WO2006058730A1 - Hydrazide compounds for combating animal pests - Google Patents

Hydrazide compounds for combating animal pests Download PDF

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Publication number
WO2006058730A1
WO2006058730A1 PCT/EP2005/012787 EP2005012787W WO2006058730A1 WO 2006058730 A1 WO2006058730 A1 WO 2006058730A1 EP 2005012787 W EP2005012787 W EP 2005012787W WO 2006058730 A1 WO2006058730 A1 WO 2006058730A1
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Prior art keywords
crc
alkyl
phenyl
formula
haloalkyl
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PCT/EP2005/012787
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French (fr)
Inventor
Michael Hofmann
Michael Rack
David G. Kuhn
Deborah L. Culbertson
Douglas Anspaugh
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Basf Aktiengesellschaft
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Priority to EP05810640A priority Critical patent/EP1819224A1/en
Priority to AU2005311429A priority patent/AU2005311429A1/en
Priority to MX2007006538A priority patent/MX2007006538A/en
Priority to BRPI0518725-7A priority patent/BRPI0518725A2/en
Priority to US11/791,919 priority patent/US20070265231A1/en
Priority to AP2007004018A priority patent/AP2007004018A0/en
Priority to JP2007543768A priority patent/JP2008521856A/en
Publication of WO2006058730A1 publication Critical patent/WO2006058730A1/en
Priority to IL183198A priority patent/IL183198A0/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/42—Hydrazines having nitrogen atoms of hydrazine groups further singly-bound to hetero 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof containing the group; Thio analogues thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • 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
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • 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
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/81—Amides; Imides
    • C07D213/82—Amides; Imides in position 3
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/20—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
    • C07D307/79—Benzo [b] furans; Hydrogenated benzo [b] furans with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • C07D307/81—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur 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
    • C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to new hydrazide compounds which are useful for combating animal pests, in particular insects, arachnids and nematodes.
  • the invention also relates to a method for combating insects, nematodes and arachnids.
  • JP 2000169461 describes inter alia thiadiazolylcarbonylhydrazones of phenylketones having insecticidal or fungicidal activity. However, the insecticidal activity of these compounds is not satisfactory.
  • Ar is an optionally substituted cyclic radical, selected from phenyl, napthyl and heterocyclic radicals, n is 0 or 1 , Y is inter alia CO or SO 2 , R 1a is H, d-Cio-alkyl, C 1 - C-io-haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 - haloalkenyl, C 2 -C 10 -alkynyl, C 2 -C 10 -haloalkynyl or optionally substituted phenyl, R 2a and R 3a are inter alia H, Ci-C 10 -alkyl, CrCio-haloalkyl, halogen, optionally substituted phenyl or cyano and R 4a is inter alia an optionally substituted aromatic radical selected from phenyl,
  • A is a cyclic radical selected from phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms as ring members which are selected, independently of one another, from O, N and S, the 5- or 6-membered heterocyclic radical may have a carbonyl group as ring member, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents R a which are selected, independently of one another, from halogen, cyano, nitro, CrC 10 -alkyl, CrC 1o -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 - C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 - haloalkynyl, CrC ⁇ -alkoxy, CrC 10 -haloalkoxy, C 2
  • R b which are selected, independently of one another, from halogen, cyano, nitro, C r Cio-alkyl, Ci-C 10 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 - C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -Ci 0 - haloalkynyl, CrCi 0 -alkoxy, CrC 10 -haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -Ci 0 - haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 -haloalkynyloxy, Ci-C 10 -alkylthio, C 1 -
  • Q is selected from the group consisting of a single bond, C r C 4 alkylidene,
  • Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents R c which are selected, independently of one another, from halogen, cyano, nitro, C 1 -C 10 - alkyl, C r Ci 0 -haloalkyl, C 3 -Ci 0 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -Ci 0 -alkenyl,
  • R 1 is selected from the group consisiting of H, Ci-C 10 -alkyl, Ci-Ci 0 -haloalkyl, C 3 -C 10 - cycloalkyl, C 3 -C 1o -halocycloalkyl, C 2 -C 1o -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 - alkynyl, C 2 -C 10 -haloalkynyl, phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for the aforementioned two last radicals to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents R a as defined above;
  • R 2 is a monovalent radical selected from H, halogen, cyano, Ci-C 1o -alkyl, C 1 -C 10 - haloalkyl, C 3 -C 1o -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -C 10 - haloalkenyl, C 2 -C 1o -alkynyl, C 3 -C 10 -haloalkynyl, d-C 10 -alkoxy, C r C 10 -haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 -haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 - haloalkynyloxy, d-C 10 -alkylthio, CrC 10 -haloalkylthio, hydroxy
  • R 3 is selected from the group consisiting of H, halogen, cyano, CrC 1o -alkyl, C 1 -C 10 - haloalkyl, C 3 -C 1o -cycloalkyl, Qrdo-halocycloalkyl, C 2 -C 1o -alkenyl, C 2 -C 10 - haloalkenyl, C 2 -C 1o -alkynyl, C 3 -C 10 -haloalkynyl, C 1 -C 1 CaIkOXy, d-do-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 1o -haloalkenyloxy, C 2 -Ci 0 -alkynyloxy, C 3 -C 10 - haloalkynyloxy, d-C ⁇ -alkylthio, CrC 1o -haloalkylthio,
  • R 4 is hydrogen or has one of the meanings given for R c or
  • N N, 0-CR 11 R 12 , S-CR 11 R 12 , N(R 13 )-CR 11 R 12 , O-C(O), O-C(S), S-C(O); N(R 13 )-C(O) or N(R 13 )-C(S);
  • R 5 is selected from the group consisiting of H, d-do-alkyl. d-do-haloalkyl, C 3 -C 10 - cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 1o -haloalkenyl, C 2 -C 10 - alkynyl, C 2 -Ci 0 -haloalkynyl, benzyl and phenyl wherein benzyl and phenyl may be substituted by 1 , 2, 3, 4 or 5 substituents R d which are selected, independently of one another, from halogen, cyano, nitro, Ci-Ci O -alkyl, C ⁇ do-haloalkyl, C 3 -C 10 - cycloalkyl, C 3 -C 10 -halocycloalkyI, C 2 -Ci 0 -alkeny
  • R 6 is selected from the group consisiting of H, Ci-C 10 -alkyl optionally substituted by CN or NO 2 , C r C 1o -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 - alkenyl, C 2 -Ci 0 -haloalkenyl, C 2 -C 10 -alkynyl, C 2 -C 10 -haloalkynyl, CrC-io-alkylthio,
  • R 7 , R 8 are selected independently of one another from H, CrC 1o -alkyl, CrCio-haloalkyl, C 3 -C 1o -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 - C 1o -alkynyl, C 3 -C 10 -haloalkynyl, phenyl, benzoyl, naphthyl or benzyl wherein the phenyl ring in the aforementioned four radicals may be substituted by 1 , 2, 3, 4 or 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, Ci-Ci O -alkyl, C r C 1o -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 - halocycloalky
  • R 9 is hydrogen, cyano, d-Ci O -alkyl, d-Cio-haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -Ci 0 - halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -haloalkenyl, C 2 -Ci 0 -alkynyl, C 3 -Ci 0 - haloalkynyl, Ci-Ci ⁇ -haloalkylsulfonyl, Ci-C 10 -alkylcarbonyl, C 1 -C 10 - haloalkylcarbonyl, R 7 R 8 N-CO-, phenyl or benzyl, wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents R b ; and
  • R 10 is hydrogen or has one of the meanings given for R c ;
  • R 11 , R 12 are selected independently of one another from H, d-C 10 -alkyl, C 1 -C 10 - haloalkyl, C 3 -Ci 0 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -Ci 0 - haloalkenyl, C 2 -Ci o -alkynyl and C 3 -Ci 0 -haloalkynyl, C r Ci 0 -alkoxy, C 1 -C 10 - haloalkoxy, d-do-alkylthio, C r C 1o -haloalkylthio, hydroxy-C r Ci 0 -alkyl, C 1 -C 10 - alkoxy-Ci-Ci 0 -alkyl, halo-Ci-Ci 0 -alkoxy-Ci-C
  • R 13 is hydrogen, cyano, Ci-Ci ⁇ -alkyl, Ci-Ci 0 -haloalkyl, C 3 -Ci 0 -cycloalkyl, C 3 -C 10 - halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -Ci ⁇ -haloalkenyl, C 2 -Ci 0 -alkynyl, C 3 -Ci 0 - haloalkynyl, CrC 10 -haloalkylsulfonyl, CrCio-alkylcarbonyl, CrC 10 - haloalkylcarbonyl, R 7 R 8 N-CO-, phenyl or benzyl, wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents R b ;
  • the compounds of the general formula I can be used for controlling pests, selected from harmful insects, arachnids and nematodes.
  • the compounds of the formula I are in particular useful from combating insects.
  • compositions for combating such pests preferably in the form of directly sprayable solutions, emulsions, pastes, oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprises a pesticidally effective amount of at least one compound of the general formula I or at least a salt thereof and at least one carrier which may be liquid and/or solid and which is prefarably agronomically acceptable, and/or at least one surfactant.
  • the invention provides a method for combating such pests, which comprises contacting said pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from an attack of or infestation by said pest, with a pesticidally effective amount of a compound of the general formula I as defined herein or a salt thereof.
  • the invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful insects, arachnids and/or nematodes, said method comprises contacting a crop with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
  • the invention also provides a method for protecting non-living materials from attack or infestation by the aforementioned pests, which method comprises contacting the nonliving material with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
  • the present invention provides both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof.
  • the compounds of the general formula I may also exist in the form of different tautomers if A or Ar carry amino or hydroxy groups. The invention comprises the single tautomers, if seperable, as well as the tautomer mixtures.
  • Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4 + ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by CrC 4 -alkyl, CrC 4 -hydroxyalkyl, C 1 -C 4 ⁇ IkOXy, C 1 -C 4 -BIkOXy-C 1 - C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C r C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC ⁇ alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • Halogen or "halo” will be taken to mean fluoro, chloro, bromo and iodo.
  • the substituent O denotes a carbonyl group.
  • O-CrC 4 -alkylidene and "S-C r C 4 -alkylidene”, respectively refer to a linear or branched alkanediyl group having 1 to 4 carbon atoms, where one valency is attached to the skeleton via an oxygen or sulfur atom, respectively.
  • d-C ⁇ -alkyl refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1- dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-di
  • C r C 4 -alkyl means for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.
  • Cio-haloalkyl refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C 4 - haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 2-chlor
  • C 1 - C 10 -haloalkyl in particular comprises CrCa-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
  • d-Cio-alkoxy and “C-i-C-io-alkylthio” refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, in any position in the alkyl group.
  • Examples include C 1 -C 4 - alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further CrC 4 -alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
  • Ci-C 10 -haloalkoxy and " refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, in any position in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C 1 -C 2 -IIaIOaIkOXy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroe
  • C r C 2 -fluoroalkoxy and C 1 -C 2 - fluoroalkylthio refer to Ci-C 2 -fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
  • C 2 -C 10 -alkenyl intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2- butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyM-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3- methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1- dimethyl-2
  • C 2 -C 10 -haloalkenyl intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -C 10 -alkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkage, in any position in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
  • C 2 -C 10 -haloalkenyloxy intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkage, , in any position in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
  • C 2 -C 10 -alkynyl refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
  • C 3 -C 10 -haloalkynyr refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 2 -C 10 -alkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkage in any position in the alkynyl group.
  • C 3 -C 10 -haloalkynyloxy refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages in any position in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
  • C 3 -C 10 -cycloalkyl refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
  • C 3 -C 10 -halocycloalkyr refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like.
  • Ci-C 10 -alkylcarbonyr refers to d-d o -alkyl which is bound to the remainder of the molecule via a carbonyl group.
  • Examples include CO-CH 3 , CO-C 2 H 5 , CO-CH 2 -C 2 H 5 , CO-CH(CH 3 ) 2 , n-butylcarbonyl, CO-CH(CHa)-C 2 H 5 , CO-CH 2 -CH(CHa) 2 , CO-C(CH 3 ) 3 , n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2- methylpentylcarbon
  • d-C 10 -alkoxycarbonyl refers to Ci-C 10 -alkoxy which is bound to the remainder of the molecule via a carbonyl group.
  • Examples include CO-OCH 3 , CO-OC 2 H 5 , CO-OCH 2 -C 2 H 5 , CO-OCH(CH 3 ) 2 , n-butoxycarbonyl, CO-OCH(CHa)-C 2 H 5 , CO-OCH 2 -CH(CHa) 2 , CO-OC(CH 3 ) 3 , n-pentoxycarbonyl, 1- methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2- dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1- dimethylpropoxycarbonyl, 1 ,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2- methylpentoxycarbonyl, 3-methyl
  • halo-Ci-C 10 -alkoxycarbonyl refers to d-Cio-haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.
  • hydroxy-C r C 10 -alkyr refers to d-do-alkyl, as defined herein, in particular to methyl, ethyl, 1 -propyl or 2-propyl, which is substituted by one radical selected from hydroxy, d-C 10 -alkoxy, C 1 -Ci 0 - haloalkoxy, CrC 10 -alkoxycarbonyl or Ci-C 10 -haIoalkoxycarbonyl.
  • the term "5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 heteroatoms which are selected, independently of one another, from O, N and S" comprises monocyclic 5- or 6-membered heteroaromatic rings and nonaromatic saturated or partially unsaturated 5- or 6-membered mono-heterocycles, which carry 1 , 2, 3, or 4 heteroatoms as ring members.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • non-aromatic rings examples include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothio
  • Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxazolyl.
  • a in formula I is a cyclic radical selected from phenyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazoloyl, pyridyl, pyrimidinyl, pyrazinyl, and pyridazinyl and where the cyclic radical may be unsubstituted or substituted as described above.
  • the aformentioned radicals are unsubstituted or substituted by 1, 2 or 3 radicals R a as defined above.
