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WO2006125637A1 - O-(phenyl/heterocyclyl)methyl oxime ether compounds for combating animal pests - Google Patents

O-(phenyl/heterocyclyl)methyl oxime ether compounds for combating animal pests Download PDF

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Publication number
WO2006125637A1
WO2006125637A1 PCT/EP2006/004982 EP2006004982W WO2006125637A1 WO 2006125637 A1 WO2006125637 A1 WO 2006125637A1 EP 2006004982 W EP2006004982 W EP 2006004982W WO 2006125637 A1 WO2006125637 A1 WO 2006125637A1
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carbonyl
alkyl
haloalkyl
alkoxy
haloalkoxy
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French (fr)
Inventor
Michael Hofmann
Jürgen LANGEWALD
David G. Kuhn
Hassan Oloumi-Sadeghi
Franz-Josef Braun
Deborah L. Culbertson
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
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    • 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
    • A01N43/08—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 oxygen as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • 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
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    • 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
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    • 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
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    • 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
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    • A01N43/22—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 rings with more than six members
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    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A01N43/38—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings condensed with carbocyclic rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • 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
    • A01N43/42—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 condensed with carbocyclic rings
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • 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
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    • 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
    • C07D333/06—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 only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/62—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes 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 carbon atoms of the hetero ring
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Definitions

  • the present invention relates to a method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one O-(phenyl/heterocyclyl) methyl oxime ether compound.
  • EP-A 4754 discloses insecticidal oxime ether compounds of the formula
  • Ar is an aromatic radical
  • R is optionally substituted alkyl, alkenyl or cycloalkyl
  • Q is inter alia furylmethyl, thienylmethyl or benzyl.
  • EP-A 1 125931 describes biocidal alkyl-subsituted (hetero)aryl-ketoxime -O-ethers of the formula
  • Ar 1 and Ar 2 independently of each other represent an optionally substituted aryl or hetaryl radical
  • m and n are independently 0, 1 , 2 or 3
  • X is O, S, SO, SO 2 , NH or NR with R being a lower alkyl group
  • Y is H, CN 1 halogen, alkyl or alkoxy
  • R a and R b independently of each other, might inter alia be hydrogen, halogen, alkyl, haloalkyl and the like
  • R c is hydrogen, alkyl, aryl, hetaryl, alkenyl, alkynyl or acyl.
  • the compounds are suggested to have herbicidal, fungicidal or insecticidal activity.
  • Ar 1 and Ar 2 independently of each other represent an optionally substituted aryl or hetaryl radical, and R is an optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl.
  • the compounds are suggested to have acaricidal, nematicidal or insecticidal activity.
  • WO 02/081429 discloses oxime ether compounds of the formula
  • A is substituted phenyl or heterocyclyl
  • B is H, alkyl or a radical C(O)R 1 , C(S)R 1 or SO 2 R 2 etc., with R 1 , R 2 being inter alia alkyl or cycloalkyl
  • R represents alkyl, alkenyl, haloalkyl or phenylalkyl
  • X is alkyl, cycloalkyl etc.
  • the present invention relates to a method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one 0-(phenyl/heterocyclyl)methyl oxime ether of the formula I
  • k 0, 1 , 2, 3 or 4;
  • Ar is an aromatic ring selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl,
  • R a independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, d-do-alkyl, CrC 10 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -Ci 0 - halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -Ci 0 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 - haloalkynyl, C 1 -C 1C aIkOXy, d-do-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -Ci 0 - haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 -haloalkynyloxy, d-do-alkylthio, C 1
  • R 1 is hydrogen, d-do-alkyl, C r C 10 -haloalkyl, d-C 10 -cyanoalkyl, d-C 10 -hydroxy- alkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -haloalkenyl, C 3 -C 10 -alkynyl or C 2 -C 10 -haloalkynyl, wherein the last 6 radicals may be substituted by cyano, nitro, hydroxy, d-do-alkoxy, d-do-haloalkoxy, CrC 10 -alkylthio, d-do-haloalkylthio, C r C 10 -alkylsulfonyl, CrC 10 -haloalkylsulfonyl, (C 1 -C 10 -
  • R 2 is hydrogen, halogen, cyano, d-Cio-alkyl, d-do-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, C 1 -C 1 CaIkOXy, d-do-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 - haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 -haloalkynyloxy, C r C 10 -alkylthio, C 1 - C 10 -haloalkylthio, hydroxy-d-C 10 -alkyl
