H), 1, 0 (d, 3H) ppm. Example 100 3-Chloro-4- [4- (4-fluorobenzylidene) cyclohexyl] amino-2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 84 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4[4(4-Fluorbenzyliden)]cyclohexylamin.was prepared analogously to Example 84 from 2-methoxymethyl-3,4-dichloropyridine and 4 [4 (4-fluorobenzylidene)] cyclohexylamine.
Ausbeute: 39 %Yield: 39%
^-NMR (100 MHz, CDCI3): δ: 8,1 (d, 1 H), 7, 1 (m, 4H), 6,5 (d, 1 H), 6,3 (s,^ -NMR (100 MHz, CDCI 3 ): δ: 8.1 (d, 1 H), 7.1 (m, 4H), 6.5 (d, 1 H), 6.3 (s,
1 H), 4,8 (d, 1 H), 4,6 (s, 2H), 3,6 (m, 1 H), 3,5 (s, 3H), 1 ,2-2,9 (m, 8H) ppm.1 H), 4.8 (d, 1 H), 4.6 (s, 2H), 3.6 (m, 1 H), 3.5 (s, 3H), 1, 2-2.9 ( m, 8H) ppm.
Beispiel 101Example 101
3-Chlor-4-[4-cis(1-cyclohexyl-1-trifluormethyl-2,2,2-trifluorethyl)cyclohexyloxy]-3-chloro-4- [4-cis (1-cyclohexyl-1-trifluoromethyl-2,2,2-trifluoroethyl) cyclohexyloxy] -
2-methoxymethyl-pyridin2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 1 1 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-cis(1-cyclohexyl-1-trifluormethyl-2,2,2-trifluorethyl)cyclohexanol. Ausbeute: 1 1 %was prepared analogously to Example 1 1 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis (1-cyclohexyl-1-trifluoromethyl-2,2,2-trifluoroethyl) cyclohexanol. Yield: 1 1%
1 H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 6,9 (d, 1 H), 4,7 (m, 1 H), 4,7 (s, 2H), 3,5 (s, 3H), 1 ,1 -2,3 (m, 20H) ppm. 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 6.9 (d, 1 H), 4.7 (m, 1 H), 4.7 (s, 2H), 3.5 (s, 3H), 1.1-2.3 (m, 20H) ppm.
Beispiel 102Example 102
3-Chlor-4-[4-cis-(1 -cyclohexyl- 1-methyl-ethyl)-cyclohexyloxy]-2-methoxymethyl- pyridin3-chloro-4- [4-cis- (1 -cyclohexyl-1-methyl-ethyl) -cyclohexyloxy] -2-methoxymethyl-pyridine
wurde hergestellt analog Beispiel 1 1 aus 2-Methoxymethyl-3,4-dichlorpyridin und 4-cis-(1-cyclohexyl-1-methyl-ethyl)-cyclohexyloxy]-2-methoxymethyl-pyridin Ausbeute: 23 % 1H-NMR (100 MHz, CDCI3): δ: 8,3 (d, 1 H), 6,8 (d, 1 H), 4,7 (m, 1 H), 4,6 (s, 2H), 3,5 (s, 3H), 0,8-2, 1 (m, 20H), 0,8 (s, 6H) ppm.was prepared analogously to Example 1 1 from 2-methoxymethyl-3,4-dichloropyridine and 4-cis- (1-cyclohexyl-1-methyl-ethyl) -cyclohexyloxy] -2-methoxymethyl-pyridine Yield: 23% 1 H-NMR (100 MHz, CDCI 3 ): δ: 8.3 (d, 1 H), 6.8 (d, 1 H), 4.7 (m, 1 H), 4.6 (s, 2H), 3.5 (s, 3H), 0.8-2, 1 (m, 20H), 0.8 (s, 6H) ppm.
Beispiel 103Example 103
2-Methoxy-3-cyano-4-(cis 4-tert. butyl-cyclohexylamino)pyridin2-methoxy-3-cyano-4- (cis 4-tert-butyl-cyclohexylamino) pyridine
1 ,63 g (5,96 mMol) 3-Cyano-4-(cis-4-tert. butyl-cyclohexylamino)-pyridon-(2) in 30 ml Methylenchlorid werden mit 0,93 g (6,26 in Mol) Trimethyloxoninium- tetrafluoroborat versetzt und 75 Minuten bei Raumtemperatur gerührt. Nach der Zugabe von 10 g Eis, 5 ml 2N Natriumhydroxy und dem Abdampfen des Methylenchlorids wird das Reaktionsprodukt mit Ethylacetat extrahiert. Die Reinigung erfolgt durch Säulenchromatographie. Ausbeute: 1 ,25 g (73 %); Rf = 0,51 (Diisopropylether) Fp. 1 13°C1.63 g (5.96 mmol) of 3-cyano-4- (cis-4-tert-butyl-cyclohexylamino) -pyridone- (2) in 30 ml of methylene chloride are mixed with 0.93 g (6.26 in mol) Trimethyloxoninium tetrafluoroborate were added and the mixture was stirred at room temperature for 75 minutes. After the addition of 10 g of ice, 5 ml of 2N sodium hydroxide and the evaporation of the methylene chloride, the reaction product is extracted with ethyl acetate. The purification is carried out by column chromatography. Yield: 1.25 g (73%); R f = 0.51 (diisopropyl ether) mp 1 13 ° C
1H-NMR (CDCI3): δ: 7,90 (d, 1 H), 6,22 (d, 1 H), 5,16 (d, 1 H), 3,80 (m, 1 H), 4,0 (s, 3H), 1 ,0-2,0 (m, 9H), 0,90 (s, 9H) ppm. 1 H-NMR (CDCI 3 ): δ: 7.90 (d, 1 H), 6.22 (d, 1 H), 5.16 (d, 1 H), 3.80 (m, 1 H) , 4.0 (s, 3H), 1.0-2.0 (m, 9H), 0.90 (s, 9H) ppm.
Beispiel 104Example 104
2-Chlor-3-cyano-4-(cis 4-tert. butyl-cyclohexylamino)-pyridin2-chloro-3-cyano-4- (cis 4-tert-butyl-cyclohexylamino) pyridine
Zu 0,4 g (1 ,46 mMol) 3-Cyano-4-(cis 4-tert. butyl-cyclohexylamino)-pyridin-(2) werden 5 ml Phosphoroxychlond und 3 Tropfen Dimethylformamid gegeben und5 ml of phosphorus oxychloride and 3 drops of dimethylformamide are added to 0.4 g (1.46 mmol) of 3-cyano-4- (cis 4-tert.butylcyclohexylamino) pyridine- (2) and
3 Stunden bis zum Rückfluß erwärmt. Anschließend wird das überschüssigeHeated to reflux for 3 hours. Then the excess
Phosphoroxychlorid im Vakuum abdestilliert, der Rückstand mit Eiswasser versetzt, die wäßrige Lösung mit 32 %iger Natriumhydroxidlösung auf pH 7,5-8 gestellt und mit Ethylacetat das Reaktionsprodukt extrahiert. Die Reinigung erfolgt durch Säulenchromatographie.Phosphorus oxychloride was distilled off in vacuo, ice water was added to the residue, the aqueous solution was adjusted to pH 7.5-8 with 32% sodium hydroxide solution and the reaction product was extracted with ethyl acetate. The purification is carried out by column chromatography.