  • Preferred radicals R a comprise halogen, CN, Ci-C 4 -alkyl, CrC 4 -alkoxy, C 1 -C 4 - haloalkoxy, C r C 4 -alkylthio and Ci-C 4 -haloalkyl, in particular F, Cl, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • wherin A is a cyclic radical selected from phenyl, thienyl, furyl, isoxazolyl, pyrazolyl, imidazolyl, pyrazinyl, pyrimidinyl and pyridyl, in particular from pyridyl, thienyl and phenyl, where the cyclic radical may be substituted by 1 , 2 or 3 substuituents R a which are as defined above and which are preferably selected, independently of one another, from halogen, C 1 -C 4 - alkyl, C r C 4 -alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkylthio and CrCrhaloalkyl, in particular from F, Cl, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, trifluorome
  • Examples of preferred radicals A comprise: - 2-thienyl, 3-bromothien-2-yl, 4-bromothien-2-yl, 5-bromothien-2-yl, 4,5- dibromothien-2-yl, 3-chlorothien-2-yl, 4-chlorothien-2-yl, 5-chlorothien-2-yl, 3- chloro-4-methylthien-2-yl, 3-methylthien-2-yl, 4-methylthien-2-yl, 5-methylthien-2- yl, 3-methoxythien-2-yl, 3-methoxy-5-(trifluoromethyl)thien-2-yl, 3-ethoxy-5- (trifluoromethyl)thien-2-yl, 2-bromo-4,5-dimethylthien-2-yl, - pyridin-2-yl, 6-methylthiopyridin-2-yl, 3-fluoropyridin-2-yl, 3-methoxypyridin-2-yl, 6-methyl
  • the cyclic radical may also be napthyl, 1 ,2,3,4-tetrahydroisochinolin-3-yl, 2- benzothienyl, benzo[1 ,3]-dioxol-5-yl, indolyl or benzimidazolyl, where the cyclic radical may be unsubstituted or substituted as described above.
  • the aformentioned radicals are unsubstituted or substituted by 1 , 2 or 3 radicals R a as defined above. Examples of these radicals A comprise:
  • A is a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms as ring members which are selected, independently of one another, from O, N and S and may also have a carbonyl group as ring member, and may have 1, 2, 3, 4 or 5 substituents R a as defined above.
  • a very preferred embodiment of the invention relates to compounds of the formula I 1 wherein A is thienyl, in particular 2-thienyl which is unsubstituted or substituted by 1 , 2 or 3 radicals R a as defined above, the radicals R a being preferably selected, independently of one another, from halogen, CrC 4 -alkyl, d-C 4 -alkoxy, CrC 4 -alkylthio, Ci-C 4 -haloalkoxy and CrC 4 -haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • A is furyl, in particular 2-furyl which is unsubstituted or substituted by 1, 2 or 3 radicals R a as defined above, the radicals R a being preferably selected, independently of one another, from halogen, C r C 4 -alkyl, C r C 4 -alkoxy, C r C 4 -alkylthio, CrC 4 -haloalkoxy and CrCVhaloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • A is pyridyl, in particular 2- or 3-pyridyl, more preferably 2-pyridyl which is unsubstituted or substituted by 1, 2 or 3 radicals R a as defined above, the radicals R a being preferably selected, independently of one another, from halogen, Cr C 4 -alkyl, C 1 -C ⁇ aIkOXy, C r C 4 -alkylthio, C r C 4 -haloalkoxy and C 1 -C 4 -haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • a further very preferred embodiment of the invention relates to compounds of the formula I, wherein A is phenyl, which is unsubstituted or substituted by 1, 2 or 3 radicals R a as defined above, the radicals R a being preferably selected, independently of one another, from halogen, Ci-C 4 -alkyl, CrC 4 -alkoxy, Ci-C 4 -haloalkoxy, C 1 -C 4 - alkylthio and C r C 4 -haloalkyl, in particular from F, Cl, Br 1 methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • Q is preferably selected from the group consisting of a single bond, -CH 2 -, -CH 2 -CH 2 -, -0-CH 2 -, -0-CH 2 -CH 2 -, 0-CH 2 -CH 2 -CH 2 -, -NH-CH 2 -CH 2 -, -NH-C(O)-CH 2 -, -S-CH 2 -, -S-CH 2 -CH 2 -, -0-CH(CH 3 )- and -S-CH(CH 3 )-, in particular from a single bond, -CH 2 -, -0-CH 2 -, -S-CH 2 -, -0-CH(CH 3 )- and -S-CH(CH 3 )-.
  • the heteroatom of Q is preferably attached to A. More preferably Q is a single bond or -CH 2 -.
  • Preferred examples of the moiety A-Q include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 4-hydroxybutyl, 5- hydroxypentyl, 2,2-dimethoxyethyl, 2,2-diethoxyethyl, methoxycarbonylmethyl or ethoxycarbonylmethyl, especially methyl.
  • R 1 is H, CrC 10 -alkyl, d-C 10 -haloalkyl, C 3 -C 10 - cycloalkyl, C 3 -C 1o -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 1o -haloalkenyl, C 2 -C 10 -alkynyl and C 2 -C 10 -haloalkynyl.
  • R 1 is preferably hydrogen, CrC ⁇ -alkyl, C 1 -C 10 - haloalkyl, more preferably hydrogen, C r C 4 -alkyl or C r C 4 -haloalkyl, and especially hydrogen.
  • R 1 is selected from the group consisting of phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S 1 it being possible for phenyl and the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents R a as defined above.
  • R 1 is pyridyl, in particular 3- pyridyl, C 3 -C 10 -cycloalkyl, phenyl and more preferably C 3 -C 6 -Cy clop ropy I
  • R 2 is preferably selected from hydrogen, halogen and Ci-C 4 -alkyl, in particular from hydrogen, fluorine chlorine, bromine, methyl or ethyl.
  • R 3 is preferably selected from hydrogen, halogen and CrC 4 -alkyl, with hydrogen being more preferred.
  • R 5 is preferably selected from hydrogen, Ci-Ci ⁇ -alkyl, C r C 1o -haloalkyl, C 3 -Ci 0 - cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, in particular from hydrogen and Ci-C 4 -alkyl.
  • R 6 is selected from the group consisiting of H, CrCi O -alkyl, which is optionally substituted by CN or NO 2 , C r Ci 0 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 - C 1o -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 2 -Ci 0 - haloalkynyl, CrCio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Ci 0 -alkylsulfonyl, C 1 -C 10 - haloalkylsulfonyl, C r Ci 0 -alkoxycarbonyl, d-Cio-haloalkoxycarbonyl, C 2 r Ci 0
  • R 6 is preferably hydrogen, C r C 4 - alkyl, d-C ⁇ haloalkyl, C r C 4 -alkylsulfonyl, C r C 4 -alkylcarbonyl, C r C 4 -alkylsulfonyl or Ci-C 4 -haloalkylsulfonyl, in particular hydrogen.
  • R 6 is CrCi ⁇ -alkylthio, Ci-C 1o -haloalkylthio, CrCio-alkylcarbonyl, where the alkyl moiety of alkylcarbonyl is substituted by 1 , 2 or 3 substituents selected from the group consisting of C r Ci 0 - alkylthio, phenylthio, phenyl and phenoxy, benzoyl (C 6 H 5 -CO-), C 3 -Cio-cycloalkylcarbonyl, R 6a -CO-, wherein R 6a is C r C 4 -alkoxycarbonyl, phenoxy, naphthyl or a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for phenoxy, naphthyl and the 5- or 6-membered heterocyclic radical to be unsubsti
  • R 6 is preferably Ci-C 4 -alkylcarbonyI, wherein the alkyl moiety of alkylcarbonyl is substituted by a radical selected from phenyl, C r C 4 -alkylthio, phenylthio and phenoxy, such as phenoxymethylcarbonyl, 2-methylsulfanylethylcarbonyl and phenylsulfanylmethylcarbonyl or benzoyl.
  • R 6 is a benzoyl or a radical of the formula R 6a -C(0)-, wherein R 6a is C r C 2 -alkoxycarbonyl, phenoxy, a 5- or 6-membered aromatic heterocyclic radical with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1 or 2 substituents R a as defined above.
  • R 6a are phenoxy, 3-isoxazolyl, 5-isoxazolyl, 2-thienyl and 2-furyl and methoxycarbonyl.
  • Ar is preferably phenyl, which is unsubstituted or substituted by 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals R c as defined above.
  • R 4 is one of the 1 to 4 radicals R c as defined above or R 4 together with R 2 is the aformentioned bivalent radical.
  • Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl and wherein two radicals R c which are bound to adjacent carbon atoms may form a 0-CH 2 -O moiety, where in said moiety 1 or 2 hydrogen atoms may be replaced by a radical R b as defined above.
  • the radical R c is halogen, cyano, nitro, Ci-C 10 -alkyl, C 1 -Ci 0 - haloalkyl, C 3 -Ci 0 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 1o -haloalkynyl, d-C ⁇ -alkoxy, C r C 1o -haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -Ci 0 -alkynyloxy, C 3 -C 1o -haloalkynyloxy, C r C 1o -alkylthio, C r C 1o -haloalkylthio, C 1 -C 10 - alkyls
  • the radicals R c are selected, independently of one another, from halogen, CN, Ci-C 4 -alkyl, C r C 4 -alkoxy, C ⁇ C ⁇ haloalkoxy and Ci-C 4 -haloalkyl, more preferably F, Cl, CN, C r C 3 -alkoxy, in particular methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy and methyl.
  • the radical R c is C r C 1o -alkylcarbonyl.
  • a further very preferred embodiment of the invention relates to compounds of the formula I, wherein Ar is furyl, in particular 2-furyl which is unsubstituted or substituted by 1 radical R c as defined above or thienyl, in particular 2-thienyl, which may be unsubstituted or substituted by 1 radical R c as defined above.
  • the radical R 2 in formula I is a monovalent radical, i.e. R 2 and R 4 together do not form a bivalent radical.
  • R 2 is preferably selected from hydrogen, halogen, CrC 4 -alkyl, C r C 4 -alkoxy, C 1 -C 4 - haloalkoxy and C r C 4 -haloalkyl. More preferably R 2 is hydrogen, fluorine, chlorine bromine, methyl or ethyl.
  • R 4 is hydrogen or a radical R c as defined above, in particular hydrogen.
  • Ar in formula I is preferably phenyl, which is unsubstituted or substituted by 1, 2, 3 or 4, in particular 1, 2 or 3 radicals R c as defined above.
  • Ar in formula I is preferably phenyl, which is unsubstituted or substituted by 1 , 2 or 3, in particular O, 1 or 2 radicals R c as defined above.
  • R b is preferably selected from halogen, Ci-C 4 -alkyl, C r C 4 -alkoxy, C 1 - C 4 -haloalkoxy and C r C 4 -haloalkyl.
  • R 7 , R 8 are preferably selected independently from one another from hydrogen and C r C 4 -alkyl.
  • R 9 is preferably selected from hydrogen, C r C 4 -alkyl and C 1 -C 4 - alkylcarbonyl, in particular hydrogen.
  • R 10 is preferably selected from hydrogen, halogen and C 1 -C 4 ⁇ yI, in particular hydrogen.
  • R 11 , R 12 are preferably selected independently from one another from hydrogen and C r C 4 -alkyl, in particular hydrogen.
  • R 13 is preferably selected from hydrogen and CrC 4 -alkyl, in particular hydrogen.
  • k is O 1 1, 2 or 3, and wherein A, Q, R 1 , R 2 , R 3 , R 5 and R c are as defined above. Amongst the compounds Ia those are preferred, wherein Q, A, R 1 , R 2 , R 3 , R 5 and R c have the meanings given as preferred.
  • Table 10 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is H, R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 15 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is H, R 5 is H and (R c ) k is 2- OCHF 2 and wherein Q and A are given in table A;
  • Table 19 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is F, R 5 is H and (R c ) k is 3- fluoro and wherein Q and A are given in table A;
  • Table 20 Compounds of the formula Ia, wherein R 1 is H 1 R 3 is H 1 R 2 is F, R 5 is H and (R c ) k is 3- difluoromethoxy and wherein Q and A are given in table A;
  • Table 25 Compounds of the formula Ia, wherein R 1 is H 1 R 3 is H, R 2 is F, R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 29 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is F, R 5 is H and (R c ) k is A- OCH 3 and wherein Q and A are given in table A;
  • Table 30 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is F, R 5 is H and (R c ) k is 2- OCHF 2 and wherein Q and A are given in table A;
  • Table 35 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is Cl, R 5 is H and (R c ) k is 3- difluoromethoxy and wherein Q and A are given in table A;
  • Table 39 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is Cl, R 5 is H and (R c ) k is A- methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
  • Table 40 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is Cl, R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 45 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is Cl, R 5 is H and (R c ) k is 2- OCHF 2 and wherein Q and A are given in table A;
  • Table 49 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is B, R 5 is H r and (R c ) k is 3- fluoro and wherein Q and A are given in table A;
  • Table 50 Compounds of the formula Ia 1 wherein R 1 is H, R 3 is H 1 R 2 is Br, R 5 is H and (R c ) k is 3- difluoromethoxy and wherein Q and A are given in table A;
  • Table 55 Compounds of the formula Ia 1 wherein R 1 is H, R 3 is H, R 2 is Br, R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 59 Compounds of the formula Ia, wherein R 1 is H, R 3 is H 1 R 2 is Br, R 5 is H and (R c ) k is 4- OCH 3 and wherein Q and A are given in table A;
  • Table 60 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is Br, R 5 is H and (R c ) k is 2- OCHF 2 and wherein Q and A are given in table A;
  • Table 65 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 3 , R 5 is H and (R c ) k is 3-difluoromethoxy and wherein Q and A are given in table A;
  • Table 69 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 3 , R 5 is H and (R c ) k is 4-methylthio-3-trifluoromethyl and wherein Q and A are in given table A.
  • Table 70 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 3 , R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 75 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 3 , R 5 is H and (R c ) k is 2-OCHF 2 and wherein Q and A are given in table A;
  • Table 79 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 2 CH 3 , R 5 is H and (R c ) k is 3-fluoro and wherein Q and A are given in table A;
  • Table 80 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 2 CH 3 , R 5 is H and (R c ) k is 3-difluoromethoxy and wherein Q and A are given in table A;
  • Table 85 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 2 CH 3 , R 5 is H and (R c ) k is 2-F and wherein Q and A are given in table A;
  • Table 89 Compounds of the formula Ia 1 wherein R 1 is H, R 3 is H, R 2 is CH 2 CH 3 , R 5 is H and (R c ) k is 4-OCH 3 and wherein Q and A are given in table A;.
  • Table 90 Compounds of the formula Ia, wherein R 1 is H, R 3 is H, R 2 is CH 2 CH 3 , R 5 is H and (R c ) k is 2-OCHF 2 and wherein Q and A are given in table A;
  • k is 0, 1 , 2 or 3, and wherein A, Q, R 1 , R 3 , R 5 and R c are as defined above and Y is as defined above.
  • Y is O, OCH 2 or S and wherein Q, A, R 1 , R 3 , R 5 and R c have the meanings given as preferred.
  • Table 367 Compounds of the formula Ia 1 wherein Y is O 1 R 1 is H, R 3 is H, R 5 is CH 3 and (R c ) k is A- Cl and wherein Q and A are given in table A;
  • Table 372 Compounds of the formula Ia, wherein Y is S 1 R 1 is H, R 3 is H, R 5 is CH 3 and (R c ) k is A- Cl, 5-NO 2 and wherein Q and A are given in table A;
  • the compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists.
  • individual compounds I are not obtainable by the route described above, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described.