  • R 3 is hydrogen, halogen, cyano, Ci-Ci O -alkyl, CrC 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 -C 10 - haloalkynyl, C ⁇ C ⁇ -alkoxy, d-Cnj-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 - haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 -haloalkynyloxy, Crdo-alkylthio, C 1 - C 10 -haloalkylthio, hydroxy-Crdo-alkyl, d-C 10 -
  • R 4 is hydrogen, halogen, cyano, nitro, hydroxy, d-C 10 -alkyl, d-do-haloalkyl, C 3 - C 10 -cycloalkyl, C 3 -Ci 0 -halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 - alkynyl, C 3 -C 10 -haloalkynyl, d-do-alkoxy, d-do-haloalkoxy, C 2 -C 10 -alkenyloxy, C 2 -C 10 -haloalkenyloxy, C 2 -C 10 -alkynyloxy, C 3 -C 10 -haloalkynyloxy, C r C 10 -alkylthio, d-C 10 -haloalkylthio, d-do-alky
  • R 5 is hydrogen, d-C 10 -alkyl, d-C 10 -haloalkyl, C 3 -C 10 -cycloalkyl or C 3 -C 10 - halocycloalkyl;
  • R 8 is a cyclic radical selected from phenyl and a saturated, unsaturated or aromatic 5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 heteroatoms as ring members which are selected, independently of one another, from oxygen, sulfur and nitrogen, and where the cyclic radical may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents R d which are selected, independently of one another, from the group consisting of halogen, cyano, nitro, hydroxy, CrC 10 -alkyl, CrC 10 -haloalkyl, C 3 -Ci 0 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -C 10 -alkenyl,
  • Ci-Ci 0 -haloalkylthio Ci-Ci O -alkylsulfinyl, C r Ci 0 -haloalkylsulfinyl, C 1 -C 10 - alkylsulfonyl, d-Ci 0 -haloalkylsulfonyl, (C r Ci 0 -alkyl)carbonyl, (C 1 -C 10 - haloalkyl)carbonyl, (d-Ci 0 -alkoxy)carbonyl, (d-Ci 0 -haloalkoxy)carbonyl, (C 2 -C 10 - alkenyloxy)carbonyl, (C 2 -C 10 -haloalkenyloxy)carbonyl, NR 25 R 26 and CO-R 25 R 26 ;
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 are selected, independently of one another, from the group consisting of hydrogen, d-C 10 -alkyl, d-C 10 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 10 -halocycloalkyl, C 2 -Ci 0 -alkenyl, C 2 -C 10 -haloalkenyl, C 2 -C 10 -alkynyl, C 3 -C 10 -haloalkynyl, (C 1 -Ci 0 - alkyl)carbonyl, (Crdo-haloalkyljcarbonyl, phenyl, phenylcarbonyl
  • the compounds of the general formula I can be used for controlling animal pests.
  • animal pest is understood to include any pests that belong to the fauna, in particular arthropod pests such as insects and arachnids and also nemtodes.
  • arthropod pests such as insects and arachnids and also nemtodes.
  • the compounds of the formula I are especially useful from combating insects.
  • the invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful pests, in particular 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 invention also provides a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a 0-(phenyl/heterocyclyl)methyl oxime ether of formula I as defined herein, or a vet- erinarily acceptable salt thereof.
  • the parasites are preferably selected from insects, in particular from the Diptera, Siphonaptera and Ixodida orders.
  • 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.
  • Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers, enantiomers) which may occur and mixtures thereof.
  • both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof can be used.
  • the compounds of the general formula I may also exist in the form of different tautomers if R 6 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 and veterinarily 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 Ci-C 4 -alkyl, C r C 4 -hydroxyalkyl, C r C 4 -alkoxy, C r C 4 -alkoxy-C r C 4 -alkyl, hydroxy-CrC ⁇ alkoxy-d-C ⁇ alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(CrC 4 - alkyl)sulfonium, and sulfoxonium ions, preferably tri(C r C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CVC-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. 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.
  • Suitable acid addition salts e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hydrochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic 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 01 indicates in each case the possible number of carbon atoms in the group.
  • Halogen will be taken to mean fluoro, chloro, bromo and iodo.
  • d-Cio-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 ,2-dimethylbutyl, 1
  • d-do-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 C 1 -C 4 - haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoro- methyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro- difluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroe
  • C 1 - C 10 -haloalkyl in particular comprises d-C 2 -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-do-alkoxy and “d-C 10 -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, at any bond 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 d-C 4 -alkylthio such as methylthio, ethylthio, propylthio, isopro- pylthio, and n-butylthio.
  • d-C 10 -haloalkoxy and " d-C 10 -haloalkylthio” refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond 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 -f luoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,
  • C 1 -C 2 - fluoroalkoxy and d-C 2 -fluoroalkylthio refer to C r 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 -alkenyr intends a branched or unbranched unsatu- rated 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-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-buteny
  • C 2 -Cio-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 linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
  • C 2 -Cio-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 linkages, respectively, at any bond 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 -Ci 0 -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 linkages at any bond 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 at any bond in the alkynyl group, where some or all of the hydrogen atoms in this 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, cyclo- heptyl, cyclooctyl and cyclodecyl.