Ausbeute: 0,24 g (56 %); Rf = 0,35 (Diisopropylether)Yield: 0.24 g (56%); R f = 0.35 (diisopropyl ether)
Fp. 150°CMp 150 ° C
1H-NMR (CDCI3): δ 8,06 (d, 1 H), 6,48 (d, 1 H), 5,34 (d, 1 H), 3,80 (m, 1 ), 1 H-NMR (CDCI 3 ): δ 8.06 (d, 1 H), 6.48 (d, 1 H), 5.34 (d, 1 H), 3.80 (m, 1),
1 ,0-2,0 (m, 9H), 0,88 (s, 9H) ppm Beispiel 105 2-Methoxy-3-cyano-4-n-octylamino-pyridin1.0-2.0 (m, 9H), 0.88 (s, 9H) ppm Example 105 2-methoxy-3-cyano-4-n-octylamino-pyridine
wie Beispiel 103 aus 3-Cyano-4-n-octylaminopyridon-(2)as example 103 from 3-cyano-4-n-octylaminopyridone- (2)
Ausbeute: 55 %; Fp. = 104°CYield: 55%; Mp = 104 ° C
1H-NMR (CDCI3): δ: 7,91 (d, 1 H, 6,22 (d, 1 H), 5,00 (m, 1 H), 3,98 (s, 3H), 1 H-NMR (CDCI 3 ): δ: 7.91 (d, 1 H, 6.22 (d, 1 H), 5.00 (m, 1 H), 3.98 (s, 3H),
3,23 (m, 2H), 1 ,2 bis 1 ,8 (m, 12H), 0,88 (t, 3H) ppm3.23 (m, 2H), 1.2 to 1.8 (m, 12H), 0.88 (t, 3H) ppm
Beispiel 106 2-Chlor-3-cyano-4-n-octylamino-pyridinExample 106 2-Chloro-3-cyano-4-n-octylamino-pyridine
wie Beispiel 104 aus 3-Cyano-4-n-octylaminopyridon-(2)as example 104 from 3-cyano-4-n-octylaminopyridone- (2)
Ausbeute: 87 %; Fp. = 85 °CYield: 87%; Mp = 85 ° C
^-NMR (CDCI3): δ: 8,06, (d, 1 H), 6,50 (d, 1 H, 5,45 (m, 1 H), 3,28 (m, 2H),^ -NMR (CDCI 3 ): δ: 8.06, (d, 1 H), 6.50 (d, 1 H, 5.45 (m, 1 H), 3.28 (m, 2H),
1 ,2 bis 1 ,8 (m, 12H), 0,88 (t, 3H)1, 2 to 1, 8 (m, 12H), 0.88 (t, 3H)
Beispiel 107 2-Methoxy-3-cyano-4-(cis-4-phenyl-cyclohexylamino)-pyridinExample 107 2-methoxy-3-cyano-4- (cis-4-phenyl-cyclohexylamino) pyridine
wie Beispiel 103 aus 3-Cyano-4-(cis-4-phenyl-cyclohexylamino)pyridon-(2) Ausbeute: 80 %as example 103 from 3-cyano-4- (cis-4-phenyl-cyclohexylamino) pyridone- (2) yield: 80%
1H-NMR (CDCI3): δ: 7,92 (d, 1 H), 7,18 bis 7,38 (m, 5H), 6,28 (d, 1 H), 5,24 (d, 1 H), 3,98 (s, 3H), 3,87 (m, 1 H), 2,63 (m, 1 H), 1 ,6 bis 2,05 (m, 8H) ppm 1 H-NMR (CDCI3): δ: 7.92 (d, 1 H), 7.18 to 7.38 (m, 5H), 6.28 (d, 1 H), 5.24 (d, 1 H), 3.98 (s, 3H), 3.87 (m, 1H), 2.63 (m, 1H), 1.6 to 2.05 (m, 8H) ppm
Beispiel 108 2-Chlor-3-cyano-4-(cis-4-phenyl-cyclohexylamino)-pyridinExample 108 2-Chloro-3-cyano-4- (cis-4-phenyl-cyclohexylamino) pyridine
wie Beispiel 104 aus 3-Cyano-4-(cis-4-phenyl-cyclohexylamino)pyridon-(2) Ausbeute: 85 %as example 104 from 3-cyano-4- (cis-4-phenyl-cyclohexylamino) pyridone- (2) yield: 85%
1H-NMR (CDCI3): δ: 8,08 (d, 1 H), 7, 16 bis 7,36 (m, 5H), 6,55 (d, 1 H), 5,40 (d, 1 H), 3,88 (m, 1 H), 2,66 (m, 1 H), 1 ,60 bis 2,10 (m, 8H) ppm B. Formulierungsbeispiele 1 H NMR (CDCI3): δ: 8.08 (d, 1 H), 7, 16 to 7.36 (m, 5H), 6.55 (d, 1 H), 5.40 (d, 1 H), 3.88 (m, 1H), 2.66 (m, 1H), 1.60 to 2.10 (m, 8H) ppm B. Formulation examples
a) Ein Stäubemittel wird erhalten, indem man 10 Gew. -Teile Wirkstoff und 90 Gew. -Teile Talkum als Inertstoff mischt und in einer Schlagmühle zerkleinert.a) A dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill.
b) Ein in Wasser leicht dispergierbares, benetzbares Pulver wird erhalten, indem man 25 Gew. -Teile Wirkstoff, 65 Gew. -Teile kaolinhaltigen Quarz als Inertstoff, 10 Gew. -Teile ligninsulfonsaures Kalium und 1 Gew. -Teil oleylmethyltaurinsaures Natrium als Netz- und Dispergiermittel mischt und in einer Stiftmühle mahlt.b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as the inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill.
c) Ein in Wasser leicht dispergierbares Dispersionskonzentrat stellt man her, indem man 40 Gew. -Teile Wirkstoff mit 7 Gew. -Teilen eines sulfobernsteinsäurehalbesters, 2 Gew. -Teilen eines Ligninsulfonsäure-Natriumsalzes und 51 Gew. -Teilen Wasser mischt und in einer Reibkugelmühle auf eine Feinheit von unter 5 Mikron vermahlt.c) A dispersion concentrate which is easily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a sulfosuccinic acid half-ester, 2 parts by weight of a lignosulfonic acid sodium salt and 51 parts by weight of water and in a attritor ground to a fineness of less than 5 microns.
d) Ein emulgierbares Konzentrat läßt sich herstellen aus 15 Gew. -Teilen Wirkstoff, 75 Gew. -Teilen Cyclohexanon als Lösungsmittel undd) An emulsifiable concentrate can be prepared from 15 parts by weight of active ingredient, 75 parts by weight of cyclohexanone as solvent and
10 Gew. -Teilen oxethyliertem Nonylphenol (10 EO) als Emulgator.10 parts by weight of ethylated nonylphenol (10 EO) as an emulsifier.
e) Ein Granulat läßt sich herstellen aus 2 bis 15 Gew.-Teilen Wirkstoff und einem inerten Granulatträgermaterial wie Attapulgit, Bimsgranulat und/oder Quarzsand. Zweckmäßigerweise verwendet man eine Suspension des Spritzpulvers aus Beispiel b) mit einem Feststoffanteil von 30 und spritzt diese auf die Oberfläche eines Attapulgitgranulats, trocknet und vermischt innig. Dabei beträgt der Gewichtsanteil des Spritzpulvers ca. 5 und der des inerten Trägermaterials ca. 95 % des fertigen Granulats. C. Biologische Beispielee) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules and / or quartz sand. A suspension of the wettable powder from example b) having a solids content of 30 is expediently used and is sprayed onto the surface of an attapulgite granulate, dried and mixed intimately. The proportion by weight of the wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate. C. Biological examples
Beispiel 1 : Phytophthora infestansExample 1: Phytophthora infestans
Tomatenpflanzen der Sorte "Rheinlands Ruhm" wurden im 3 bis 4 Blattstadium mit wäßrigen Suspensionen der beanspruchten Verbindungen gleichmäßig tropfnaß benetzt. Nach dem Antrocknen wurden die Pflanzen mit einer Zoosporangien-Suspension von Phytophthora infestans inokuliert und für 2 Tage unter optimalen Infektionsbedingungen in einer Klimakammer gehalten. Danach wurden die Pflanzen bis zur Symptomausprägung im Gewächshaus weiterkultiviert. Die Befallsbonitur erfolgte ca. 1 Woche nach Inokulation. Der Befallsgrad der Pflanzen wurden in % befallener Blattfläche im Vergleich zu den unbehandelten, zu 100 % infizierten Kontrollpflanzen ausgedrückt.Tomato plants of the "Rheinlands Ruhm" cultivar were wetted to drip wet levels in the 3 to 4 leaf stage with aqueous suspensions of the claimed compounds. After drying, the plants were inoculated with a zoosporangia suspension of Phytophthora infestans and kept in a climatic chamber for 2 days under optimal infection conditions. The plants were then cultivated further in the greenhouse until the symptoms developed. The infection was assessed approximately 1 week after inoculation. The degree of infestation of the plants was expressed in% infected leaf area in comparison to the untreated, 100% infected control plants.
Bei 250 mg Wirkstoff/I Spritzbrühe zeigt die folgende Substanz eine vollständige Befallsunterdrückung:At 250 mg active ingredient / I spray mixture, the following substance shows complete suppression of the infection:
Verbindung aus Beispiel 6Compound from example 6
Beispiel 2: Plasmopara viticolaExample 2: Plasmopara viticola
Weinsämlinge der Sorten "Riesling/Ehrenfelder" wurden ca. 6 Wochen nach der Aussaat mit wäßrigen Suspensionen der beanspruchten Verbindungen tropfnaß behandelt. Nach dem Antrocknen des Spritzbelages wurden die Pf lanzen mit einer Zoosporangiensuspension von Plasmopara viticola inokuliert und tropfnaß für 4 bis 5 Stunden in eine Klimakammer mit 23°C und 80 bis 90 % rel. Luftfeuchte gestellt.Wine seedlings of the "Riesling / Ehrenfelder" varieties were treated to runoff with aqueous suspensions of the claimed compounds about 6 weeks after sowing. After the spray coating had dried on, the plants were inoculated with a zoosporangia suspension of Plasmopara viticola and dripping wet for 4 to 5 hours in a climatic chamber at 23 ° C. and 80 to 90% rel. Humidity set.