  • the preparation of the compounds of formula I may lead to them being obtained as isomer mixtures (stereoisomers, enantiomers). If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
  • Acyl hydrazones of the formula Il are known in the art, e.g. from PCT/EP 2004/005681 , or they can be obtained applying synthesis methods described for example in WO 87/06133 by analogy.
  • suitable hydrazides III can be reacted with aldehydes, esters or ketones IV according to scheme 3 to form acyl hydrazones of the formula II.
  • the compounds of formula I are effective through contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and/or ingestion (bait, or plant part).
  • the compounds of the formula I are in particular suitable for efficiently controlling nematodes and insects. In particular, they are suitable for controlling the following pests:
  • beetles Coldoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis,
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles mac ⁇ lipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, May
  • Thrips e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
  • homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisa tabaci, Bemisa argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis, and
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melan
  • plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloido- gyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterode- ra species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphe- lenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belono- laimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelen- chus species; Ring nematodes, Criconema species
  • the compounds of the formula I and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amhlyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephal ⁇ s appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • arachnoidea
  • Tetranychidae spp. such as Tetranych ⁇ s cinnaba ⁇ nus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.
  • the formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants.
  • Solvents/auxiliaries which are suitable, are essentially:
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone, gamma-butyrolactone
  • pyrrolidones NMP, NOP
  • acetates glycols, fatty acid dimethylamides, fatty acids and fatty acid esters.
  • solvent mixtures may also be used.
  • carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.
  • emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylpheny
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient.
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • a compound according to the invention 20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
  • a dispersant for example polyvinylpyrrolidone
  • a compound according to the invention 40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength).
  • This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • a compound according to the invention in an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.
  • Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.
  • Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor- stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.
  • a compound according to the invention is ground finely and associated with 95.5% carriers.
  • Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.
  • the active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil and such concentrates are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
  • the active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
  • UUV ultra-low-volume process
  • compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :100 to 100:1.
  • Organophosphates Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;
  • Pyrethroids Bifenthrin, Cyfluthrin, Cypermethrin, alpha-Cypermethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda- Cyhalothrin, Permethrin, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Zeta- Cypermethrin;
  • Arthropod growth regulators a) chitin synthesis inhibitors: benzoylureas: Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;
  • Fungicides are those selected from the group consisting of
  • acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,
  • amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph
  • anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl
  • antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin
  • azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol
  • dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin,
  • dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, • heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thiophanate-methyl, tiadinil, tricyclazole, triforine, • copper fungicides such as Bordeaux mixture, copper acetate, copper
  • nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl
  • phenylpyrroles such as fenpiclonil or fludioxonil
  • strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, • sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid
  • compositions are particularly useful for protecting plants against infestation of said pests or to combat these pests in infested plants.
  • the compounds of formula I are also suitable for the treatment of seeds.
  • compositions for seed treatments include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water soluble powders SS and emulsion ES.
  • Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
  • Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.5 to 80% of the active ingredient, from 0,05 to 5 % of a wetter, from 0.5 to 15 % of a dispersing agent, from 0,1 to 5 % of a thickener, from 5 to 20 % of an anti-freeze agent, from 0,1 to 2 % of an anti-foam agent, from 1 to 20 % of a pigment and/or a dye, from 0 to 15 % of a sticker /adhesion agent, from 0 to 75 % of a filler/vehicle, and from 0,01 to 1 % of a preservative.
  • Suitable pigments or dyes for seed treatment formulations are pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • Suitable adhesives are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
  • Compositions which are useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • compounds of formula I are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • Formulations of compounds of formula I as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C 1 dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the compounds of formula I and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of formula I and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N 1 N- diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2- hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as ⁇ (+/-)- 3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)- Eucamalol (1), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyp
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of aliphatic acids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and di-ethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is mostly done by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
  • the compounds of formula I and its compositions can be used for protecting non-living material, in particular cellulose-based materials such as wooden materials e.g. trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • cellulose-based materials such as wooden materials e.g. trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the compounds of formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula I or with a salt thereof or with a composition, containing a pesticidally effective amount of a compound of formula I or a salt thereof.
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the application rates of the mixture are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
  • HPLC column RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany).
  • Furan-2-carboxylic acid N'-[3-(2-fluorophenyl)-2-methyl-allyl]-N-methyl-hydrazide To 114 mg (0.4 mmol) of furan-2-carboxylic acid N-methyl-N'-[2-methyl-3-(2- fluorophenyl)-allylidene]-hydrazide and 38 mg (0.64 mmol) of dimethylamine- borane complex in 1 ml of dichloromethane which were cooled to O 0 C 456 mg (2.4 mmol) of p-toluenesulfonic acid monohydrate in 2ml of dichloromethand/methanol 3:1were added.
  • the heteroatom of the moiety Q is attached to the radical A
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Cotton plants at the cotyledon stage were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
  • the active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ® surfactant.
  • Pepper plants in the 2 nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 25 0 C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
  • Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions.
  • the test compound was diluted to a concentration of 500 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone:water, plus 0.01 % Kinetic ® surfactant.
  • Thrips potency of each compound was evaluated by using a floral-immersion technique.
  • Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28 0 C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish.
  • the level of thrips mortality was extrapolated from pre-treatment thrips numbers.
  • Nasturtium plants grown in Metro mix in the 1 st leaf-pair stage were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days.

Abstract

The present invention relates to new hydrazide compounds which are useful for combating animal pests, in particular insects, arachnids and nematodes and to the salts thereof. The invention also relates to a method for combating insects, nematodes and arachnids. The hydrazide compounds of the invention are described by the general formula (I) wherein ..… is absent or a covalent bond; A is an optionally substituted cyclic radical selected from phenyl, naphthyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, the 5- or 6-membered heterocyclic radical may have a carbonyl group as ring member; Q is selected from the group consisting of a single bond, C1-C4 alkylidene, O-C1-C4 alkylidene, S-C1-C4 alkylidene and NR9-C1-C4 alkylidene, wherein the alkylidene group in the last four mentioned radicals is unsubstituted or carries 1, 2, 3 or 4 substituents selected from OH, =O, halogen, C1-C4 haloalkyl and C1-C4 alkoxy; or A-Q may together be C1-C10-alkyl, which may be substituted by 1 or 2 substituents selected from the group consisting of =O, OH, C1-C4-alkoxy, C1-C4-alkylthio, halogen or C1-C4-alkylcarbonyloxy, X is C=O, C=S or SO2; Ar is an optionally substituted aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl; and R1 to R6 and R9 are as described in the claims and the specification.

Description

Hydrazide Compounds for Combating Animal Pests
The present invention relates to new hydrazide compounds which are useful for combating animal pests, in particular insects, arachnids and nematodes. The invention also relates to a method for combating insects, nematodes and arachnids.
In spite of commercial pesticides available today, damage to crops, both growing and harvested, the damage of non-living material, in particular cellulose based materials such as wood or paper, and other nuisance, such as transmission of diseases, caused by animal pests still occur.
JP 2000169461 describes inter alia thiadiazolylcarbonylhydrazones of phenylketones having insecticidal or fungicidal activity. However, the insecticidal activity of these compounds is not satisfactory.
A. M. Islam et al., Egyptian Jornal of Chemistry 1986, 29(4) S. 405-431 (CASREACT 111 :173716) discloses several naphthalin-2-yl sulfonylhydrazones of aromatic aldehydes, which were screened against cotton leaf worm (Spodoptera literalis). However, the activity of these compounds against other pests is not satisfactory.
Therefore, there is continuing need to provide compounds which are useful for combating insects, nematodes and arachnids.
T.M. Temerk et al. Bull. Soc. Chim. BeIg. 89(7), 1980, S. 489-498 describe the polarographic reduction in accordance with the following scheme:
Figure imgf000002_0001
lnternational application PCT/EP 2004/005681 discloses compounds of the general formula
Figure imgf000002_0002
wherein Ar is an optionally substituted cyclic radical, selected from phenyl, napthyl and heterocyclic radicals, n is 0 or 1 , Y is inter alia CO or SO2, R1a is H, d-Cio-alkyl, C1- C-io-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyl or optionally substituted phenyl, R2a and R3a are inter alia H, Ci-C10-alkyl, CrCio-haloalkyl, halogen, optionally substituted phenyl or cyano and R4a is inter alia an optionally substituted aromatic radical selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl. These compounds are active against insects and arachnids.
It is an object of the present invention to provide further compounds having a good activity against insects, nematodes and/or arachnids and thus are useful for combating said pests.
The inventors of the present application surprisingly found that this object is achieved by compounds of formula I as defined below and the salts thereof. These compounds have not yet been described, except for a compound of formula I, wherein A and Ar are unsubstituted phenyl, Q is a single bond, X is C=O and R1, R2, R3, R5 and R6 are hydrogen.
Therefore, the present invention relates to compounds of the general formula I
Figure imgf000003_0001
and to the salts thereof, wherein
is absent or a covalent bond;
A is a cyclic radical selected from phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms as ring members which are selected, independently of one another, from O, N and S, the 5- or 6-membered heterocyclic radical may have a carbonyl group as ring member, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents Ra which are selected, independently of one another, from halogen, cyano, nitro, CrC10-alkyl, CrC1o-haloalkyl, C3-C10-cycloalkyl, C3- C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, CrC^-alkoxy, CrC10-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC1o-alkylthio, C1- ό
Cio-haloalkylthio, Ci-C10-alkylsulfinyl, Ci-C10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, hydroxy, NR7R8, CrC^-alkoxycarbonyl, CrC^-haloalkoxycarbonyl, Ca-C^-alkenyloxycarbonyl, C2-C10-haloalkenyloxy- carbonyl, CrC^-alkylcarbonyl, d-C^-haloalkylcarbonyl, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by
1 , 2, 3, 4 or 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, CrCio-alkyl, Ci-C10-haloalkyl, C3-C10-cycloalkyl, C3- C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-Ci0- haloalkynyl, CrCi0-alkoxy, CrC10-haloalkoxy, C2-C10-alkenyloxy, C2-Ci0- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, Ci-C10-alkylthio, C1-
Cio-haloalkylthio, Ci-C10-alkylsulfiπyl, CrCi0-haloalkylsulfinyl, C1-Ci0- alkylsulfonyl, CrC10-haioalkylsulfonyl, hydroxy, NR7R8, CrCio-alkoxycarbonyl, CrC10-haloalkoxycarbonyl,
Figure imgf000004_0001
C2-C10- haloalkenyloxycarbonyl, CrC10-alkylcarbonyl, Ci-Cio-haloalkylcarbonyl and R7R8N-CO-, wherein in each case two radicals Ra which are bound to adjacent carbon atoms may form a CH=CH-CH=CH moiety or a 0-CH2-O moiety, where in these two moieties 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above;
Q is selected from the group consisting of a single bond, CrC4 alkylidene,
0-Ci-C4 alkylidene, S-Ci-C4 alkylidene and NR^C1-C4 alkylidene, wherein the alkylidene group in the last four mentioned radicals is unsubstituted or carries 1 ,
2, 3 or 4 substituents selected from OH, =0, halogen, CrC4 haloalkyl and CrC4 alkoxy;
or the moiety A-Q may together be CrCi0-alkyl, which may be substituted by 1 or 2 substituents selected from the group consisting of =0, OH, CrC4-alkoxy, CrC4- alkylthio, halogen or CrC4-alkylcarbonyloxy;
X is C=O, C=S or SO2;
Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from halogen, cyano, nitro, C1-C10- alkyl, CrCi0-haloalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl,
C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, C1-C10- haloalkoxy, C2-C10-alkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, C1-C10- alkylthio, CrC^-haloalkylthio, CrCiO-alkylsulfinyl, Ci-Ci0-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-Cio-haloalkylsulfonyl, hydroxy, NR7R8, CrCi0-alkoxycarbonyl, Ci-CiQ-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-haloalkenyloxy- carbonyl, d-C10-alkylcarbonyl, d-do-haloalkylcarbonyl, d-C10-alkylcarbonyloxy, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above and wherein two radicals Rc which are bound to adjacent carbon atoms may form a 0-CH2-O moiety, where in said moiety 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above;
R1 is selected from the group consisiting of H, Ci-C10-alkyl, Ci-Ci0-haloalkyl, C3-C10- cycloalkyl, C3-C1o-halocycloalkyl, C2-C1o-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C2-C10-haloalkynyl, phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for the aforementioned two last radicals to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Ra as defined above;
R2 is a monovalent radical selected from H, halogen, cyano, Ci-C1o-alkyl, C1-C10- haloalkyl, C3-C1o-cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl, C2-C10- haloalkenyl, C2-C1o-alkynyl, C3-C10-haloalkynyl, d-C10-alkoxy, CrC10-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, d-C10-alkylthio, CrC10-haloalkylthio, hydroxy-CrC1o-alkyl, d- C1o-alkoxy-CrC1o-alkyl, halo-d-do-alkoxy-d-do-alkyl, d-do-alkoxycarbonyl- d-do-alkyl, halo-d-do-alkoxycarbonyl-d-do-alkyl and phenyl which may be substituted by 1, 2, 3, 4 or 5 substituents Rb as defined above;
R3 is selected from the group consisiting of H, halogen, cyano, CrC1o-alkyl, C1-C10- haloalkyl, C3-C1o-cycloalkyl, Qrdo-halocycloalkyl, C2-C1o-alkenyl, C2-C10- haloalkenyl, C2-C1o-alkynyl, C3-C10-haloalkynyl, C1-C1CaIkOXy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C1o-haloalkenyloxy, C2-Ci0-alkynyloxy, C3-C10- haloalkynyloxy, d-C^-alkylthio, CrC1o-haloalkylthio, hydroxy-CrC1o-alkyl, C1- C-io-alkoxy- CrC1o-alkyl, halo-d-do-alkoxy-d-do-alkyl, d-do-alkoxycarbonyl- d-do-alkyl, halo-d-do-alkoxycarbonyl-d-dcralkyl and phenyl which may be substituted by 1, 2, 3, 4 or 5 substituents Rb as defined above;
R4 is hydrogen or has one of the meanings given for Rc or
R4 together with R2 is a bivalent radical Y, which is selected from O, S, CR10=N,
N=N, 0-CR11R12, S-CR11R12, N(R13)-CR11R12, O-C(O), O-C(S), S-C(O); N(R13)-C(O) or N(R13)-C(S);
R5 is selected from the group consisiting of H, d-do-alkyl. d-do-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C1o-haloalkenyl, C2-C10- alkynyl, C2-Ci0-haloalkynyl, benzyl and phenyl wherein benzyl and phenyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rd which are selected, independently of one another, from halogen, cyano, nitro, Ci-CiO-alkyl, C^do-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyI, C2-Ci0-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, Ci-C10-alkoxy, CrC^-haloalkoxy, C2-C10-alkenyloxy,
C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC1o-alkylthio, Crdo-haloalkylthio, CrC^-alkylsulfinyl, CrC-io-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC^-haloalkylsulfonyl, hydroxy, NR7R8, CrC1o-alkoxycarbonyl, CrC^-haloalkoxycarbonyl, C2-C1o-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC1o-alkylcarbonyl, d-C^-haloalkylcarbonyl and
R7R8N-CO-;
R6 is selected from the group consisiting of H, Ci-C10-alkyl optionally substituted by CN or NO2, CrC1o-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyl, CrC-io-alkylthio,
CrC^-haloalkylthio, CrC1o-alkylsulfinyl, Ci-C10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC1o-haloalkylsulfonyl, CrC1o-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C1o-haloalkenyloxycarbonyl, CrC^-alkylcarbonyl, where the alkyl moiety of alkylcarbonyl may be unsubstituted or substituted by 1 , 2 or 3 substituents selected from the group consisting of CrC1o-alkylthio, phenylthio, phenyl and phenoxy, C1-C10- haloalkylcarbonyl, C2-C1o-alkenylcarbonyl,
Figure imgf000006_0001
CrC1o-alkoxy- Ci-Cio-alkyl, halo-CrC^-alkoxy-CrC^-alkyl, CrC^-alkoxycarbonyl-CrC^-alkyl, halo-CrC^-alkoxycarbonyl-CrCuj-alkyl, R7R8N-CO-, benzoyl (C6H5-CO-), C3- C10-cycloalkylcarbonyl, R6a-CO-, wherein R6a is C1-C4-alkoxycarbonyl, phenoxy, naphthyl or a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for phenoxy, naphthyl and the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents Ra as defined above, and benzyl wherein benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above;
R7, R8 are selected independently of one another from H, CrC1o-alkyl, CrCio-haloalkyl, C3-C1o-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2- C1o-alkynyl, C3-C10-haloalkynyl, phenyl, benzoyl, naphthyl or benzyl wherein the phenyl ring in the aforementioned four radicals may be substituted by 1 , 2, 3, 4 or 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, Ci-CiO-alkyl, CrC1o-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C1 o-alkenyl, C2-C1o-haloalkenyl, CrC10-alkoxy, C1-C10- haloalkoxy, CrC1o-alkylthio, C^C^-haloalkylthio, CrCi0-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, d-do-alkoxycarbonyl, d-do-haloalkoxycarbonyl, C2- C10-alkenyloxycarbonyl, C2-Ci o-haloalkenyloxycarbonyl, d-do-alkylcarbonyl and Crdo-haloalkylcarbonyl;
R9 is hydrogen, cyano, d-CiO-alkyl, d-Cio-haloalkyl, C3-C10-cycloalkyl, C3-Ci0- halocycloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0- haloalkynyl, Ci-Ciθ-haloalkylsulfonyl, Ci-C10-alkylcarbonyl, C1-C10- haloalkylcarbonyl, R7R8N-CO-, phenyl or benzyl, wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb; and
R10 is hydrogen or has one of the meanings given for Rc;
R11, R12 are selected independently of one another from H, d-C10-alkyl, C1-C10- haloalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Ci0- haloalkenyl, C2-Ci o-alkynyl and C3-Ci0-haloalkynyl, CrCi0-alkoxy, C1-C10- haloalkoxy, d-do-alkylthio, CrC1o-haloalkylthio, hydroxy-CrCi0-alkyl, C1-C10- alkoxy-Ci-Ci0-alkyl, halo-Ci-Ci0-alkoxy-Ci-C1o-alkyl, Ci-C1o-alkoxycarbonyl-d- Ciθ-alkyl, halo-d-do-alkoxycarbonyl-d-Cicralkyl, one of the radicals R11 or R12 may also be d-do-alkylsulfonyl, Ci-C1o-haloalkylsulfonyl, d-C1o-alkoxycarbonyl, Ci-C1o-haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, Ci-Cio-alkylcarbonyl, d-do-haloalkylcarbonyl or R7R8N-CO-.
R13 is hydrogen, cyano, Ci-Ciθ-alkyl, Ci-Ci0-haloalkyl, C3-Ci0-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-Ciθ-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0- haloalkynyl, CrC10-haloalkylsulfonyl, CrCio-alkylcarbonyl, CrC10- haloalkylcarbonyl, R7R8N-CO-, phenyl or benzyl, wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb;
except for a compound of formula I, wherein A and Ar are unsubstituted phenyl, Q is a single bond, X is C=O and R1, R2, R3, R5 and R6 are hydrogen.
Due to their excellent activity, the compounds of the general formula I can be used for controlling pests, selected from harmful insects, arachnids and nematodes. The compounds of the formula I are in particular useful from combating insects.
Accordingly, the invention further provides compositions for combating such pests, preferably in the form of directly sprayable solutions, emulsions, pastes, oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprises a pesticidally effective amount of at least one compound of the general formula I or at least a salt thereof and at least one carrier which may be liquid and/or solid and which is prefarably agronomically acceptable, and/or at least one surfactant.
Furthermore, the invention provides a method for combating such pests, which comprises contacting said pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from an attack of or infestation by said pest, with a pesticidally effective amount of a compound of the general formula I as defined herein or a salt thereof.
The invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful insects, arachnids and/or nematodes, said method comprises contacting a crop with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
The invention also provides a method for protecting non-living materials from attack or infestation by the aforementioned pests, which method comprises contacting the nonliving material with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.
Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers, enantiomers) which may occur and mixtures thereof. Stereoisomeric centers are e.g. the carbon atom of the C(R2)=C(R3) group and the C(R1) moiety. The present invention provides both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof. The compounds of the general formula I may also exist in the form of different tautomers if A or Ar carry amino or hydroxy groups. The invention comprises the single tautomers, if seperable, as well as the tautomer mixtures.
Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by CrC4-alkyl, CrC4-hydroxyalkyl, C1-C4^IkOXy, C1-C4-BIkOXy-C1- C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(CrC4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CrC^alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
"Halogen" or "halo" will be taken to mean fluoro, chloro, bromo and iodo.
The term Crd-alkylidene refers to a linear or branched alkanediyl group having 1 to 4 carbon atoms such as methylene (= CH2), 1 ,2-ethandiyl (= CH2CH2), 1 ,1-ethandiyl (= CH(CH3)), 1,2-propandiyl, 1 ,3-propandiyl, 2,2-propandiyl, 1 ,4-butandiyl and the like. According to the invention CrC4-alkanediyl is unsubstituted or may carry 1 , 2, 3 or 4 substituents selected from OH, =0, halogen C1-C4 haloalkyl and C1-C4 alkoxy. The substituent =O denotes a carbonyl group.
The terms "O-CrC4-alkylidene" and "S-CrC4-alkylidene", respectively refer to a linear or branched alkanediyl group having 1 to 4 carbon atoms, where one valency is attached to the skeleton via an oxygen or sulfur atom, respectively.
The term "d-C^-alkyl" as used herein (and also in CrC10-alkyIsulfinyl and C1-C10- alkylsulfonyl) refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2- dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1- dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. CrC4-alkyl means for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.
The term "CrC^-haloalkyl" as used herein (and also in CrC^-haloalkylsulfinyl and C1- Cio-haloalkylsulfonyl) refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4- haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term C1- C10-haloalkyl in particular comprises CrCa-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.
Similarly, "d-Cio-alkoxy" and "C-i-C-io-alkylthio" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, in any position in the alkyl group. Examples include C1-C4- alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further CrC4-alkylthio such as methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.
Accordingly, the terms "Ci-C10-haloalkoxy" and "
Figure imgf000010_0001
refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, in any position in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C1-C2-IIaIOaIkOXy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2- difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy, further CrC2-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1 -fluoroethylthio, 2- fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio and the like. Similarly the terms CrC2-fluoroalkoxy and C1-C2- fluoroalkylthio refer to Ci-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
The term "C2-C10-alkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2- butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyM-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3- methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1- dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1- propenyl, 1 -ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1- methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1- methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1- methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1- methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1- dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2- butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3- dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2- butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl- 1 -butenyl, 1 -ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2- ethyl-3-butenyl, 1 ,1,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2- methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
The term "C2-C10-haloalkenyl" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
Similarly, the term "C2-C10-alkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkage, in any position in the alkenyl group, for example ethenyloxy, propenyloxy and the like. Accordingly, the term "C2-C10-haloalkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkage, , in any position in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.
The term "C2-C10-alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
The term "C3-C10-haloalkynyr as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
The term "C2-C10-alkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkage in any position in the alkynyl group.
Similarly, the term "C3-C10-haloalkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages in any position in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.
The term "C3-C10-cycloalkyl" as used herein refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl.
The term "C3-C10-halocycloalkyr as used herein refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like. The term "Ci-C10-alkylcarbonyr as used herein refers to d-do-alkyl which is bound to the remainder of the molecule via a carbonyl group. Examples include CO-CH3, CO-C2H5, CO-CH2-C2H5, CO-CH(CH3)2, n-butylcarbonyl, CO-CH(CHa)-C2H5, CO-CH2-CH(CHa)2, CO-C(CH3)3, n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2- methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1,1- dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethyIbutylcarbonyl, 2,2- dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutyIcarbonyl, 1- ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2-trimethylpropylcarbonyl, 1 ,2,2- trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1 -ethyl-2- methylpropylcarbonyl.
The term "d-C10-alkoxycarbonyl" as used herein refers to Ci-C10-alkoxy which is bound to the remainder of the molecule via a carbonyl group. Examples include CO-OCH3, CO-OC2H5, CO-OCH2-C2H5, CO-OCH(CH3)2, n-butoxycarbonyl, CO-OCH(CHa)-C2H5, CO-OCH2-CH(CHa)2, CO-OC(CH3)3, n-pentoxycarbonyl, 1- methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2- dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1- dimethylpropoxycarbonyl, 1 ,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2- methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1 ,1- dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl, 1 ,3-dimethylbutoxycarbonyl, 2,2- dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1- ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1 ,1 ,2-trimethylpropoxycarbonyl, 1 ,2,2- trimethylpropoxycarbonyl, 1 -ethyl- 1 -methyl propoxycarbonyl or 1 -ethyl-2- methylpropoxycarbonyl.
The term "halo-Ci-C10-alkoxycarbonyl" as used herein refers to d-Cio-haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.
The terms "hydroxy-CrC10-alkyr, "Crdo-alkoxy-CrCio-alkyr, "halo-d-Cio-alkoxy-Cr C10-alkyl", "d-do-alkoxycarbonyl-Ci-do-alkyl", "halo-Crdo-alkoxycarbonyl-CrC^- alkyl" as used herein, refer to d-do-alkyl, as defined herein, in particular to methyl, ethyl, 1 -propyl or 2-propyl, which is substituted by one radical selected from hydroxy, d-C10-alkoxy, C1-Ci0- haloalkoxy, CrC10-alkoxycarbonyl or Ci-C10-haIoalkoxycarbonyl.
The term "5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 heteroatoms which are selected, independently of one another, from O, N and S" comprises monocyclic 5- or 6-membered heteroaromatic rings and nonaromatic saturated or partially unsaturated 5- or 6-membered mono-heterocycles, which carry 1 , 2, 3, or 4 heteroatoms as ring members. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
Examples for non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like.
Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxazolyl.
With respect to the use according to the invention of the compounds of formula I, particular preference is given to the following meanings of the substituents, in each case on their own or in combination:
Preference is given to compounds of formula I, wherein A in formula I is a cyclic radical selected from phenyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazoloyl, pyridyl, pyrimidinyl, pyrazinyl, and pyridazinyl and where the cyclic radical may be unsubstituted or substituted as described above. In particular the aformentioned radicals are unsubstituted or substituted by 1, 2 or 3 radicals Ra as defined above.
Preferred radicals Ra comprise halogen, CN, Ci-C4-alkyl, CrC4-alkoxy, C1-C4- haloalkoxy, CrC4-alkylthio and Ci-C4-haloalkyl, in particular F, Cl, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
More preference is given to compounds of formula I, wherin A is a cyclic radical selected from phenyl, thienyl, furyl, isoxazolyl, pyrazolyl, imidazolyl, pyrazinyl, pyrimidinyl and pyridyl, in particular from pyridyl, thienyl and phenyl, where the cyclic radical may be substituted by 1 , 2 or 3 substuituents Ra which are as defined above and which are preferably selected, independently of one another, from halogen, C1-C4- alkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio and CrCrhaloalkyl, in particular from F, Cl, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, trifluoromethoxy and difluoromethoxy.
Examples of preferred radicals A comprise: - 2-thienyl, 3-bromothien-2-yl, 4-bromothien-2-yl, 5-bromothien-2-yl, 4,5- dibromothien-2-yl, 3-chlorothien-2-yl, 4-chlorothien-2-yl, 5-chlorothien-2-yl, 3- chloro-4-methylthien-2-yl, 3-methylthien-2-yl, 4-methylthien-2-yl, 5-methylthien-2- yl, 3-methoxythien-2-yl, 3-methoxy-5-(trifluoromethyl)thien-2-yl, 3-ethoxy-5- (trifluoromethyl)thien-2-yl, 2-bromo-4,5-dimethylthien-2-yl, - pyridin-2-yl, 6-methylthiopyridin-2-yl, 3-fluoropyridin-2-yl, 3-methoxypyridin-2-yl, 6-methylpyridin-2-yl, 5-nitropyrid i n-2-yl , 3-fluoropyridin-2-yl, 6-bromopyridin-2-yl, 6-chloropyridin-2-yl, 4-chloropyridin-2-yl, 3,6-dichloropyridin-2-yl, 6-fluoropyridin- 2-yl, 5-(trifluoromethyl)pyridin-2-yl, 4-(trifluoromethyl)pyridin-2-yl, 6- (trifluoromethyl)pyridin-2-yl, 6-hydroxypyridin-2-yl, 6-methoxypyridin-2-yl, 3- hydroxypyridin-2-yl, 6-phenylpyridin-2-yl, pyridin-3-yl, 6-chloropyridin-3-yl, 2,6- dichloropyridin-3-yl, 5,6-dichloropyridin-3-yl, 2,6-dichloro-4-methylpyridin-3-yl, 6- fluoropyridin-3-yl, 6-bromopyridin-3-yl, 5-bromopyridin-3-yl, 2-phenoxypyridin-3- yl, 1-methyl-2-hydroxypyridin-3-yl, pyridin-4-yl, 2-chloropyridin-4-yl, 2,6- dichloropyridin-4-yl, - phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyI, 2,4-difluorophenyl, 2,5- difluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3- dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichIorophenyl, 2- chloro-6-fluorophenyl, 2-chloro-4-fluorophenyl, 1 ,2,3,4,5-pentafluorophenyl, 2- bromophenyl, 3-bromophenyl, 4-bromophenyl, 5-bromo-2-chlorophenyl, 4-chloro- 2-methyl phenyl, 3-fluoro-4-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4- methylphenyl, 2,6-dimethylphenyl, 2-(trifluoromethyl)phenyl, 3- (trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 2-fluoro-4- (trifluoromethyl)phenyl, 3,5-bis(trifluoromethyl)phenyl, 4-tert.-butyl-phenyl, 2- methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,4-dimethoxyphenyl, 3,4,5- trimethoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2-methoxy-3-
(methylthio)phenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl, 2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 4-hydroxy-3-methoxyphenyl, 2-fluoro-4- hydroxyphenyl, 2-aminophenyl, 3-aminophenyl, 4-aminophenyl, 6-amino-2- fluorophenyl, 4-(dimethylamino)phenyl, 4-phenylphenyl, 4-(methylsulfonyl)-2- nitrophenyl,
5-methylpyrazin-2-yl, 3-aminopyrazin-2-yl,
2-furyl, 5-bromofuran-2-yl, 2-methylfuran-3-yl
5-isoxazolyl, 3-methylisoxazolyl, 3-(1-methylethyl)isoxazolyl, 5-
(chloromethyl)isoxazolyl, 5-(hydroxymethyl)isoxazolyl, - 1,3-bis(1,1,1-trifluoroeth-2-yl)pyrazol-4-yl, 1-methyl-3-(trifluoromethyl)pyrazol-5-yl, 3-methylimidazol-2-yl, 4-methylimididazol-5-yl, 4-amino-2-methylpyrimidin-2-yl, 6-hydroxy-2-methylpyrimidin-4-yl,
The cyclic radical may also be napthyl, 1 ,2,3,4-tetrahydroisochinolin-3-yl, 2- benzothienyl, benzo[1 ,3]-dioxol-5-yl, indolyl or benzimidazolyl, where the cyclic radical may be unsubstituted or substituted as described above. In particular the aformentioned radicals are unsubstituted or substituted by 1 , 2 or 3 radicals Ra as defined above. Examples of these radicals A comprise:
3-hydroxynapth-2-yl, 2-benzothienyl, 3-chloro-2-benzothienyl, 1-naphthyl, 2- naphthyl, 3-indolyl, 2-benzimidazolyl, 6,7-dimethoxy-3-methyl-1 , 2,3,4- tetrahydroisochinolinyl.