Nach einer Inkubationszeit von 7 Tagen im Gewächshaus wurden die Pflanzen nochmals über Nacht in die Klimakammer gestellt, um die Sporulation des Pilzes anzuregen. Anschließend erfolgte die Befallsauswertung. Der Befallsgrad wurde in % befallener Blattfläche im Vergleich zu den unbehandelten, zu 100 % infizierten Kontrollpflanzen ausgedrückt.After an incubation period of 7 days in the greenhouse, the plants were again placed in the climatic chamber overnight in order to stimulate the sporulation of the fungus. The infestation was then assessed. The degree of infestation was expressed in% affected leaf area compared to the untreated, 100% infected control plants.
Bei 250 mg Wirkstoff/I Spritzbrühe zeigt die folgende Substanz eine vollständige Befallsunterdrückung:At 250 mg active ingredient / I spray mixture, the following substance shows complete suppression of the infection:
Verbindung aus Beispiel 5Compound from example 5
Beispiel 3: Pyrenophora teresExample 3: Pyrenophora teres
Gerstenpflanzen der Sorte "Igri" wurden im 2-Blatt-Stadium mit einer wäßrigen Suspension der beanspruchten Verbindungen tropfnaß behandelt. Nach dem Antrocknen des Spritzbelages wurden die Pflanzen mit einer wäßrigen Sporensuspension von Pyrenophora teres inokuliert und für 16 Stunden in einer Klimakammer bei 100 % rel. Luftfeuchte inkubiert. Anschließend wurden die infizierten Pflanzen im Gewächshaus bei 25 °C und 80 % rel. Luftfeuchte weiterkultiviert.Barley plants of the "Igri" variety were treated to runoff with an aqueous suspension of the claimed compounds at the 2-leaf stage. After the spray coating had dried on, the plants were inoculated with an aqueous spore suspension of Pyrenophora teres and for 16 hours in a climatic chamber at 100% rel. Incubated humidity. The infected plants were then in a greenhouse at 25 ° C and 80% rel. Humidity continued to be cultivated.
Ca. 1 Woche nach Inokulation wurde der Befall ausgewertet und der Befallsgrad in % befallener Blattfläche im Vergleich zu unbehandelten, zu 100 % infizierten Kontrollen bonitiert.Approximately The infestation was evaluated 1 week after inoculation and the degree of infestation in% affected leaf area compared to untreated, 100% infected controls.
Bei 250 mg/l Spritzbrühe zeigt die folgende Substanz eine vollständige Befallsunterdrückung:At 250 mg / l spray mixture, the following substance shows complete suppression of the infection:
Verbindugn aus Beispiel 18Compound from Example 18
Beispiel 4: Erysiphe graminisExample 4: Erysiphe graminis
Gerstenpflanzen wurden im 3-Blattstadium mit Konidien des Gerstenmehltaus (Erysiphe graminis f. sp. hordei) stark inokuliert und in einem Gewächshaus bei 20°C und einer relativen Luftfeuchte von 90 bis 95 % aufgestellt. 24 Stunden nach Inokulation wurden die Pflanzen mit den nachfolgend aufgeführten Verbindungen in den angegebenen Wirkstoffkonzentrationen gleichmäßig benetzt. Nach einer Inkubationszeit von 10 Tagen wurden die Pflanzen auf Befall mit Gerstenmehltau untersucht. Der Befallsgrad wurde in % befallener Blattfläche im Vergleich zu unbehandelten, zu 100 % infizierten Kontrollpflanzen ausgedrückt.Barley plants were heavily inoculated in the 3-leaf stage with conidia of barley mildew (Erysiphe graminis f. Sp. Hordei) and placed in a greenhouse at 20 ° C and a relative humidity of 90 to 95%. 24 hours after inoculation, the plants were wetted uniformly with the compounds listed below in the stated active compound concentrations. After an incubation period of 10 days, the plants were examined for infestation with barley mildew. The degree of infestation was expressed in% infected leaf area compared to untreated, 100% infected control plants.
Bei 250 mg Wirkstoff/I Spritzbrühe zeigen die folgenden Substanzen eine vollständige Befallsunterdrückung:At 250 mg active ingredient / I spray liquor, the following substances show complete suppression of infestation:
Verbindung aus Beispiel 6 und Beispiel 5Compound from Example 6 and Example 5
Beispiel 5:Example 5:
Mit Bohnenspinnmilben (Tetranychus urticae, Vollpopulation) stark befallene Bohnenpflanzen (Phaseolus v.) wurden mit der wässrigen Verdünnung eines Spritzpulverkonzentrates, das 250 ppm des jeweiligen Wirkstoffes enthielt, gespritzt.Bean plants heavily infested with bean spider mites (Tetranychus urticae, full population) (Phaseolus v.) Were sprayed with the aqueous dilution of a wettable powder concentrate which contained 250 ppm of the respective active ingredient.
Die Mortalität der Milben wurde nach 7 Tagen kontrolliert. 100 % Abtötung wurde mit den Verbindungen gemäß Beispiel 5 und 1 1 erreicht.The mite's mortality was checked after 7 days. 100% kill was achieved with the compounds according to Examples 5 and 11.
Beispiel 6:Example 6:
Mit Schwarzer Bohnenblattlaus (Aphis fabae) stark besetzte Ackerbohnen (Vicia faba) werden mit wäßrigen Verdünnungen von Spritzpulverkonzentraten mit 250 ppm Wirkstoffgehalt bis zum Stadium des beginnenden Abtropfens besprüht. Die Mortalität der Blattläuse wird nach 3 Tagen bestimmt. Eine 100 %ige Abtötung kann mit den Verbindungen gemäß Beispiel 6 und 5 erzielt werden. Beispiel 7:Field beans (Vicia faba) heavily infested with black bean aphid (Aphis fabae) are sprayed with aqueous dilutions of wettable powder concentrates with an active substance content of 250 ppm until the stage of dripping begins. The aphid mortality is determined after 3 days. A 100% kill can be achieved with the compounds according to Examples 6 and 5. Example 7:
Mit Weißer Fliege (Trialeurodes vaporariorum) stark besetzte Bohnenpflanzen wurden mit wäßrigen Suspensionen von Spritzpuiverkonzentraten (250 ppm Wirkstoffgehalt) bis zum beginnenden Abtropfen gespritzt. Nach Aufstellung der Pflanzen im Gewächshaus erfolgte nach 14 Tagen die mikroskopische Kontrolle mit dem Ergebnis jeweils 100 %iger Mortalität bei den Präparaten mit den Wirkstoffen der Beispiele 6, 5 und 1 1.Bean plants heavily infested with whitefly (Trialeurodes vaporariorum) were sprayed with aqueous suspensions of spray concentrate (250 ppm active ingredient content) until drip started. After the plants had been placed in the greenhouse, microscopic control was carried out after 14 days, with the result in each case 100% mortality in the preparations with the active compounds of Examples 6, 5 and 11.
Beispiel 8:Example 8:
L3-Larven der Käferart Diabrotica undecimpunctata wurden auf Filterpapierscheiben gesetzt, die mit je 2 ml einer wäßrigen Verdünnung eines Spritzpulverkonzentrates das 250 ppm Wirkstoff enthielt, getränkt waren und in verschlossenen Petrischalen bei Raumtemperatur (23 °C) 3 Tage aufbewahrt. Danach wurde die Mortalität der Larven kontrolliert.L3 larvae of the beetle species Diabrotica undecimpunctata were placed on filter paper discs, each of which was soaked with 2 ml of an aqueous dilution of a wettable powder concentrate which contained 250 ppm of active ingredient, and kept in sealed petri dishes at room temperature (23 ° C.) for 3 days. The larval mortality was then checked.
Eine 100 %ige Abtötung wurde mit Verbindungen gemäß den Beispielen 6 und 5 erreicht.A 100% kill was achieved with compounds according to Examples 6 and 5.
Beispiel 9:Example 9:
24 Stunden alte Imagines der Stubenfliege (Musca domestica) wurden in Glasspetrischalen gesetzt. Boden und Deckel waren mit je 2 ml einer wäßrigen Verdünnung eines Spritzpulverkonzentrates, das 250 ppm Wirkstoff enthielt beschichtet worden. Durch Abtrocknen an der Luft war er als Belag auf den Glasflächen vorhanden.24-hour-old house fly (Musca domestica) adults were placed in glass petri dishes. Bottom and lid were each coated with 2 ml of an aqueous dilution of a wettable powder concentrate which contained 250 ppm of active ingredient. By drying in the air, it was present as a coating on the glass surfaces.
3 Stunden nach dem Aufsetzen der Tiere und dem Verschließen der Schalen wurde die Mortalität kontrolliert.Mortality was checked 3 hours after the animals had been put on and the trays closed.
Ein 100 %ige Abtötung wurde mit der Verbindung aus Beispiel 18 erreicht. Patentansprüche:A 100% kill was achieved with the compound from Example 18. Claims:
1. Verbindungen der Formel 1 und deren Salze,1. Compounds of formula 1 and their salts,
worin wherein
(1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend aus(1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, is selected from the group consisting of
R-O-CH2-,RO-CH 2 -,
R-O-CO-,R-O-CO-,
Halogen-(C1-C4)-alkoxymethyl,Halogen (C 1 -C 4 ) alkoxymethyl,
Halogen-(C.,-C4)-alkenyloxymethyl,Halogen- (C., - C 4 ) -alkenyloxymethyl,
Halogen-(C1-C )-alkoxycarbonyl,Halogen (C 1 -C) alkoxycarbonyl,
Halogen-(C,-C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist;Halogen (C, -C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4;
und die übrigen 4-x Reste R1, R2, R3 und R4, die gleich oder verschieden sind, ausgewählt werden aus der Gruppe bestehend ausand the remaining 4-x radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, are selected from the group consisting of
(CrC4)-Alkyl,(C r C 4 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(CrC4)-Alkoxy,(C r C 4 ) alkoxy,
(C2-C4)-Alkenyloxy,(C 2 -C 4 ) alkenyloxy,
Halogen-(CrC4)-alkyl,Halogen (C r C 4 ) alkyl,
Halogen-(C2-C4)-alkenyl,Halogen (C 2 -C 4 ) alkenyl,
Halogen-(C.|-C4)-alkoxy,Halogen (C. | -C 4 ) alkoxy,
Halogen-(C2-C4)-alkenyloxyHalogen (C 2 -C 4 ) alkenyloxy
(CrC4)-Alkylthio, (C r C 4 ) alkylthio,

Claims

(CrC4)-Alkylsulfinyl,(C r C 4 ) alkylsulfinyl,
(CrC4)-Alkylsu.fonyl.(C r C 4 ) alkylsu.fonyl.
Aryl, substituiertes Amino,Aryl, substituted amino,
Halogen undHalogen and
Wasserstoff;Hydrogen;
(1 ) (CrC10)-Alkyl,(1) (C r C 10 ) alkyl,
(C2-C10)-Alkenyl,(C 2 -C 10 ) alkenyl,
(C2-C10)-Alkinyl,(C 2 -C 10 ) alkynyl,
(C3-C8)-Cycloalkyl oder(C 3 -C 8 ) cycloalkyl or
Aralkyl bedeutet;Aralkyl;
Aryl wie unten unter (5a) definiert ist; Arylkyl Aryl-(CrC4)-alkyl bedeutet;Aryl as defined below under (5a); Arylkyl means aryl (C r C 4 ) alkyl;
(2) X O, S, NH, NR oder NOR bedeutet und R wie oben unter (1 ) definiert ist.(2) X denotes O, S, NH, NR or NOR and R is as defined under (1) above.
(3) Y - Z zusammen einen (C5-C ) Kohlenwasserstoff rest bedeutet, der unverzweigt oder verzweigt ist und bei dem eine oder mehrere, vorzugsweise bis zu drei CH2 durch Heteroatomgruppen wie O, NR5, S, SO, SO2 oder SiR6R7 ersetzt sein können, wobei R5 Wasserstoff, (C-,-C4)- Alkyl oder (C-|-C4)-Acyl, und R6 und R7, die gleich oder verschieden sind, unabhängig voneinander (C1-C4)-Alkyl, Phenyl oder substituiertes Phenyl bedeuten, und wobei dieser (C5-C12)-Kohlenwasserstoffrest mit den möglichen vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) gegebenenfalls mit einer oder mehreren, gleichen oder verschiedenen Resten aus der Reihe(3) Y - Z together means a (C 5 -C) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 is formed by heteroatom groups such as O, NR 5 , S, SO, SO 2 or SiR 6 R 7 can be replaced, wherein R 5 is hydrogen, (C -, - C 4 ) alkyl or (C- | -C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently from each other are (C 1 -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) hydrocarbon radical with the possible above-mentioned variations (replacement by heteroatom radical (s)) optionally with one or more, the same or various remnants from the series
(CrC7)-Alkyl,(C r C 7 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(C2-C4)-Alkinyl,(C 2 -C 4 ) alkynyl,
(C3-C7)-Cycloalkyl,(C 3 -C 7 ) cycloalkyl,
(C3-C7)-Cycloalkenyl,(C 3 -C 7 ) cycloalkenyl,
Halogen, Halogen-(CrC4)-alkyl, Halogen-(C1-C4)-alkoxy, Hydroxy undHalogen, Halogen (C r C 4 ) alkyl, halogen (C 1 -C 4 ) alkoxy, hydroxy and
(C1-C4)-Acyl, substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt,(C 1 -C 4 ) acyl is substituted; or, if not covered by the above definitions,
(4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren, gleichen oder verschiedenen Resten aus der Reihe(4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, one or more, identical or different radicals from the series
(CrC7)-Alkyl,(C r C 7 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(C3-C7)-Alkinyl,(C 3 -C 7 ) alkynyl,
(C3-C7)-Cycloalkyl,(C 3 -C 7 ) cycloalkyl,
(C3-C7)-Cycloalkenyl,(C 3 -C 7 ) cycloalkenyl,
Halogen,Halogen,
Halogen-(CrC4)-alkyl,Halogen (C r C 4 ) alkyl,
Halogen-fC- C^-alkoxy,Halogen-fC- C ^ -alkoxy,
Hydroxy undHydroxy and
(C,-C4)-Acyl substituiert ist; und(C, -C 4 ) acyl is substituted; and
(5) Z(5) Z
(a) Aryl, O-Aryl oder Aryl-(C C4)-alkyl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren, gleichen oder verschiedenen Resten aus der Reihe(a) Aryl, O-aryl or aryl- (CC 4 ) -alkyl, where aryl is a phenyl group, optionally with one or more, identical or different radicals from the series
Halogen,Halogen,
(C3-C8)-Cycloalkyl,(C 3 -C 8 ) cycloalkyl,
(C3-C8)-Cycloalkenyl,(C 3 -C 8 ) cycloalkenyl,
Phenoxy, substituiertes Phenoxy,Phenoxy, substituted phenoxy,
Phenylthio, substituiertes Phenylthio,Phenylthio, substituted phenylthio,
Phenyl, substitutiertes Phenyl, NO2, OPhenyl, substituted phenyl, NO 2 , O
-C-R8,-CR 8 ,
Acetoxy,Acetoxy,
Hydroxy,Hydroxy,
Cyano,Cyano,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
O-SiR9R10R1 1,O-SiR 9 R 10 R 1 1 ,
NR12R13 NR 12 R 13
S(O)R14,S (O) R 14 ,
SO2R14,SO 2 R 14 ,
(CrC12)-Alkyl,(C r C 12 ) alkyl,
(C2-C12)-Alkenyl,(C 2 -C 12 ) alkenyl,
(CrC12)-Alkoxy und(C r C 12 ) alkoxy and
(C.,-C12)-Alkylthio substituiert ist; und(C., - C 12 ) alkylthio is substituted; and
R8 (CrC7)-Alkyl, Halogen-(CrC7)-alkyl, (C3-C7)-Cycloalkyl,R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 3 -C 7 ) cycloalkyl,
Halogen-(C3-C7)-cycloalkyl, (C1-C7)-Alkoxy, Phenyl oder substituiertes Phenyl bedeutet;Halogen- (C 3 -C 7 ) cycloalkyl, (C 1 -C 7 ) alkoxy, phenyl or substituted phenyl;