Another embodiment of the invention relates to compounds of the formula I wherein A is a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms as ring members which are selected, independently of one another, from O, N and S and may also have a carbonyl group as ring member, and may have 1, 2, 3, 4 or 5 substituents Ra as defined above.
A very preferred embodiment of the invention relates to compounds of the formula I1 wherein A is thienyl, in particular 2-thienyl which is unsubstituted or substituted by 1 , 2 or 3 radicals Ra as defined above, the radicals Ra being preferably selected, independently of one another, from halogen, CrC4-alkyl, d-C4-alkoxy, CrC4-alkylthio, Ci-C4-haloalkoxy and CrC4-haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
Another very preferred embodiment of the invention relates to compounds of the formula I, wherein A is furyl, in particular 2-furyl which is unsubstituted or substituted by 1, 2 or 3 radicals Ra as defined above, the radicals Ra being preferably selected, independently of one another, from halogen, CrC4-alkyl, CrC4-alkoxy, CrC4-alkylthio, CrC4-haloalkoxy and CrCVhaloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
Another very preferred embodiment of the invention relates to compounds of the formula I, wherein A is pyridyl, in particular 2- or 3-pyridyl, more preferably 2-pyridyl which is unsubstituted or substituted by 1, 2 or 3 radicals Ra as defined above, the radicals Ra being preferably selected, independently of one another, from halogen, Cr C4-alkyl, C1-C^aIkOXy, CrC4-alkylthio, CrC4-haloalkoxy and C1-C4-haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2- trifluoroethyl, trifluoromethoxy and difluoromethoxy.
A further very preferred embodiment of the invention relates to compounds of the formula I, wherein A is phenyl, which is unsubstituted or substituted by 1, 2 or 3 radicals Ra as defined above, the radicals Ra being preferably selected, independently of one another, from halogen, Ci-C4-alkyl, CrC4-alkoxy, Ci-C4-haloalkoxy, C1-C4- alkylthio and CrC4-haloalkyl, in particular from F, Cl, Br1 methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
X is preferably C=O.
Q is preferably selected from the group consisting of a single bond, -CH2-, -CH2-CH2-, -0-CH2-, -0-CH2-CH2-, 0-CH2-CH2-CH2-, -NH-CH2-CH2-, -NH-C(O)-CH2-, -S-CH2-, -S-CH2-CH2-, -0-CH(CH3)- and -S-CH(CH3)-, in particular from a single bond, -CH2-, -0-CH2-, -S-CH2-, -0-CH(CH3)- and -S-CH(CH3)-. The heteroatom of Q is preferably attached to A. More preferably Q is a single bond or -CH2-.
Preference is also given to compounds of the formula I, wherein the moiety A-Q is CrC-io-alkyl, which may be substituted by 1 or 2 substituents selected from the group consisting of =0, OH, Ci-C4-alkoxy, CrC4-alkylthio, halogen or CrC4-alkylcarbonyloxy, in particular from =0, OH and CrC2-alkoxy. Preferred examples of the moiety A-Q include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, 4-hydroxybutyl, 5- hydroxypentyl, 2,2-dimethoxyethyl, 2,2-diethoxyethyl, methoxycarbonylmethyl or ethoxycarbonylmethyl, especially methyl.
In one embodiment of this invention R1 is H, CrC10-alkyl, d-C10-haloalkyl, C3-C10- cycloalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2-C1o-haloalkenyl, C2-C10-alkynyl and C2-C10-haloalkynyl. In this embodiment R1 is preferably hydrogen, CrC^-alkyl, C1-C10- haloalkyl, more preferably hydrogen, CrC4-alkyl or CrC4-haloalkyl, and especially hydrogen. In a further embodiment of this invention R1 is selected from the group consisting of phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S1 it being possible for phenyl and the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Ra as defined above. In this embodiment preference is given to compounds I1 wherein R1 is pyridyl, in particular 3- pyridyl, C3-C10-cycloalkyl, phenyl and more preferably C3-C6-Cy clop ropy I, R2 is preferably selected from hydrogen, halogen and Ci-C4-alkyl, in particular from hydrogen, fluorine chlorine, bromine, methyl or ethyl.
R3 is preferably selected from hydrogen, halogen and CrC4-alkyl, with hydrogen being more preferred.
R5 is preferably selected from hydrogen, Ci-Ciθ-alkyl, CrC1o-haloalkyl, C3-Ci0- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, in particular from hydrogen and Ci-C4-alkyl.
In a further embodiment R6 is selected from the group consisiting of H, CrCiO-alkyl, which is optionally substituted by CN or NO2, CrCi0-haloalkyl, C3-C10-cycloalkyl, C3- C1o-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C2-Ci0- haloalkynyl, CrCio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Ci0-alkylsulfonyl, C1-C10- haloalkylsulfonyl, CrCi0-alkoxycarbonyl, d-Cio-haloalkoxycarbonyl, C2-Ci0- alkenyloxycarbonyl, C2-C10-haloalkenyloxycarbonyl, CrC1o-alkylcarbonyl, Ci-Ci0- haloalkylcarbonyl, hydroxy-CrC1o-alkyl, CrC1o-alkoxy- CrC10-alkyl, halo-CrCi0- alkoxy-Ci-Ciθ-alkyl, CrCi0-alkoxycarbonyl-Ci-Cio-alkyl, halo-CrCio-alkoxycarbonyl-Cr Ciθ-alkyl, R7R8N-CO- and benzyl wherein benzyl may be substituted by 1, 2, 3, 4 or 5 substituents Rb as defined above. In this embodiment R6 is preferably hydrogen, CrC4- alkyl, d-C^haloalkyl, CrC4-alkylsulfonyl, CrC4-alkylcarbonyl, CrC4-alkylsulfonyl or Ci-C4-haloalkylsulfonyl, in particular hydrogen.
Preference is also given to compounds of the formula I1 wherein R6 is CrCiθ-alkylthio, Ci-C1o-haloalkylthio, CrCio-alkylcarbonyl, where the alkyl moiety of alkylcarbonyl is substituted by 1 , 2 or 3 substituents selected from the group consisting of CrCi0- alkylthio, phenylthio, phenyl and phenoxy,
Figure imgf000018_0001
benzoyl (C6H5-CO-), C3-Cio-cycloalkylcarbonyl, R6a-CO-, wherein R6a is CrC4-alkoxycarbonyl, phenoxy, naphthyl or a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for phenoxy, naphthyl and the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1, 2, 3, 4 or 5 substituents Ra as defined above. In this embodiment R6 is preferably Ci-C4-alkylcarbonyI, wherein the alkyl moiety of alkylcarbonyl is substituted by a radical selected from phenyl, CrC4-alkylthio, phenylthio and phenoxy, such as phenoxymethylcarbonyl, 2-methylsulfanylethylcarbonyl and phenylsulfanylmethylcarbonyl or benzoyl. Preference is also given to compounds of the formula I, wherein R6 is a benzoyl or a radical of the formula R6a-C(0)-, wherein R6a is CrC2-alkoxycarbonyl, phenoxy, a 5- or 6-membered aromatic heterocyclic radical with 1 or 2 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1 or 2 substituents Ra as defined above. Example of preferred radicals R6a are phenoxy, 3-isoxazolyl, 5-isoxazolyl, 2-thienyl and 2-furyl and methoxycarbonyl.
Ar is preferably phenyl, which is unsubstituted or substituted by 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals Rc as defined above. A skilled person will appreciate that in case of R4 being different from hydrogen, R4 is one of the 1 to 4 radicals Rc as defined above or R4 together with R2 is the aformentioned bivalent radical.
Another embodiment of the invention relates to compounds I, wherein Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl and wherein two radicals Rc which are bound to adjacent carbon atoms may form a 0-CH2-O moiety, where in said moiety 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above. In one embodiment the radical Rc is halogen, cyano, nitro, Ci-C10-alkyl, C1-Ci0- haloalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C1o-haloalkynyl, d-C^-alkoxy, CrC1o-haloalkoxy, C2-C10-alkenyloxy, C2-Ci0-alkynyloxy, C3-C1o-haloalkynyloxy, CrC1o-alkylthio, CrC1o-haloalkylthio, C1-C10- alkylsulfinyl, CrC^-haloalkylsulfinyl, CrC1o-alkylsulfonyl, CrC1o-haloalkylsulfonyl, hydroxy, NR7R8, CrC1o-alkoxycarbonyl, Ci-C1o-haloalkoxycarbonyl, C2-C10- alkenyloxycarbonyl, C^C-io-haloalkenyloxycarbonyl, CrC^-alkylcarbonyl, C1-C10- haloalkylcarbonyl, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above. Preferably the radicals Rc are selected, independently of one another, from halogen, CN, Ci-C4-alkyl, CrC4-alkoxy, C^C^haloalkoxy and Ci-C4-haloalkyl, more preferably F, Cl, CN, CrC3-alkoxy, in particular methoxy, trifluoromethyl, difluoromethyl, trifluoromethoxy, difluoromethoxy and methyl. In another embodiment the radical Rc is CrC1o-alkylcarbonyl.
A further very preferred embodiment of the invention relates to compounds of the formula I, wherein Ar is furyl, in particular 2-furyl which is unsubstituted or substituted by 1 radical Rc as defined above or thienyl, in particular 2-thienyl, which may be unsubstituted or substituted by 1 radical Rc as defined above.
In a preferred embodiment of the invention the radical R2 in formula I is a monovalent radical, i.e. R2 and R4 together do not form a bivalent radical. In this embodiment R2 is preferably selected from hydrogen, halogen, CrC4-alkyl, CrC4-alkoxy, C1-C4- haloalkoxy and CrC4-haloalkyl. More preferably R2 is hydrogen, fluorine, chlorine bromine, methyl or ethyl. In this embodiment R4 is hydrogen or a radical Rc as defined above, in particular hydrogen. In this embodiment Ar in formula I is preferably phenyl, which is unsubstituted or substituted by 1, 2, 3 or 4, in particular 1, 2 or 3 radicals Rc as defined above.
Another embodiment of the invention relates to compounds of the formula I1 wherein R4 together with R2 is a bivalent radical Y as defined above and which is preferably selected from O, S, CH=N, O-CH2, O-C(O) or NH-C(O), where in the last 4 moieties either the carbon atom or the heteroatom is attached to the phenyl ring, in particular from O, S1 0-CH2, and O-C(O), where in the two last moieties the heteroatom is attached to the phenyl ring. More preferably R4 and R2 together are an oxygen atom or O-C(O) in particular O. In this embodiment Ar in formula I is preferably phenyl, which is unsubstituted or substituted by 1 , 2 or 3, in particular O, 1 or 2 radicals Rc as defined above.
Apart from that, Rb is preferably selected from halogen, Ci-C4-alkyl, CrC4-alkoxy, C1- C4-haloalkoxy and CrC4-haloalkyl.
If present, R7, R8 are preferably selected independently from one another from hydrogen and CrC4-alkyl.
If present, R9 is preferably selected from hydrogen, CrC4-alkyl and C1-C4- alkylcarbonyl, in particular hydrogen.
If present, R10 is preferably selected from hydrogen, halogen and C1-C4^yI, in particular hydrogen.
If present, R11, R12 are preferably selected independently from one another from hydrogen and CrC4-alkyl, in particular hydrogen.
If present, R13 is preferably selected from hydrogen and CrC4-alkyl, in particular hydrogen.
A very preferred embodiment of the invention relates to compounds of the general formula Ia:
Figure imgf000020_0001
wherein k is O1 1, 2 or 3, and wherein A, Q, R1, R2, R3 , R5 and Rc are as defined above. Amongst the compounds Ia those are preferred, wherein Q, A, R1, R2, R3 , R5 and Rc have the meanings given as preferred.