R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C,-C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten;R 9 , R 10 and R 1 1 are identical or different and independently of one another are (C, -C 4 ) -alkyl, phenyl and / or substituted phenyl;
R12 und R13 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (C,-C4)-Alkyl und/oder (C1-C4)-Acyl bedeuten;R 12 and R 13 are identical or different and independently of one another are hydrogen, (C, -C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl;
R14 (CrCι0)-Alkyl, Phenyl oder substituiertes Phenyl bedeutet; wobei in (C.,-C12)-Alkyl, (C2-C12)-Alkenyl, (CrC12)-Alkoxy undR 14 is (C r Cι 0 ) alkyl, phenyl or substituted phenyl; where in (C., - C 12 ) alkyl, (C 2 -C 12 ) alkenyl, (C r C 12 ) alkoxy and
(Cι-(C 2)-Alkylthio gegebenenfalls eine oder mehrere CH2-Gruppen durch CO und/oder Heteroatome/Gruppen, wie O, S, SO, SO2, NR5 oder SiR6R7 ersetzt sind;(C 1 -C 2 -alkylthio optionally one or more CH 2 groups are replaced by CO and / or heteroatoms / groups, such as O, S, SO, SO 2 , NR 5 or SiR 6 R 7 ;
R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (CrC12)-Alkylrest, der (CrC12)-Alkoxyrest und der (CrC12)- Alkylthiorest mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e) bzw. CO) außerdem mit einer oder mehreren gleichen oder verschiedenen der nachstehenden Resten aus der Reihe Halogen, Halogen-(C1-C4)-alkoxy, Hydroxy, (C3-C8)- Cycloalkyl, (C3-C8)-Cycloalkenyl, (C1-C4)-Acyl, Phenoxy, substituiertes Phenoxy, Phenyl, substituiertes Phenyl, Phenylthio und substituiertes Phenylthio substituiert sein können; oder (b) (C3-C8)-Cycloalkyl oder (C5-C8)-Cycloalkenyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl- oder (C5-C8)-Cycloalkenyl-Rest gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der ReiheR 5 , R 6 and R 7 have the meaning as above under (3); the (C r C 12) -alkyl (C r C 12) alkoxy and (C r C 12) - alkylthio group, with or without the aforementioned variations (replacement by heteroatom radical (s) and CO) in addition with one or several identical or different of the following radicals from the series halogen, halogen (C 1 -C 4 ) alkoxy, hydroxy, (C 3 -C 8 ) cycloalkyl, (C 3 -C 8 ) cycloalkenyl, (C 1 - C 4 ) acyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio and substituted phenylthio may be substituted; or (b) is (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 is phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl radical, optionally with one or more identical or different radicals from the series
(CrC18)-Alkyl,(C r C 18 ) alkyl,
(C2-C18)-Alkenyl,(C 2 -C 18 ) alkenyl,
(CrC12)-Alkoxy,(C r C 12 ) alkoxy,
(C2-C12)-Acyl,(C 2 -C 12 ) acyl,
(C^C^J-Alkyl-oxycarbonyl,(C ^ C ^ J-alkyl-oxycarbonyl,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
NR16R17,NR 16 R 17 ,
Hydroxyl,Hydroxyl,
Oxo,Oxo,
Halogen,Halogen,
Aryl,Aryl,
(CrC18)-Alkandiyl,(C r C 18 ) alkanediyl,
(C,-C18)-Alkandiyldioxy(C, -C 18 ) alkanediyl dioxy
(C|-C.| 3)-Alkyl-oximino,(C | -C. | 3 ) alkyl oximino,
Aryl-(C1-C4)-alkyloximino undAryl- (C 1 -C 4 ) alkyloximino and
(C2-C18)-Alkyliden substituiert sind und in den genannten(C 2 -C 18 ) alkylidene are substituted and in the above
(CrC18)-, (C2-C18)-, (CrC12)-, (C2-C12)- und (CrC13)-(C r C 18 ) -, (C 2 -C 18 ) -, (C r C 12 ) -, (C 2 -C 12 ) - and (C r C 13 ) -
Kohlenwasserstoff-Resten eine oder mehrere CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 8, vorzugsweise 3 bis 6 C-Atome und gegebenenfalls Heteroatomreste dieser Kohlenwasserstoff-Reste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren, vorzugsweise bis zu drei, im Falle von Halogen bis zur Maximalanzahl an gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl, substituiertes Phenyl, Phenylthio und substituiertes Phenylthio substituiert sind; R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben; und R16 und R17 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (C.|-C6)-Alkyl, (C-|-C6)- Alkoxy, (CrC4)-Acyl, (C3-C6)-Cycloalkyl, Phenyl und substituiertes Phenyl bedeuten.Hydrocarbon residues one or more CH 2 groups can be replaced by heteroatoms / groups such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as in (3) and moreover 3 to 8, preferably 3 to 6, C atoms and optionally heteroatom radicals of these hydrocarbon radicals can form a cycle and these hydrocarbon radicals with or without the variations (replacement by heteroatom radical (s) and / or cycle formation) optionally with one or more, preferably up to three, in the case of halogen up to Maximum number of identical or different radicals from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl, substituted phenyl, phenylthio and substituted phenylthio are substituted; R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a); and R 16 and R 17 are identical or different and independently of one another are hydrogen, (C. | -C 6 ) -alkyl, (C- | -C 6 ) -alkoxy, (C r C 4 ) -acyl, (C 3 - C 6 ) cycloalkyl, phenyl and substituted phenyl.
2. Verbindungen der Formel 1 gemäß Anspruch 1 und deren Salze, worin (1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend aus2. Compounds of formula 1 according to claim 1 and their salts, wherein (1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, is selected from the group consisting of
R-O-CH2-,RO-CH 2 -,
R-O-CO-,R-O-CO-,
Halogen-(C1-C4)-alkoxymethyl,Halogen (C 1 -C 4 ) alkoxymethyl,
Halogen-(C1-C4)-alkenyloxymethyl,Halogen (C 1 -C 4 ) alkenyloxymethyl,
Halogen-(C|-C4)-alkoxycarbonyl,Halogen (C | -C 4 ) alkoxycarbonyl,
Halogen-(C1-C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist; und die übrigen 4-x Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt werden aus der Gruppe bestehend ausHalogen (C 1 -C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4; and the remaining 4-x radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, are selected from the group consisting of
(CrC4)-Alkyl,(C r C 4 ) alkyl,
(C2-C4)-Alkenyl,(C 2 -C 4 ) alkenyl,
(CrC4)-Alkoxy,(C r C 4 ) alkoxy,
(C2-C4)-Alkenyloxy,(C 2 -C 4 ) alkenyloxy,
Halogen-(CrC4)-alkyl,Halogen (C r C 4 ) alkyl,
Halogen-(C2-C4)-alkenyl,Halogen (C 2 -C 4 ) alkenyl,
Halogen-(CrC4)-alkoxy,Halogen (C r C 4 ) alkoxy,
Halogen-(C2-C4)-alkenyloxyHalogen (C 2 -C 4 ) alkenyloxy
(CrC4)-Alkylthio,(C r C 4 ) alkylthio,
(CrC4)-Alkylsulfinyl,(C r C 4 ) alkylsulfinyl,
(CrC4)-Alkylsulfonyl,(C r C 4 ) alkylsulfonyl,
Aryl, substituiertes Amino,Aryl, substituted amino,
Halogen undHalogen and
Wasserstoff; R (CrC7)-Alkyl,Hydrogen; R (C r C 7 ) alkyl,
(C2-C7)-Alkenyl,(C 2 -C 7 ) alkenyl,
(C2-C7)-Alkinyl,(C 2 -C 7 ) alkynyl,
(C3-C6)-Cycloalkyl bedeutet;Is (C 3 -C 6 ) cycloalkyl;
(2) X O, S, NH, NR oder NOR bedeutet und R wie oben unter (1 ) definiert ist.(2) X denotes O, S, NH, NR or NOR and R is as defined under (1) above.