Examples of compounds Ia are given in the following tables 1 to 180:
Table 1 :
Compounds of the formula Ia, wherein R1 is H1 R3 is H1 R2 is H1 R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 2:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is H1 R5 is H and (Rc)k is A- fluoro and wherein Q and A are given in table A;
Table 3:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is H1 R5 is H and (Rc)k is A- chloro and wherein Q and A are given table A;
Table 4: Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is H1 R5 is H and (Rc)k is 3- fluoro and wherein Q and A are given in table A;
Table 5:
Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is H1 R5 is H and (Rc)k is 3- difluoromethoxy and wherein Q and A are given in table A;
Table 6:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H, R2 is H1 R5 is H and (Rc)k is 3- trifluoromethyl and wherein Q and A are given in table A;
Table 7:
Compounds of the formula Ia, wherein R1 is H1 R3 is H1 R2 is H, R5 is H and (Rc)k is A- fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 8:
Compounds of the formula Ia1 wherein R1 is H, R3 is H1 R2 is H, R5 is H and (Rc)k is A- methoxy-3-trifluoromethyl and wherein Q and A are in given table A;
Table 9: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is A- methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
Table 10: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 11:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is 2- CH3 and wherein Q and A are given in table A;
Table 12:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is 2- OCH3 and wherein Q and A are given in table A;
Table 13:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is 2-
CF3 and wherein Q and A are given in table A;
Table 14:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is A- OCH3 and wherein Q and A are given in table A;
Table 15: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is H, R5 is H and (Rc)k is 2- OCHF2 and wherein Q and A are given in table A;
Table 16:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 17:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is 4- fluoro and wherein Q and A are given in table A;
Table 18:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is A- chloro and wherein Q and A are given in table A;
Table 19: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is 3- fluoro and wherein Q and A are given in table A;
Table 20: Compounds of the formula Ia, wherein R1 is H1 R3 is H1 R2 is F, R5 is H and (Rc)k is 3- difluoromethoxy and wherein Q and A are given in table A;
Table 21:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is 3- trifluoromethyl and wherein Q and A are given in table A;
Table 22:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is F1 R5 is H and (Rc)k is A- fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 23:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is F1 R5 is H and (Rc)k is A- methoxy-3-trifluoromethyl and wherein Q and A are given in table A;
Table 24:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is F, R5 is H and (Rc)k is A- methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
Table 25: Compounds of the formula Ia, wherein R1 is H1 R3 is H, R2 is F, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 26:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is F1 R5 is H and (Rc)k is 2- CH3 and wherein Q and A are given in table A;
Table 27:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is 2- OCH3 and wherein Q and A are given in table A;
Table 28:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H, R2 is F1 R5 is H and (Rc)k is2-
CF3 and wherein Q and A are given in table A;
Table 29: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is A- OCH3 and wherein Q and A are given in table A;
Table 30: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is F, R5 is H and (Rc)k is 2- OCHF2 and wherein Q and A are given in table A;
Table 31:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and k is 0 (i.e. (Rc)κ is absent) and wherein Q and A are given in table A;
Table 32:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is Cl, R5 is H and (Rc)k is A- fluoro and wherein Q and A are given in table A;
Table 33:
Compounds of the formula Ia, wherein R1 is H1 and R3 is H, R2 is Cl, R5 is H and (Rc)k is
4-chloro and wherein Q and A are given in table A;
Table 34:
Compounds of the formula Ia, wherein R1 is H, and R3 is H, R2 is Cl, R5 is H and (Rc)k is 3-fluoro and wherein Q and A are given in table A;
Table 35: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 3- difluoromethoxy and wherein Q and A are given in table A;
Table 36:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 3- trifluoromethyl and wherein Q and A are given in table A;
Table 37:
Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is A- fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 38:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is A- methoxy-3-trifluoromethyl and wherein Q and A are given in table A;
Table 39: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is A- methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
Table 40: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 41:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 2- CH3 and wherein Q and A are given in table A;
Table 42:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 2- OCH3 and wherein Q and A are given in table A;
Table 43:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 2-
CF3 and wherein Q and A are given in table A;
Table 44:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is A- OCH3 and wherein Q and A are given in table A;
Table 45: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Cl, R5 is H and (Rc)k is 2- OCHF2 and wherein Q and A are given in table A;
Table 46:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Br, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 47:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Br, R5 is H and (Rc)k is A- fluoro and wherein Q and A are given in table A;
Table 48:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is Br, R5 is H and (Rc)k is A- chloro and wherein Q and A are given in table A;
Table 49: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is B, R5 is H r and (Rc)k is 3- fluoro and wherein Q and A are given in table A;
Table 50: Compounds of the formula Ia1 wherein R1 is H, R3 is H1 R2 is Br, R5 is H and (Rc)k is 3- difluoromethoxy and wherein Q and A are given in table A;
Table 51:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is Br1 R5 is H and (Rc)k is 3- trifluoromethyl and wherein Q and A are given in table A;
Table 52:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is Br1 R5 is H and (R°)k is A- fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 53:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is Br, R5 is H and (Rc)k is A- methoxy-3-trifluoromethyl and wherein Q and A are given in table A;
Table 54:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is Br1 R5 is H and (Rc)k is A- methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
Table 55: Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is Br, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 56:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H1 R2 is Br, R5 is H and (Rc)k is 2- CH3 and wherein Q and A are given in table A;
Table 57:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is Br1 R5 is H and (Rc)k is 2- OCH3 and wherein Q and A are given in table A;
Table 58:
Compounds of the formula Ia1 wherein R1 is H1 R3 is H, R2 is Br1 R5 is H and (Rc)k is2-
CF3 and wherein Q and A are given in table A;
Table 59: Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is Br, R5 is H and (Rc)k is 4- OCH3 and wherein Q and A are given in table A;
Table 60: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is Br, R5 is H and (Rc)k is 2- OCHF2 and wherein Q and A are given in table A;
Table 61 :
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 62:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 4-fluoro and wherein Q and A are given in table A;
Table 63:
Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is
4-chloro and wherein Q and A are given in table A;
Table 64:
Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 3-fluoro and wherein Q and A are given in table A;
Table 65: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 3-difluoromethoxy and wherein Q and A are given in table A;
Table 66:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 3-trifluoromethyl and wherein Q and A are given in table A;
Table 67:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 4-fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 68:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is
4-methoxy-3-trifluoromethyl and wherein Q and A are given in table A; and
Table 69: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 4-methylthio-3-trifluoromethyl and wherein Q and A are in given table A.
Table 70: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 71 :
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 2-CH3 and wherein Q and A are given in table A;
Table 72:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 2-OCH3 and wherein Q and A are given in table A;
Table 73:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is
2-CF3 and wherein Q and A are given in table A;
Table 74:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 4-OCH3 and wherein Q and A are given in table A;
Table 75: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH3, R5 is H and (Rc)k is 2-OCHF2 and wherein Q and A are given in table A;
Table 76:
Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 77:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 4-fluoro and wherein Q and A are given in table A;
Table 78:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 4-chloro and wherein Q and A are given in table A;
Table 79: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 3-fluoro and wherein Q and A are given in table A;
Table 80: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 3-difluoromethoxy and wherein Q and A are given in table A;
Table 81 :
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 3-trifluoromethyl and wherein Q and A are given in table A;
Table 82:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 4-fluoro-3-trifluoromethyl and wherein Q and A are given in table A;
Table 83:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (R°)k is 4-methoxy-3-trifluoromethyl and wherein Q and A are given in table A;
Table 84:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 4-methylthio-3-trifluoromethyl and wherein Q and A are given in table A;
Table 85: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 2-F and wherein Q and A are given in table A;
Table 86:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 2-CH3 and wherein Q and A are given in table A;
Table 87:
Compounds of the formula Ia, wherein R1 is H, R3 is H1 R2 is CH2CH3, R5 is H and (Rc)k is 2-OCH3 and wherein Q and A are given in table A;
Table 88:
Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is2-CF3 and wherein Q and A are given in table A;
Table 89: Compounds of the formula Ia1 wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 4-OCH3 and wherein Q and A are given in table A;.
Table 90: Compounds of the formula Ia, wherein R1 is H, R3 is H, R2 is CH2CH3, R5 is H and (Rc)k is 2-OCHF2 and wherein Q and A are given in table A;
Tables 91 to 180:
Compounds of the formula Ia, wherein R1, R2, R3 and (Rc)k are as defined in one of the tables 1 to 90, Q and A are given in table A and R5 is methyl instead of hydrogen.
Table A:
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0002
In table A the heteroatom of the moiety Q is attached to the radical A.
Another very preferred embodiment of the invention relates to compounds of the general formula Ia':
Figure imgf000064_0001
wherein k is 0, 1 , 2 or 3, and wherein A, Q, R1, R2, R3, R5, R6 and Rc are as defined above. Amongst the compounds Ia' those are preferred, wherein Q, A, R1, R2, R3 , R5, R6 and Rc have the meanings given as preferred.
Examples of compounds Ia' are given in the following tables 181 to 360:
Tables 181 to 270:
Compounds of the formula Ia1, wherein R1 is H, R3 is H, R2 is H, R5 is H, R6 is CH3 and (Rc)k are as defined in one of the tables 1 to 90 and Q and A are given in table A .
Tables 271 to 360:
Compounds of the formula Ia', wherein R1 is H, R3 is H, R2 is H, R5 is CH3, R6 is CH3 and (Rc)k are as defined in one of the tables 1 to 90 and Q and A are given in table A.
Another very preferred embodiment of the invention relates to compounds of the general formula Ib:
Figure imgf000065_0001
wherein k is 0, 1 , 2 or 3, and wherein A, Q, R1, R3, R5 and Rc are as defined above and Y is as defined above. Amongst the compounds Ia those are preferred, wherein Y is O, OCH2 or S and wherein Q, A, R1, R3 , R5 and Rc have the meanings given as preferred.
Examples of compounds Ib are given in the following tables 361 to 378:
Table 361 :
Compounds of the formula Ia, wherein Y is O, R1 is H, R3 is H, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 362:
Compounds of the formula Ia, wherein Y is O, R1 is H, R3 is H, R5 is CH3 and k is 0 (i.e.
(Rc)k is absent) and wherein Q and A are given in table A;
Table 363:
Compounds of the formula Ia, wherein Y is S1 R1 is H, R3 is H, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A; Table 364:
Compounds of the formula Ia, wherein Y is S1 R1 is H1 R3 is H, R5 is CH3 and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 365:
Compounds of the formula Ia, wherein Y is O, R1 is H, R3 is H, R5 is H and (Rc)k is 4-CI and wherein Q and A are given in table A;
Table 366:
Compounds of the formula Ia, wherein Y is S, R1 is H, R3 is H1 R5 is H and (Rc)k is 4-CI and wherein Q and A are given in table A;
Table 367: Compounds of the formula Ia1 wherein Y is O1 R1 is H, R3 is H, R5 is CH3 and (Rc)k is A- Cl and wherein Q and A are given in table A;
Table 368:
Compounds of the formula Ia, wherein Y is S, R1 is H, R3 is H, R5 is CH3 and (Rc)k is A- Cl and wherein Q and A are given in table A;
Table 369:
Compounds of the formula Ia, wherein Y is O, R1 is H, R3 is H1 R5 is H and (Rc)k is A- Cl1 5-NO2 and wherein Q and A are given in table A;
Table 370:
Compounds of the formula Ia, wherein Y is S, R1 is H, R3 is H, R5 is H and (Rc)k is A-
Cl, 5-NO2 and wherein Q and A are given in table A;
Table 371:
Compounds of the formula Ia, wherein Y is O, R1 is H, R3 is H, R5 is CH3 and (Rc)k is A- Cl, 5-NO2 and wherein Q and A are given in table A;
Table 372: Compounds of the formula Ia, wherein Y is S1 R1 is H, R3 is H, R5 is CH3 and (Rc)k is A- Cl, 5-NO2 and wherein Q and A are given in table A;
Table 373: DO
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is H and k is 0 (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 374:
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is CH3 and k is O (i.e. (Rc)k is absent) and wherein Q and A are given in table A;
Table 375:
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is H and (Rc)k is 4-CI and wherein Q and A are given in table A;
Table 376:
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is CH3 and (Rc)k is 4-CI and wherein Q and A are given in table A;
Table 377:
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is H and (Rc)k is 4-CI, 5-NO2 and wherein Q and A are given in table A;
Table 378:
Compounds of the formula Ia, wherein Y is OCH2 (the oxygen atom is attached to the phenyl ring), R1 is H, R3 is H, R5 is CH3 and (Rc)k is 4-CI, 5-NO2 and wherein Q and A are given in table A.
The compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists.
Scheme 1:
Figure imgf000067_0001
Compounds of formula I1 wherein R6 is H are obtainable from compounds Il by hydrogenation of the C=N-double bond in Il according to standard methods of organic chemistry well known in the art and described e.g. in US 2002022730, Tetrahedron 1994, 50, 4399-4428, Tetrahedron 2002, 58, 7925-7932 or Trends in Heterocyclic Chemistry 1997, VoI 5, 17-36.
Hydrazides I carrying substituents R6 different from hydrogen are obtainable by functionalyzing hydrazides I with R6 = H by well known methods such as described in Letters in Peptide Science 2003, 10, 1-9, J. Am. Chem. Soc. 2004, 126, 5366-5367 or Synthetic Communications 2002, 32, 3603-3610 (see scheme 2).
Scheme 2:
Figure imgf000068_0001
If individual compounds I are not obtainable by the route described above, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described. The preparation of the compounds of formula I may lead to them being obtained as isomer mixtures (stereoisomers, enantiomers). If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
Acyl hydrazones of the formula Il are known in the art, e.g. from PCT/EP 2004/005681 , or they can be obtained applying synthesis methods described for example in WO 87/06133 by analogy. For instance, suitable hydrazides III can be reacted with aldehydes, esters or ketones IV according to scheme 3 to form acyl hydrazones of the formula II.
Scheme 3:
Figure imgf000068_0002
(III) (IV) (H)
The compounds of formula I are effective through contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and/or ingestion (bait, or plant part). The compounds of the formula I are in particular suitable for efficiently controlling nematodes and insects. In particular, they are suitable for controlling the following pests:
Insects:
from the order of the lepidopterans {Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana,
Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pirn, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles macυlipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,
thrips (Thysanoptera), e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata and Solenopsis invicta,
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisa tabaci, Bemisa argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis- nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii,
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis, and
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
Nematodes :
plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloido- gyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterode- ra species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphe- lenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belono- laimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelen- chus species; Ring nematodes, Criconema species, Criconemella species, Cricone- moides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus des- tructor, Ditylenchus dipsaci and other Ditylenchus species; AwI nematodes, Dolichodo- rus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylen- chus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemi- criconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Tri- chodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species. The compounds of the formula I and their salts are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amhlyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalυs appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidas and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychυs cinnabaήnus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
For use in a method according to the present invention, the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.
The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries, which are suitable, are essentially:
- water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
The following are examples of formulations: 1. Products for dilution with water
A Soluble concentrates (SL)
10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active ingredient dissolves upon dilution with water. B Dispersible concentrates (DC)
20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.
C Emulsifiable concentrates (EC)
15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). Dilution with water gives an emulsion.
D Emulsions (EW, EO)
40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.
E Suspensions (SC, OD)
In an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.
F Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.
G Water-dispersible powders and water-soluble powders (WP, SP) 75 parts by weight of a compound according to the invention are ground in a rotor- stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.
2. Products to be applied undiluted
H Dustable powders (DP)
5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product. I Granules (GR, FG, GG, MG)
0.5 parts by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.
J ULV solutions (UL)
10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.
The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1%.
The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
Compositions of this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients. These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :100 to 100:1.