(3) Y - Z zusammen wie im Anspruch 1 definiert ist und gegebenenfalls mit einer oder mehreren gleichen oder verschiedenen Resten aus der Reihe(3) Y - Z together as defined in claim 1 and optionally with one or more identical or different radicals from the series
(CrC7)-Alkyl, Halogen,(C r C 7 ) alkyl, halogen,
Halogen-(CrC4)-alkyl, Halogen-(C1-C4)-alkoxy und (C1-C4)-Acyl substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt, (4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren gleichen oder verschiedenen Resten aus der ReiheHalogen (C r C 4 ) alkyl, halogen (C 1 -C 4 ) alkoxy and (C 1 -C 4 ) acyl; or, if not covered by the above definitions, (4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, one or more identical or different radicals from the series
(CrC7)-Alkyl, Halogen,(C r C 7 ) alkyl, halogen,
Halogen-(C1-C4)-alkyl und Halogen-(C1-C4)-alkoxy substituiert ist; undHalogen (C 1 -C 4 ) alkyl and halogen (C 1 -C 4 ) alkoxy is substituted; and
(5) Z(5) Z
(a) Aryl, O-Aryl oder Aryl-(C1-C4)-alkyl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der Reihe(a) Aryl, O-aryl or aryl- (C 1 -C 4 ) -alkyl, where aryl is a phenyl group, optionally with one or more identical or different radicals from the series
Halogen,Halogen,
(C3-C8)-Cycloalkyl,(C 3 -C 8 ) cycloalkyl,
(C3-C8)-Cycloalkenyl,(C 3 -C 8 ) cycloalkenyl,
Phenoxy, substituiertes Phenoxy,Phenoxy, substituted phenoxy,
Phenyl, substitutiertes Phenyl, OPhenyl, substituted phenyl, O
-C-R8,-CR 8 ,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
O-SiR9R10R1 1 ,O-SiR 9 R 10 R 1 1 ,
NR12R13 NR 12 R 13
(C1-Cl 2)-Alkyl,(C 1 -C l 2 ) alkyl,
(C2-C12)-Alkenyl und(C 2 -C 12 ) alkenyl and
(C,-C12)-Alkoxy substituiert ist; und(C, -C 12 ) alkoxy is substituted; and
R8 (CrC7)-Alkyl, Halogen-(CrC7)-alkyl, (C5-C6)-Cycloalkyl, (Cr R 8 (C r C 7 ) alkyl, halogen (C r C 7 ) alkyl, (C 5 -C 6 ) cycloalkyl, (C r
C7)-Alkoxy, Phenyl oder substituiertes Phenyl bedeutet;C 7 ) alkoxy, phenyl or substituted phenyl;
R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C1-C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten;R 9 , R 10 and R 1 1 are the same or different and independent are (C 1 -C 4 ) alkyl, phenyl and / or substituted phenyl;
R12 und R13 gleich oder verschieden sind und unabhängig voneinander Wasserstoff, (C1-C4)-Alkyl und/oder (C1-C4)-Acyl bedeuten; wobei in (C C12)-Alkyl, (C2-C12)-Alkenyl und (C.,-C12)- Alkoxy gegebenenfalls eine oder mehrere CH2-Gruppen durch CO und/oder Heteroatome/Gruppen, wie O, S, SO, SO2, NR5 oder SiR6R7 ersetzt sind;R 12 and R 13 are identical or different and independently of one another are hydrogen, (C 1 -C 4 ) -alkyl and / or (C 1 -C 4 ) -acyl; where in (CC 12 ) alkyl, (C 2 -C 12 ) alkenyl and (C., - C 12 ) alkoxy optionally one or more CH 2 groups by CO and / or heteroatoms / groups, such as O, S , SO, SO 2 , NR 5 or SiR 6 R 7 are replaced;
R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (C.,-Cι2)-Alkylrest und der (C^C^J-Alkoxyrest mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e) bzw. CO) außerdem mit einer oder mehreren gleichen oder verschiedenen der nachstehenden Resten aus der Reihe Halogen, Halogen-(C C4)-alkoxy, (C3-C6)-Cycloalkyl, (C1-C4)-Acyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sein kann; oder Halogen F oder Cl bedeutet; (b) (C3-C6)-Cycloalkyl oder (C5-C8)-Cycloalkenyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl- oder (C5-C8)-Cycloalkenyl-Rest gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der ReiheR 5 , R 6 and R 7 have the meaning as above under (3); the (C., -Cι 2 ) alkyl radical and the (C ^ C ^ J-alkoxy radical with or without the aforementioned variations (replacement by heteroatom radical (s) or CO) also with one or more identical or different of the radicals below the series halogen, halogen (CC 4 ) alkoxy, (C 3 -C 6 ) cycloalkyl, (C 1 -C 4 ) acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl; or halogen F or Is Cl; (b) is (C 3 -C 6 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 is phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl or (C 5 -C 8 ) cycloalkenyl radical optionally with one or more identical or different radicals from the series
(CrC18)-Alkyl,(C r C 18 ) alkyl,
(C2-C18)-Alkenyl,(C 2 -C 18 ) alkenyl,
(CrC12)-Alkoxy,(C r C 12 ) alkoxy,
(C2-C12)-Acyl,(C 2 -C 12 ) acyl,
(C-| -C-, 2)-Alkyl-oxycarbony I,(C- | -C-, 2 ) -alkyloxycarbony I,
SiR9R10R1 1 ,SiR 9 R 10 R 1 1 ,
Hydroxyl,Hydroxyl,
Oxo,Oxo,
Halogen, Aryl,Halogen, Aryl,
(CrC18)-Alkandiyl, (Cj-C, 8)-Alkandiyldioxy (C-|-C13)-Alkyl-oximino, Aryl-(C1-C4)-alkyloximino und(C r C 18 ) alkanediyl, (C j -C, 8 ) alkanediyldioxy (C- | -C 13 ) alkyl oximino, aryl (C 1 -C 4 ) alkyloximino and
(C2-C18)-Alkyliden substituiert sind und in den genannten (C C18)-, (C2-C18)-, (C C12)-, (C2-C12)- und (Cj-C^)- Kohlenwasserstoff-Resten eine oder mehrere CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 6 C-Atome und gegebenenfalls Heteroatomreste dieser Kohlenwasserstoff- Reste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sind; R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben.(C 2 -C 18 ) alkylidene are substituted and in the (CC 18 ) -, (C 2 -C 18 ) -, (CC 12 ) -, (C 2 -C 12 ) - and (C j -C ^) - Hydrocarbon radicals one or more CH 2 groups can be replaced by heteroatoms / groups such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as in (3) and moreover 3 to 6 carbon atoms and optionally heteroatom residues of these hydrocarbon residues can form a cycle and these hydrocarbon residues with or without the variations (replacement by heteroatom residue (s) and / or cycle formation) optionally with one or more identical or different residues from the series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl; R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
3. Verbindungen der Formel 1 gemäß Anspruch 1 oder 2 und deren Salze, worin3. Compounds of formula 1 according to claim 1 or 2 and their salts, wherein
(1 ) die Anzahl x der Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt wird aus der Gruppe bestehend aus(1) the number x of the radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, is selected from the group consisting of
R-O-CH2-,RO-CH 2 -,
R-O-CO-,R-O-CO-,
Halogen-(C1-C4)-alkoxymethyl,Halogen (C 1 -C 4 ) alkoxymethyl,
Halogen-(C1-C4)-alkenyloxymethyl,Halogen (C 1 -C 4 ) alkenyloxymethyl,
Halogen-(C1-C4)-alkoxycarbonyl,Halogen (C 1 -C 4 ) alkoxycarbonyl,
Halogen-(C-,-C4)-alkenyloxycarbonyl und Cyano; und x 1 , 2, 3 oder 4 ist;Halogen (C -, - C 4 ) alkenyloxycarbonyl and cyano; and x is 1, 2, 3 or 4;
und die übrigen 4-x Reste R1 , R2, R3 und R4, die gleich oder verschieden sind, ausgewählt werden aus der Gruppe bestehend ausand the remaining 4-x radicals R 1 , R 2 , R 3 and R 4 , which are the same or different, are selected from the group consisting of
(CrC3)-Alkyl,(C r C 3 ) alkyl,
(C2-C3)-Alkenyl,(C 2 -C 3 ) alkenyl,
(C,-C3)-Alkoxy,(C, -C 3 ) alkoxy,
(C2-C5)-Alkenyloxy,(C 2 -C 5 ) alkenyloxy,
Halogen-(C1-C3)-alkyl,Halogen (C 1 -C 3 ) alkyl,
Halogen-(C2-C9)-alkenyl,Halogen (C 2 -C 9 ) alkenyl,
Halogen-(C1-C3)-alkoxy,Halogen (C 1 -C 3 ) alkoxy,
Halogen-(C2-C3)-alkenyloxyHalogen (C 2 -C 3 ) alkenyloxy
Halogen undHalogen and