The following list of pesticides together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations, but not to impose any limitation:
Organophosphates: Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;
Carbamates: Alanycarb, Bendiocarb, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Fenoxycarb, Furathiocarb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate;
Pyrethroids: Bifenthrin, Cyfluthrin, Cypermethrin, alpha-Cypermethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda- Cyhalothrin, Permethrin, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tralomethrin, Zeta- Cypermethrin;
Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: Chlorfluazuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;
Various: Abamectin, Acequinocyl, Acetamiprid, Amitraz, Azadirachtin, Bifenazate, Cartap, Chlorfenapyr, Chlordimeform, Cyromazine, Diafenthiuron, Dinetofuran, Diofenolan, Emamectin, Endosulfan, Ethiprole, Fenazaquin, Fipronil, Formetanate, Formetanate hydrochloride, Hydramethylnon, Imidacloprid, Indoxacarb, Metaflumizon (= 4-{(2Z)-2-({[4-(trifluoro-rnethoxy)anilino] carbonyl} hydrazono)-2-[3-(trifluoromethyl)- phenyljethyl} benzo-nitrile), Nitenpyram, Pyridaben, Pymetrozine, Spinosad, Sulfur, Tebufenpyrad, Thiamethoxam, Thiacloprid, Thiocyclam, Spiromesifen, Spirodiclofen, Pyridalyl and the pesticide of the following formula as described in WO 98/05638:
Figure imgf000077_0001
Fungicides are those selected from the group consisting of
• acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl,
• amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph
• anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, • antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
• azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol
• dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin,
• dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, • heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thiophanate-methyl, tiadinil, tricyclazole, triforine, • copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate,
• nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl
• phenylpyrroles such as fenpiclonil or fludioxonil,
• sulfur • other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, nnetrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamid
• strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, • sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid
• cinnemamides and analogs such as dimethomorph, flumetover or flumorph.
The aforementioned compositions are particularly useful for protecting plants against infestation of said pests or to combat these pests in infested plants. However, the compounds of formula I are also suitable for the treatment of seeds.
Compositions for seed treatments include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water soluble powders SS and emulsion ES. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.5 to 80% of the active ingredient, from 0,05 to 5 % of a wetter, from 0.5 to 15 % of a dispersing agent, from 0,1 to 5 % of a thickener, from 5 to 20 % of an anti-freeze agent, from 0,1 to 2 % of an anti-foam agent, from 1 to 20 % of a pigment and/or a dye, from 0 to 15 % of a sticker /adhesion agent, from 0 to 75 % of a filler/vehicle, and from 0,01 to 1 % of a preservative.
Suitable pigments or dyes for seed treatment formulations are pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57:1, pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Stickers / adhesion agents are added to improve the adhesion of the active materials on the seeds after treatment. Suitable adhesives are block copolymers EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers. Compositions which are useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW1 EO, ES)
E Suspensions (SC, OD, FS) F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Dustable powders (DP, DS)
For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, compounds of formula I are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 0C1 dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
The compounds of formula I and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula I and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N1N- diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2- hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)- 3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)- Eucamalol (1), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is mostly done by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
The compounds of formula I and its compositions can be used for protecting non-living material, in particular cellulose-based materials such as wooden materials e.g. trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
In the methods according to the invention the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula I or with a salt thereof or with a composition, containing a pesticidally effective amount of a compound of formula I or a salt thereof.
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant). In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and / or insecticide.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
In the treatment of seed, the application rates of the mixture are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
The present invention is now illustrated in further detail by the following examples.
The products were characterized by coupled High Performance Liquid
Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany).
Elution: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water in a ratio of from 5:95 to 95:5 in 5 minutes at 40 0C.
In the examples the following abbreviations are used:
m.p.: melting point THF: tetrahydrofuran MS: Quadrupol electrospray ionisation, 80 V (positiv modus) RT: retention time
Example 1 (compound A-90 of table B):
1.1 Furan-2-carboxylic acid N-methyl-hydrazide
To a mixture of 3.0 g (65 mmol) of methyl hydrazine in 35 ml of dichloromethane 0.85 g (6.5 mmol) of furan-2-carboxylic acid chloride in 35 ml of dichloromethane were added at O0C within 1 hour. The mixture was allowed to warm to room temperature and stirred for 3 hours. After evaporation of the solvent the resulting oil was sufficiently pure for further reactions (HPLC/MS: RT = 0.707 min, m/z = 140 [M+H]+).
1.2 Furan-2-carboxylic acid N-methyl-N'-[2-methyl-3-(2-fluorophenyl)-allylidene]- hydrazide
A mixture of 95 mg (0.66 mmol) of furan-2-carboxylic acid N-methyl-hydrazide and 98 mg (0.6 mmol) of 2-methyl-3-(2-fluorophenyl) acrolein in 5 ml of methanol was heated to reflux overnight. After cooling to room temperature and evaporation of the solvent 168 mg (0.59 mmol, 98%) of the desired product were obtained. The compound was sufficiently pure for subsequent reactions (> 90% according to HPLC/MS; RT = 3.640 min, m/z = 287 [M+H]+).
1.3 Furan-2-carboxylic acid N'-[3-(2-fluorophenyl)-2-methyl-allyl]-N-methyl-hydrazide To 114 mg (0.4 mmol) of furan-2-carboxylic acid N-methyl-N'-[2-methyl-3-(2- fluorophenyl)-allylidene]-hydrazide and 38 mg (0.64 mmol) of dimethylamine- borane complex in 1 ml of dichloromethane which were cooled to O0C 456 mg (2.4 mmol) of p-toluenesulfonic acid monohydrate in 2ml of dichloromethand/methanol 3:1were added. Upon stirring the resulting mixture at O0C for 30 min 2.5 ml of Na2CO3 solution (10% w/v) were added and the mixture was heated to reflux for 30 min. After cooling to room temperature the organic phase was separated and the aqueous phase was extracted twice with dichloromethane. The combined organic phases were dried over MgSO4 and concentrated in vacuo. 95 mg (0.33 mmol, 83%) of furan-2-carboxylic acid N'-[3- (2-fluorophenyl)-2-methyl-allyl]-N-methyl-hydrazide were obtained which were > 90% pure according to HPLC/MS (RT = 3.217 min, m/z = 289 [M+H]+).
Example 2 (compound A-1 of table B):
2.1 2-Fluorobenzoic acid N'-(3-(3-fluorophenyl)-2-methyl-allylidene) hydrazide The title compound was obtained by analogy to the method outlined in example 1.2 by reacting 2-fluorobenzoic acid hydrazide with 2-methyl-3-(3-fluorophenyl) acrolein.
2.2 2-Fluorobenzoic acid N'-[3-(3-fluorophenyl)-2-methyl-allyl] hydrazide
In a three-necked round-bottom flask (50 ml), fitted with a reflux condenser and a thermometer 1.00 g (3.33 mmol, 1.0 eq) of 2-fluorobenzoic acid N'-(3-(3- fluorophenyl)-2-methyl-allylidene) hydrazide and 314.7 mg (5.34 mmol, 1.6 eq) of dimethylamine-borane complex were equilibrated for 5 min in 10 ml of CH2CI2 at
O0C. Then 3.804 g (20.00 mmol, 6.0 eq) of p-toluenesulfonic acid monohydrate were added as a solution in 6 ml of CH2CI2/Me0H 3:1. After stirring at 0° for 30 minutes 12.5 ml of Na2CO3 solution (10% w/v) and 4 ml MeOH were added and the mixture was refluxed for a further 30 minutes. After cooling to room temperature the organic phase was separated and the aqueous phase was extracted twice with CH2CI2. The combined organic phases were dried over MgSO4 and concentrated in vacuo. 0.956 g (3.17 mmol, 95 %) of 2-fluorobenzoic acid NT-(3-(3-fluorophenyl)-2-methyl-allyl) hydrazide were obtained which were > 95% pure according to HPLC/MS (1H-NMR, de-DMSO, 500MHz; δ = 1.9 (s, 3H), 3.5 (d, 2H), 5.5 (pt, 1H), 6.5 (s, 1H), 7.0-7.15 (m, 3H),
7.2-7.3 (m, 2H), 7.3-7.4 (m, 1 H), 7.4-7.55 (m, 2H), 9.75 (d, 1H)).
The compounds A2 to A321 given in table B, compounds B1 to B56 given in table C, compounds C1 and C2 given in table D, compounds D1 and D2 given in table E, compounds E1 to E38 given in table F, compound F1 given in table G, compounds G1 to G3 given in table H, compounds H1 to H55 given in table J, compounds J1 to J26 given in table K and compounds K1 to K10 given in table L were obtained by analogy to the methods of examples 1 and 2.
Table B
Figure imgf000085_0001
Figure imgf000085_0002
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0002
Table C:
Figure imgf000102_0001
Figure imgf000102_0003
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0002
The heteroatom of the moiety Q is attached to the radical A
Table D:
Figure imgf000105_0001
Figure imgf000106_0003
Table E:
Figure imgf000106_0001
Figure imgf000106_0004
Table F
Figure imgf000106_0002
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0002
Table G:
Figure imgf000109_0001
Figure imgf000109_0003
Table H
Figure imgf000110_0001
Figure imgf000110_0003
Table J:
Figure imgf000110_0002
10
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0002
Table K
Figure imgf000114_0001
Figure imgf000114_0003
Figure imgf000115_0001
Figure imgf000116_0002
Table L
Figure imgf000116_0001
Figure imgf000116_0003
Figure imgf000117_0001
The action of the compounds of the formula I against pests was demonstrated by the following experiments:
I Activity against insects
1.1 Cotton aphid {aphis gossypii)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Cotton plants at the cotyledon stage (one plant per pot) were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.
In this test, compounds A10, A11 , A16, A19, A21 , A44, A47, A63, A68, B11, B20 and B25 at 300 ppm showed over 75% mortality in comparison with untreated controls.
1.2 Green Peach Aphid (Myzus persicae)
The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.
Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour photoperiod) at about 250C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.
In this test, compounds compounds A13, A51 , A70, A74, A75, A79, A80, A81 ,
A83, B1 , B22 and B34 at 300 ppm showed over 75% mortality in comparison with untreated controls. 1.3 Orchid thrips (dichromothrips corbetti)
Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound was diluted to a concentration of 500 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone:water, plus 0.01 % Kinetic® surfactant.
Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 280C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish.
The level of thrips mortality was extrapolated from pre-treatment thrips numbers.
In this test, compounds A1, A2, A12, A141 , A149, A 155, A173, A218, A223, A260, A301 , A303, A305, A319, C1, E3 and E42 at 300 ppm showed over 75% mortality in comparison with untreated controls.
1.4 Bean Aphid (Aphis fabae)
Nasturtium plants grown in Metro mix in the 1st leaf-pair stage (variety 'Mixed Jewel') were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days.
In this test, compounds A93, A141 , A305, E1 , E3 and K6 at 300 ppm showed 75% mortality in comparison with untreated controls.