Wasserstoff; R (CrC5)-Alkyl,Hydrogen; R (C r C 5 ) alkyl,
(C2-C5)-Alkenyl,(C 2 -C 5 ) alkenyl,
(C3-C6)-Cycloalkyl bedeutet;Is (C 3 -C 6 ) cycloalkyl;
(2) X O oder NH bedeutet;(2) X represents O or NH;
(3) Y - Z zusammen einen (C5-C12) Kohlenwasserstoffrest bedeutet, der unverzweigt oder verzweigt ist und bei dem eine oder mehrere, vorzugsweise bis zu drei CH2 durch Heteroatomgruppen wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5 (CrC4)-Acyl, und R6 und R7, die gleich oder verschieden sind, unabhängig voneinander (C,-C4)-Alkyl, Phenyl oder substituiertes Phenyl bedeuten, und wobei dieser (C5-C12)- Kohlenwasserstoffrest mit den möglichen vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) gegebenenfalls mit einer oder mehreren gleichen oder verschiedenen Resten aus der Reihe(3) Y - Z together means a (C 5 -C 12 ) hydrocarbon radical which is unbranched or branched and in which one or more, preferably up to three, CH 2 have been replaced by heteroatom groups such as O, NR 5 or SiR 6 R 7 where R 5 is (C r C 4 ) acyl, and R 6 and R 7 , which are the same or different, independently of one another are (C, -C 4 ) alkyl, phenyl or substituted phenyl, and wherein this (C 5 -C 12 ) - hydrocarbon radical with the possible aforementioned variations (replacement by heteroatom radical (s)), if appropriate with one or more identical or different radicals from the series
(CrC5)-Alkyl, Fluor, Chlor, Halogen-(C.,-C4)-alkyl und Halogen-(C1-C3)-alkoxy substituiert ist; oder, falls von den vorstehenden Definitionen nicht umfaßt,(C r C 5 ) alkyl, fluorine, chlorine, Halogen (C., - C 4 ) alkyl and halogen (C 1 -C 3 ) alkoxy is substituted; or, if not covered by the above definitions,
(4) Y eine Bindung oder ein bivalenter Kohlenwasserstoffrest mit 1 bis 6 C-Atomen ist, der mit einer oder mehreren gleichen oder verschiedenen Resten aus der Reihe(4) Y is a bond or a divalent hydrocarbon radical with 1 to 6 carbon atoms, one or more identical or different radicals from the series
(CrC5)-Alkyl, Fluor, Chlor(C r C 5 ) alkyl, fluorine, chlorine
Halogen-(C|-C3)-alkyl und Halogen-(C1-C4)-alkoxy substituiert ist; undHalogen (C | -C 3 ) alkyl and halogen (C 1 -C 4 ) alkoxy is substituted; and
(5) Z(5) Z
(a) Aryl oder O-Aryl bedeutet, wobei Aryl eine Phenylgruppe ist, die gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der Reihe(a) Aryl or O-aryl, where aryl is a phenyl group, optionally with one or more identical or different radicals from the series
Halogen,Halogen,
(C3-C6)-Cycloalkyl,(C 3 -C 6 ) cycloalkyl,
(C3-C8)-Cycloalkenyl,(C 3 -C 8 ) cycloalkenyl,
Phenoxy, substituiertes Phenoxy,Phenoxy, substituted phenoxy,
Phenyl, substituiertes Phenyl,Phenyl, substituted phenyl,
SiR9R10R1 1,SiR 9 R 10 R 1 1 ,
O-SiR9R10R1 1,O-SiR 9 R 10 R 1 1 ,
(CrC6)-Alkyl und(C r C 6 ) alkyl and
(C-|-C7)-Alkoxy substituiert ist; und(C- | -C 7 ) alkoxy is substituted; and
R9, R10 und R1 1 gleich oder verschieden sind und unabhängig voneinander (C1-C4)-Alkyl, Phenyl und/oder substituiertes Phenyl bedeuten; wobei (C- CgJ-Alkyl und (C-|-C7)-Alkoxy gegebenenfalls eine oder mehrere CH2-Gruppen durch Heteroatome/Gruppen, wie O, S, NR5 oder SiR6R7 ersetzt sind;R 9 , R 10 and R 1 1 are the same or different and independently of one another are (C 1 -C 4 ) alkyl, phenyl and / or substituted phenyl; where (C-CgJ-alkyl and (C- | -C 7 ) alkoxy) optionally one or more CH 2 groups are replaced by heteroatoms / groups such as O, S, NR 5 or SiR 6 R 7 ;
R5, R6 und R7 haben die Bedeutung wie oben unter (3); der (Cι-C6)-Alkylrest und der (C-,-C7)-Alkoxyreste mit oder ohne den vorgenannten Variationen (Ersatz durch Heteroatomrest(e)) außerdem mit einer oder mehreren gleichen oder verschiedenen der nachstehenden Resten aus der Reihe Halogen, (C5-C6)-Cycloalkyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl, substituiert sein kann; Halogen Fluor oder Chlor ist; oder (b) (C3-C6)-Cycloalkyl bedeutet, wobei eine CH2-Gruppe des Carbocyclus durch NR15 ersetzt sein kann; R15 Phenyl oder substituiertes Phenyl bedeutet und der (C3-C8)- Cycloalkyl-Rest gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der Reihe:R 5 , R 6 and R 7 have the meaning as above under (3); the (-CC 6 ) -alkyl radical and the (C -, - C 7 ) -alkoxy radicals with or without the abovementioned variations (replacement by heteroatom radical (s)) also with one or more identical or different of the radicals from the halogen series below , (C 5 -C 6 ) cycloalkyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl may be substituted; Halogen is fluorine or chlorine; or (b) denotes (C 3 -C 6 ) cycloalkyl, where a CH 2 group of the carbocycle can be replaced by NR 15 ; R 15 denotes phenyl or substituted phenyl and the (C 3 -C 8 ) cycloalkyl radical optionally with one or more identical or different radicals from the series:
(CrC12)-Alkyl,(C r C 12 ) alkyl,
(C2-C18)-Alkenyl,(C 2 -C 18 ) alkenyl,
(CrC12)-Alkoxy,(C r C 12 ) alkoxy,
(C2-C12)-Acyl,(C 2 -C 12 ) acyl,
(C1-Cl 2)-Alkyl-oxycarbonyl,(C 1 -C l 2 ) alkyloxycarbonyl,
SiR9R10R1 1,SiR 9 R 10 R 1 1 ,
Hydroxyl,Hydroxyl,
Oxo,Oxo,
Halogen,Halogen,
Aryl,Aryl,
(C,-C18)-Alkandiyl,(C, -C 18 ) alkanediyl,
(C C18)-Alkandiyldioxy(CC 18 ) alkanediyl dioxy
(C, -C8)-Alkyl-oximino,(C, -C 8 ) alkyl oximino,
Aryl-(C1-C4)-alkyloximino undAryl- (C 1 -C 4 ) alkyloximino and
(C2-C12)-Alkyliden substituiert sind und in den genannten(C 2 -C 12 ) alkylidene are substituted and in the above
(CrC12)-, (C2-C12)- und (CrC8)- Kohlenwasserstoff-Resten eine oder mehrere CH2-Gruppen durch Heteroatome/Gruppen, wie O, NR5 oder SiR6R7 ersetzt sein können, wobei R5, R6 und R7 die Bedeutung wie unter (3) haben und darüber hinaus 3 bis 6 C-Atome und/oder Heteroatomrest(e) dieser Kohlenwasserstoff-Reste einen Cyclus bilden können und diese Kohlenwasserstoff-Reste mit oder ohne den Variationen (Ersatz durch Heteroatomrest(e) und/oder Cyclusbildung) gegebenenfalls mit einem oder mehreren gleichen oder verschiedenen Resten aus der Reihe Halogen, Halogenalkyl, Cycloalkyl, Acyl, Phenoxy, substituiertes Phenoxy, Phenyl und substituiertes Phenyl substituiert sind; R9, R10, R1 1 und Aryl die Bedeutungen wie unter (5 a) haben.(C r C 12 ) -, (C 2 -C 12 ) - and (C r C 8 ) - hydrocarbon residues one or more CH 2 groups can be replaced by heteroatoms / groups such as O, NR 5 or SiR 6 R 7 , where R 5 , R 6 and R 7 have the meaning as in (3) and also 3 to 6 C -Atoms and / or heteroatom residue (s) of these hydrocarbon residues can form a cycle and these hydrocarbon residues with or without the variations (replacement by heteroatom residue (s) and / or cycle formation) optionally with one or more identical or different residues from the Series halogen, haloalkyl, cycloalkyl, acyl, phenoxy, substituted phenoxy, phenyl and substituted phenyl; R 9 , R 10 , R 1 1 and aryl have the meanings as under (5 a).
4. Verbindungen der Formel 1 gemäß einem der Ansprüche 1 bis 3 und deren Salze, worin die unter (5b) definierten Substituenten von Cycloalkyl oder Cycloalkenyl bezüglich Y cis-orientiert sind.4. Compounds of formula 1 according to any one of claims 1 to 3 and their salts, wherein the substituents of cycloalkyl or cycloalkenyl defined under (5b) are cis-oriented with respect to Y.
5. Verbindung gemäß Anspruch 4, die einen unter (5b) definierten Substituenten tragen, der sich in der 4-Position von Cyclohexyl befindet.5. A compound according to claim 4, which carry a substituent defined under (5b) which is in the 4-position of cyclohexyl.
6. Verfahren zur Herstellung von Verbindungen der Formel 1 , dadurch gekennzeichnet, daß man Verbindungen der Formel 26. A process for the preparation of compounds of formula 1, characterized in that compounds of formula 2
in der R1 , R2, R3 und R4 wie oben definiert sind und L eine Abgangsgruppe ist, mit den entsprechenden Aminen, Alkoholen, Phenolen oder Mercaptanen umsetzt, oder unter Bildung von Verbindungen der Formel 1 , worin Z wie unter (5b) definiert ist, solche Verbindungen der Formel 1 , worin R1 , R2, R3, R4, X und Y wie oben definiert sind und Z für einen ungesättigten carbocyclischen, wie Cycloalkyl oder Cycloalkenyl unter (5b) definiert substituierten Rest steht, hydriert, und die so erhaltenen Verbindungen der Formel 1 gegebenenfalls in ihr Salz überführt.in which R 1 , R 2 , R 3 and R 4 are as defined above and L is a leaving group, with the corresponding amines, alcohols, phenols or mercaptans, or to form compounds of the formula 1, in which Z is as described in (5b ) is defined, those compounds of formula 1, wherein R 1 , R 2 , R 3 , R 4 , X and Y are as defined above and Z is an unsaturated carbocyclic radical, such as cycloalkyl or cycloalkenyl under (5b), substituted, hydrogenated, and the compounds of formula 1 thus obtained are optionally converted into their salt.
7. Mittel enthaltend mindestens eine Verbindung gemäß einem der Ansprüche 1 bis 5 und mindestens ein Formulierungsmittel.7. Agent containing at least one compound according to one of claims 1 to 5 and at least one formulation agent.
8. Fungizides Mittel gemäß Anspruch 7, enthaltend eine fungizid wirksame Menge mindestens einer Verbindung gemäß einem der Ansprüche 1 bis 5 zusammen mit den für diese Anwendung üblichen Zusatz- oder Hilfsstoffen.8. Fungicidal composition according to claim 7, containing a fungicidally effective amount of at least one compound according to one of claims 1 to 5 together with the additives or auxiliaries customary for this application.
9. Insektizides, akarizides oder nematizides Mittel gemäß Anspruch 7, enthaltend eine wirksame Menge mindestens einer Verbindung gemäß einem der Ansprüche 1 bis 5 zusammen mit den für diese Anwendung üblichen Zusatz¬ oder Hilfsstoffen.9. Insecticidal, acaricidal or nematicidal composition according to claim 7, containing an effective amount of at least one compound according to one of claims 1 to 5 together with the additives or auxiliaries customary for this application.
10. Pflanzenschutzmittel, enthaltend eine fungizid, insektizid, akarizid oder nematizid wirksame Menge mindestens einer Verbindung gemäß einem der Ansprüche 1 bis 5 und mindestens einem weiteren Wirkstoff, vorzugsweise aus der Reihe der Fungizide, Insektizide, Lockstoffe, Sterilantien, Akarizide, Nematizide und Herbizide zusammen mit den für diese Anwendung üblichen Hilfs- und Zusatzstoffen.10. Plant protection agents containing a fungicidal, insecticidal, acaricidal or nematicidal effective amount of at least one compound according to one of claims 1 to 5 and at least one further active ingredient, preferably from the series of fungicides, insecticides, attractants, sterilants, acaricides, nematicides and herbicides together with the auxiliaries and additives customary for this application.
1 1 . Mittel zur Anwendung im Holzschutz oder als Konservierungsmittel in Dichtmassen, in Anstrichfarben, in Kühlschmiermitteln für die Metallbearbeitung oder in Bohr- und Schneidölen, enthaltend eine wirksame Menge mindestens einer Verbindung gemäß einem der Ansprüche 1 bis 5 zusammen mit den für diese Anwendungen üblichen Hilfs- und Zusatzstoffen. 1 1. Agents for use in wood protection or as preservatives in sealing compounds, in paints, in cooling lubricants for metalworking or in drilling and cutting oils, containing an effective amount of at least one compound according to one of claims 1 to 5 together with the auxiliaries and customary for these applications Additives.
12. Verbindung gemäß einem der Ansprüche 1 bis 5 oder Mittel gemäß Anspruch 7, zur Anwendung als Tierarzneimittel, vorzugsweise bei der Bekämpfung von Endo- oder Ektoparasiten.12. A compound according to any one of claims 1 to 5 or agent according to claim 7, for use as a veterinary medicinal product, preferably for combating endo- or ectoparasites.
13. Verfahren zur Herstellung eines Mittels gemäß einem der Ansprüche 7 bis 12, dadurch gekennzeichnet, daß man den Wirkstoff und die weiteren Zusätze zusammen gibt und in eine geeignete Anwendungsform bringt.13. A process for the preparation of an agent according to any one of claims 7 to 12, characterized in that the active ingredient and the other additives are added together and brought into a suitable form of use.
14. Verwendung einer Verbindung gemäß einem der Ansprüche 1 bis 5 oder Mittels gemäß einem der Ansprüche 7, 8, 10 und 1 1 als Fungizid.14. Use of a compound according to one of claims 1 to 5 or agent according to one of claims 7, 8, 10 and 1 1 as a fungicide.
15. Verwendung einer Verbindung der Formel 1 gemäß einem der Ansprüche 1 bis 5 oder eines Mittels gemäß einem der Ansprüche 7, 8 und 1 1 als Holzschutzmittel oder als Konservierungsmittel in Dichtmitteln, in Anstrichfarben, in Kühlschmiermitteln für die Metallbearbeitung oder in Bohr- und Schneidölen.15. Use of a compound of formula 1 according to one of claims 1 to 5 or an agent according to one of claims 7, 8 and 1 1 as a wood preservative or as a preservative in sealants, in paints, in cooling lubricants for metalworking or in drilling and cutting oils .
16. Verfahren zur Bekämpfung von phytopathogenen Pilzen, dadurch gekennzeichnet, daß man auf diese oder die von ihnen befallenen Pflanzen, Flächen oder Substrate oder auf Saatgut eine fungizid wirksame Menge einer Verbindung gemäß einem der Ansprüche 1 bis 5 oder eines Mittels gemäß einem der Ansprüche 7, 8, 10 und 1 1 appliziert.16. A method of combating phytopathogenic fungi, characterized in that a fungicidally effective amount of a compound according to any one of claims 1 to 5 or an agent according to any one of claims 7 is placed on these or the plants, surfaces or substrates or on infested by them or on seeds , 8, 10 and 1 1 applied.
17. Verfahren zur Bekämpfung von Schadinsekten, Acarina und Nematoden, bei welchem man auf diese oder die von ihnen befallenen Pflanzen, Flächen oder Substrate eine wirksame Menge einer Verbindung gemäß einem der Ansprüche17. A method for controlling insect pests, acarina and nematodes, in which an effective amount of a compound according to any one of the claims is applied to these or the plants, areas or substrates which they attack
1 bis 5 oder eines Mittels gemäß einem der Ansprüche 7, 9 und 10 appliziert.1 to 5 or an agent according to one of claims 7, 9 and 10 applied.
18. Verwendung von Verbindungen gemäß einem der Ansprüche 1 bis 5 oder eines Mittels gemäß einem der Ansprüche 7, 8 und 10 zur Bekämpfung von Schadinsekten, Acarina und Nematoden. 18. Use of compounds according to one of claims 1 to 5 or an agent according to one of claims 7, 8 and 10 for controlling insect pests, acarina and nematodes.
19. Saatgut, behandelt oder beschichtet mit einer wirksamen Menge einer Verbindung gemäß einem der Ansprüche 1 bis 5 oder eines Mittels gemäß einem der Ansprüche 7, 8, 10 und 1 1. 19. Seed, treated or coated with an effective amount of a compound according to one of claims 1 to 5 or an agent according to one of claims 7, 8, 10 and 11.
EP94926234A 1993-09-14 1994-09-02 Substituted pyridines, process for producing them and their use as pesticides and fungicides Withdrawn EP0719255A1 (en)

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DE4331181A DE4331181A1 (en) 1993-09-14 1993-09-14 Substituted pyridines, processes for their preparation and their use as pesticides and fungicides
PCT/EP1994/002930 WO1995007890A1 (en) 1993-09-14 1994-09-02 Substituted pyridines, process for producing them and their use as pesticides and fungicides

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US5650417A (en) 1997-07-22
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AU7615194A (en) 1995-04-03
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KR960704848A (en) 1996-10-09

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