Claims

We claim:
1. An hydrazide compound of the general formula I
Figure imgf000120_0001
and the salts thereof, wherein
is absent or a covalent bond;
A is a cyclic radical selected from phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms as ring members which are selected, independently of one another, from O, N and S, the 5- or 6- membered heterocyclic radical may have a carbonyl group as ring member and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents Ra which are selected, independently of one another, from halogen, cyano, nitro, C1- do-alkyl, Ci-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, Ci-C10- alkoxy, d-C^-haloalkoxy, C2-C1o-alkenyloxy, C2-C10-haloalkenyloxy, C2- C10-alkynyloxy, C3-C1o-haloalkynyloxy, CrC1o-alkylthio, CrC^-haloalkylthio,
CrCio-alkylsulfinyl, CrC1o-haloalkylsulfinyl, CrC1o-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrC1o-alkoxycarbonyl, Ci-C10- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC-io-alkylcarbonyl, CrCio-haloalkylcarbonyl, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1 , 2, 3, 4 or 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, C1-C10- alkyl, Ci-C1o-haloalkyl, C3-C1o-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C1o-haloalkynyl, C1-C10- alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-
C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC1o-alkylthio, CrC^-haloalkylthio, d-Cio-alkylsulfinyl, CrCiθ-haloalkylsulfinyl, CrC^-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrC10-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC1o-alkylcarbonyl, CrC10-haloalkylcarbonyl and
R7R8N-CO-, wherein in each case two radicals Ra which are bound to adjacent carbon atoms may form a CH=CH-CH=CH moiety or a 0-CH2-O moiety, where in these two moieties 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above;
Q is selected from the group consisting of a single bond, C1-C4 alkylidene,
0-Ci-C4 alkylidene, S-C1-C4 alkylidene and NR9-Ci-C4 alkylidene, wherein the alkylidene group in the last four mentioned radicals is unsubstituted or carries 1, 2, 3 or 4 substituents selected from OH, =0, halogen, CrC4 haloalkyl and C1-C4 alkoxy; or
A-Q may together be d-C^-alkyl, which may be substituted by 1 or 2 substituents selected from the group consisting of =0, OH, CrC4-alkoxy, CrC4-alkylthio, halogen or CrC^alkylcarbonyloxy;
X is C=O, C=S or SO2;
Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from halogen, cyano, nitro, d-Cio-alkyl, Ci-Cio-haloalkyl, C3-C10-cycloalkyl, C3-
C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3- C10-haloalkynyl, CrC10-alkoxy, CrC10-haloalkoxy, C2-Ci0-alkenyloxy, C2- C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC^-alkylthio, Crdo-haloalkylthio, Ci-C10-alkylsulfinyl, CrCio-haloalkylsulfinyl, d-do-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrCio-alkoxycarbonyl, Ci-C10- haloalkoxycarbonyl, CrC-io-alkenyloxycarbonyl, C2-C10-haloalkenyloxy- carbonyl, CrC-io-alkylcarbonyl, d-do-haloalkylcarbonyl, C1-C10- alkylcarbonyloxy, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above, and wherein two radicals Rc which are bound to adjacent carbon atoms may form a 0-CH2-O moiety, where in said moiety 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above;
R1 is selected from the group consisiting of H, CrC10-alkyl, CrCi0-haloalkyl,
C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C1 (j-alkynyl, C2-C1o-haloalkynyl, phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for the aforementioned two last radicals to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Ra as defined above;
R2 is a monovalent radical selected from H1 halogen, cyano, CrC10-alkyl, C1- Cio-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-
Cio-haloalkenyl, C2-C10-alkynyl, C3-Ci0-haloalkynyl, C1-C10-BIkOXy, C1-C10- haloalkoxy, C2-C1o-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-Ci0-haloalkynyloxy, CrC1o-alkylthio, Ci-C1o-haloalkylthio, hydroxy-Cr C-io-alkyl, CrCi0-alkoxy-Ci-C10-alkyl, halo-CrC10-alkoxy-CrC1o-alkyl, C1- do-alkoxycarbonyl-CrdQ-alkyl, halo-CrC^-alkoxycarbonyl-CrC^-alkyl and phenyl which may be substituted by 1, 2, 3, 4 or 5 substituents Rb as defined above;
R3 is selected from the group consisiting of H, halogen, cyano, CrC10-alkyl,
Figure imgf000122_0001
C3-Ci0-cycloalkyl, C3-C10-halocycioalkyl, C2-C10-alkenyl,
C2-C10-haloalkenyl, C2-C10-alkynyl, C3-Ci0-haloalkynyl, Ci-C1o-alkoxy, C1- C1o-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10- alkynyloxy, C3-C1o-haloalkynyloxy, CrC^-alkylthio, CrC^-haloalkylthio, hydroxy-CrC10-alkyl, CrC^-alkoxy- CrCiO-alkyl, halo-CrCnj-alkoxy-Cr Cio-alkyl, CrC1o-alkoxycarbonyl-CrC1o-alkyl, halo-CrC10-alkoxycarbonyl-
CrC10-alkyl and phenyl which may be substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above;
R4 is hydrogen or has one of the meanings given for Rc or
R4 together with R2 is a bivalent radical, which is selected from O, S, CR10=N, N=N, 0-CR11R12, S-CR11R12, N(R13)-CR11R12, O-C(O), O-C(S), S-C(O); N(R13)-C(O) or N(R13)-C(S);
R5 is selected from the group consisiting of H, CτC1o-alkyl, CrC10-haloalkyl,
C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C1o-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C2-C10-haloalkynyl, benzyl and phenyl wherein benzyl and phenyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rd which are selected, independently of one another, from halogen, cyano, nitro, C1-C10- alkyl, C^C^-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-Ci0-haloalkynyl, C1-C10- alkoxy, CrC10-haloalkoxy, C2-C1o-alkenyloxy, C2-C10-haloalkenyloxy, C2- C1o-alkynyloxy, C3-C1o-haloalkynyloxy, CrC10-alkylthio, CrC1o-haloalkylthio, C-C^-alkylsulfinyl, CrC10-haloalkylsulfinyl, CrC^-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrCio-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-Ci0-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, d-do-alkylcarbonyl, CrCio-haloalkylcarbonyl and R7R8N-CO-;
R6 is selected from the group consisiting of H, d-do-alkyl, which is optionally substituted by CN or NO2, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C1 o-alkynyl, C2-C10- haloalkynyl, Ci-C1o-alkylthio, CrC10-haloalkylthio, CrC10-alkylsulfinyl, C1- Cto-haloalkylsulfinyl, d-do-alkylsulfonyl, d-do-haloalkylsulfonyl, C1-C10- alkoxycarbonyl, where the alkyl moiety of alkylcarbonyl may be unsubstituted or substituted by 1 , 2 or 3 substituents selected from the group consisting of CrCi0-alkylthio, phenylthio, phenyl and phenoxy, C1- C1o-haloalkoxycarbonyl, C2-C10-alkenylcarbonyl, Crdo-alkenyloxycarbonyl, Ca-C-io-haloalkenyloxycarbonyl, d-C1o-alkylcarbonyl, C1-C10- haloalkylcarbonyl, hydroxy-CrC1o-alkyl, d-do-alkoxy- d-do-alkyl, halo-
Ci-C1o-alkoxy-d-C1o-alkyl, CrC1o-alkoxycarbonyl-CrCi0-alkyl, halo-d-do- alkoxycarbonyl-Crdo-alkyl R7R8N-CO-, benzoyl (C6H5-CO-), C3-C10- cycloalkylcarbonyl, R6a-CO-, wherein R6a is C1-C4-alkoxycarbonyl, phenoxy, naphthyl or a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, it being possible for phenoxy, naphthyl and the 5- or 6-membered heterocyclic radical to be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Ra as defined above, and benzyl wherein benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above;
R7, R8 are selected independently of one another from H, CrC1o-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-Ci0-alkynyl, C3-C1o-haloalkynyl, phenyl, benzoyl, naphthyl or benzyl wherein the phenyl ring in the aforementioned four radicals may be substituted by 1 , 2, 3, 4 or 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, d-C1o-alkyl, d-C1o-haloalkyl, C3-Cio-cycloalkyl, C3-Ci0-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, CrC1o-alkoxy, d-do-haloalkoxy, d-do-alkylthio, CrC1o-haloalkylthio, C1- C1o-alkylsulfonyl, d-C10-haloalkylsulfonyl, hydroxy, CrC1o-alkoxycarbonyl, d-C1o-haloalkoxycarbonyl, C2-C1o-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC1o-alkylcarbonyl and CrC1o-haloalkylcarbonyl;
R9 is hydrogen, d-C1o-alkyl, CrC1o-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C1o-alkynyl, C3-C10- haloalkynyl, C^C^-haloalkylsulfonyl, CrC-iQ-alkylcarbonyl, C1-C10- haloalkylcarbonyl, R7R8N-CO-, phenyl, benzoyl, naphthyl or benzyl, wherein the phenyl ring in the aforementioned four radicals may be substituted by 1 , 2, 3, 4 or 5 substituents Rb; and
R10 is hydrogen or has one of the meanings given for Rc;
R11, R12 are selected independently of one another from H, CrC10-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl and C3-C1o-haloalkynyl, C1-C10^IkOXy, C1-C10- haloalkoxy, Ci-C10-alkylthio, CrC1o-haloalkylthio, hydroxy-CrC1o-alkyl, C1-
C^-alkoxy-CrC^-alkyl, halo-CrC^-alkoxy-CrC^-alkyl, C1-C10- alkoxycarbonyl-CrC1o-alkyl, halo-CrC^-alkoxycarbonyl-CrC^-alkyl, one of the radicals R11 or R12 may also be CrC^-alkylsulfonyl, C1-C10- haloalkylsulfonyl, CrC1o-alkoxycarbonyl, CrC^-haloalkoxycarbonyl, C2- C1o-alkenyloxycarbonyl, C2-C1o-haloalkenyloxycarbonyl, C1-C10- alkylcarbonyl, C^C^-haloalkylcarbonyl or R7R8N-CO-.
R13 is hydrogen, cyano, CrC10-alkyl, CrC1o-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C1 o-alkynyl, C3-C10- haloalkynyl, CrC^-haloalkylsulfonyl, CrC1o-alkylcarbonyl, C1-C10- haloalkylcarbonyl, R7R8N-CO-, phenyl or benzyl, wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb;
except for a compound of formula I, wherein A and Ar are unsubstituted phenyl, Q is a single bond, X is C=O and R1, R2, R3, R5 and R6 are hydrogen.
2. The compound as claimed in claim 1 , wherein
A is a cyclic radical selected from phenyl and a 5- or 6-membered heterocyclic radical with 1 to 4 heteroatoms which are selected, independently of one another, from O, N and S, and where the cyclic radical may have 1 , 2, 3, 4 or 5 substituents Ra which are selected, independently of one another, from halogen, cyano, nitro, Ci-C1o-alkyl, C1- C1o-haloalkyl, C3-C1o-cycloalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2- C1o-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC-io-alkoxy, C1-C10- haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C1o-alkynyloxy, C3-C1o-haloalkynyloxy, CrC^-alkylthio, CrC1o-haloalkylthio, C1-C10- alkylsulfinyl, CrC^-haloalkylsulfinyl, CrC10-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrC1o-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C1o-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, CrC10-alkylcarbonyl, d-do-haloalkylcarbonyl, R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1 , 2, 3, 4 or 5 substituents Rb which are selected, independently of one another, from halogen, cyano, nitro, CrC10- alkyl, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-Ci0-haloalkynyl, C1-C10- alkoxy, CrC^-haloalkoxy, C2-C10-alkenyloxy, C2-Ci0-haloalkenyloxy, C2- C-io-alkynyloxy, C3-Ci0-haloalkynyloxy, CrC1o-alkylthio, CrC10-haloalkylthio, Ci-C1o-alkylsulfinyl, CrC^-haloalkylsulfinyl, CrC-io-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, Ci-C1o-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C1o-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, d-do-alkylcarbonyl, C-i-C-io-haloalkylcarbonyl and R7R8N-CO-, wherein two radicals Ra which are bound to adjacent carbon atoms may form a CH=CH-CH=CH moiety or a 0-CH2-O moiety, where in these two moieties 1 or 2 hydrogen atoms may be replaced by a radical Rb as defined above;
Ar is an aromatic radical selected from phenyl, naphthyl, pyridyl, pyrimidyl, furyl and thienyl, where the aromatic radical may carry 1 , 2, 3, 4 or 5 substituents Rc which are selected, independently of one another, from halogen, cyano, nitro, CrC10-alkyl, d-C^-haloalkyl, C3-C10-cycloalkyl, C3- C1o-halocycloalkyl, C2-C10-alkenyl, C2-C1o-haloalkenyl, C2-C10-alkynyl, C3- C10-haloalkynyl, CrC1o-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2- C10-alkynyloxy, C3-C1o-haloalkynyloxy, CrC1o-alkylthio, d-do-haloalkylthio, CrCiϋ-alkylsulfinyl, CrC^-haloalkylsulfinyl, CrC1o-alkylsulfonyl, C1-C10- haloalkylsulfonyl, hydroxy, NR7R8, CrC1o-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C10-alkenyloxycarbonyl, C2-C10-haloalkenyloxy- carbonyl, CrC-io-alkylcarbonyl,
Figure imgf000125_0001
R7R8N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above;
R1 is selected from the group consisiting of H, CrC^-alkyl, CrC^-haloalkyl,
C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C1 o-alkenyl, C2-C10-haloalkenyl, C2-Ci0-alkynyl and C2-C10-haloalkynyl ;
R6 is selected from the group consisiting of H1 d-C-io-alkyl, which is optionally substituted by CN or NO2, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C1o-alkynyl, C2-C10- haloalkynyl, d-C^-alkylsulfinyl, d-C^-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, CrC10-alkoxycarbonyl, C1-C10- haloalkoxycarbonyl, C2-C1o-alkenyloxycarbonyl, C2-C10- haloalkenyloxycarbonyl, d-C^-alkylcarbonyl, CrC^-haloalkylcarbonyl, hydroxy-CrC10-alkyl, CrC1o-alkoxy- Ci-C1o-alkyl, halo-CrC^-alkoxy-Cr C1o-alkyl, CrC^-alkoxycarbonyl-CrC^-alkyl, halo-CrC1o-alkoxycarbonyl-
CrC1o-alkyl R7R8N-CO- and benzyl wherein benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents Rb as defined above; and
R7, R8 are selected independently of one another from H, Ci-C10-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C1o-alkynyl, C3-C1o-haloalkynyl, phenyl or benzyl wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents which are selected, independently of one another, from halogen, cyano, nitro, C1- C10-alkyl, CrC^-haloalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, CrCi0-alkoxy, Ci-Cio-haloalkoxy, C1-C10- alkylthio, Ci-C10-haloalkylthio, d-C^-alkylsulfonyl, CrC1o-haloalkylsulfonyl, hydroxy, CrC1o-alkoxycarbonyl, d-C^-haloalkoxycarbonyl, C2-C10- alkenyloxycarbonyl, C2-C10-haloalkenyloxycarbonyl, CrC^-alkylcarbonyl and d-Cio-haloalkylcarbonyl.
3. The compound as claimed in claim 1 , wherein Ar in formula I is phenyl, which is unsubstituted or substituted by 1, 2, 3 or 4 radicals Rc as defined above.
4. The compound as claimed in claim 1 , wherein X in formula I is C=O.
5. The compound as claimed in claim 1 , wherein A in formula I is a cyclic radical selected from phenyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazoloyl, pyridyl, pyrimidinyl, pyrazinyl, and pyridazinyl and where the cyclic radical may be substituted by 1 , 2 or 3 substituents Ra as defined above.
6. The compound as claimed in claim 1 , wherein A in formula I is a cyclic radical selected from phenyl, thienyl, and pyridyl, where the cyclic radical may be substituted by 1 , 2 or 3 substituents Ra which are selected, independently of one another, from halogen, Ci-C4-alkyl, d-C4-alkoxy, CrC4-haloalkoxy and Ci-C4- haloalkyl.
7. The compound as claimed in claim 1 , wherein A in formula I is 2-thienyl which may be substituted by 1 , 2 or 3 substituents Ra which are selected, independently of one another, from halogen, CrC4-alkyl, C1-C4-BIkOXy, CrC4-haloalkoxy and CrC4-haloalkyl.
8. The compound as claimed in claim 1, wherein Q in formula I is selected from a single bond, -CH2-, 0-CH2-, -S-CH2-, -0-CH(CH3)- and -S-CH(CH3)-.
9. The compound as claimed in claim 1 , wherein Q and A together are CrC1o-alkyl which may be substituted by 1 or 2 substituents selected from the group consisting of =0, OH and and CrC2-alkoxy.
10. The compound of the general formula I as defined in claim 1 or a salt thereof, wherein R1 is selected from the group consisting of hydrogen CrC^-alkyl and C1- Cio-haloalkyl.
11. The compound as claimed in claim 1 , wherein R2 in formula I is selected from hydrogen, halogen and CrC4-alkyl.
12. The compound as claimed in claim 1, wherein R3 in formula I is selected from hydrogen, halogen and CrC^alkyl.
13. The compound as claimed in claim 1 , wherein R3 in formula I is hydrogen.
14. The compound as claimed in claim 1 , wherein R4 is hydrogen or a radical Rc as defined above.
15. The compound as claimed in claim 14, wherein Ar is phenyl, which is unsubstituted or substituted by 1, 2 or 3 radicals Rc which are selected, independently of one another, from halogen, CN, Ci-C4-alkyl, CrC4-alkoxy, C-i- C4-haloalkoxy and C-ι-C4-haloalkyl.
16. The compound as claimed in claim 1 , wherein R4 together with R2 is -O-.
17. The compound as claimed in claim 16 wherein Ar in formula I is phenyl, which is unsubstituted or which may carry 1, 2 or 3 radicals Rc which are selected, independently of one another, from halogen, CN, CrQ-alkyl, C1-C4^IkOXy1 C1-
C4-haloalkoxy and d-C4-haloalkyl.
18. The compound as claimed in claim 1 , wherein R5 is selected from the group consisiting of H, CrC10-alkyl, CrC^-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl.
19. The compound as claimed in claim 1, wherein R6 is hydrogen.
20. A composition for combating pests, selected from insects, arachnids and nematodes, which comprises a pesticidally effective amount of at least one compound of the general formula I as defined in claim 1 and at least one inert carrier and/or at least one surfactant.
21. A method for combating pests, selected from insects, arachnids and nematodes, which comprises contacting said pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from an attack of or infestation by said pest, with a pesticidally effective amount of a compound of the general formula I as defined in claim 1 or a salt thereof.
22. The method as claimed in claim 21 , wherein the pests are insects.
23. A method for protecting crops from attack or infestation by pests, selected from insects, arachnids and nematodes, the method comprising contacting a crop with a pesticidally effective amount of at least one compound of formula I as defined in claim 1 or with a salt thereof.
24. A method for protecting non-living materials from attack or infestation by pests, selected from insects, arachnids and nematodes, the method comprising contacting the non-living material with a pesticidally effective amount of at least one compound of formula I as defined in claim 1 or with a salt thereof.
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