  • C 3 -C 10 -halocycloalkyl refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, 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.
  • CrC ⁇ -alkylcarbonyl refers to Crdo-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 J 2 , n-butylcarbonyl, CO-CH(CH 3 )-C 2 H 5> CO-CH 2 -CH(CH 3 ) 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- methylpentylcarbonyl
  • d-do-alkoxycarbonyl refers to CrC 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(CH 3 ) 2) CO-OC(CH 3 J 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-methylpentoxycarbon
  • halo-d-do-alkoxycarbonyl refers to d-C 10 -haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.
  • hydroxy-d-do-alkyl 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-do-alkoxy, C 1 -C 10 - haloalkoxy, C r C 10 -alkoxycarbonyl or d-do-haloalkoxycarbonyl.
  • 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, pyr- rolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, di- oxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperaz- inyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihy- drothiopyrany
  • 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 isoxa- zolyl.
  • R 1 is preferably hydrogen, d-do-alkyl, d-C 10 -haloalkyl, more preferably hydrogen, C 1 - d-alkyl or d-C 4 -haloalkyl, and especially hydrogen.
  • R 1 is phenyl or pyridyl.
  • R 2 is preferably selected from hydrogen, halogen, cyano and d-C 4 -alkyl, in particular from hydrogen, fluorine chlorine, bromine, cyano, methyl or ethyl.
  • R 3 is preferably selected from hydrogen, halogen and d-C 4 -alkyl, with hydrogen being more preferred.
  • R 5 is preferably selected from hydrogen and d-do-alkyl, in particular from hydrogen and Crd-alkyl.
  • R 8 in formula I is a cyclic radical selected from phenyl, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, oxadiazolyl or thiadiazolyl, and where the cyclic radical may be unsubstituted or substituted as de- scribed above.
  • the aformentioned radicals are unsubstituted or substituted by 1 , 2 or 3 radicals R d as defined above.
  • Preferred radicals R d comprise halogen, CN, d-d-alkyl, d-d-alkoxy, C 1 -C 4 - haloalkoxy, d-C 4 -alkylthio and d-C 4 -haloalkyl, in particular F, Cl, CN 1 methyl, meth- oxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoro- methoxy and difluoromethoxy.
  • R 8 is a cyclic radical selected from phenyl, thienyl, furyl, isoxazolyl, pyrazolyl, oxadiazolyl, imidazolyl, pyraz- inyl, pyrimidyl and pyridyl, in particular from pyridyl, oxadiazolyl, thienyl and phenyl, where the cyclic radical may be substituted by 1 , 2 or 3 substuituents R d which are as defined above and which are preferably selected, independently of one another, from halogen, CN, d-d-alkyl, d-C 4 -alkoxy, d-C 4 -haloalkoxy, C r C 4 -alkylthio and C 1 -C 4 - haloalkyl, in particular from F, Cl, CN, methyl, methoxy, ethoxy, methylthi
  • 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
  • a very preferred embodiment of the invention relates to compounds of the formula I 1 wherein R 6 is thienyl, in particular 2-thienyl which is unsubstituted or substituted by 1 , 2 or 3 radicals R d as defined above, the radicals R d being preferably selected, independently of one another, from halogen, CrC 4 -alkyl, CrC-alkoxy, C r C 4 -alkylthio, C 1 -C 4 - haloalkoxy and Ci-C 4 -haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoro- methyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • R 6 is furyl, in particular 2-furyl which is unsubstituted or substituted by 1 , 2 or 3 radicals R d as defined above, the radicals R d being preferably selected, inde- pendently of one another, from halogen, Ci-C 4 -alkyl, C 1 -C ⁇ aIkOXy, CrC ⁇ alkylthio, C 1 - C 4 -haloalkoxy and C 1 -C 4 -HaIOaIKyI, in particular from F, Cl, Br, methyl, methoxy, di- fluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • R 8 is pyridyl, in particular 2- or 3-pyridyl, more preferably 2-pyridyl which is unsubstituted or substituted by 1 , 2 or 3 radicals R d as defined above, the radicals R d being preferably selected, independently of one another, from halogen, C 1 - C 4 -alkyl, C 1 -C ⁇ aIkOXy, CrC ⁇ alkylthio, C ⁇ Crhaloalkoxy and Ci-C 4 -haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • R ⁇ is oxadiazolyl, in particular 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl or 1 ,3,4-oxadiazol-2-yl, which is unsubstituted or carries a radical R d as defined above, the radical R d being preferably selected, from C r C 4 -alkyl, C 3 -C ⁇ -cycloalkyl and C 1 -C 4 - haloalkyl, in particular from methyl, ethyl, tert-butyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and cyclopropyl.
  • a further very preferred embodiment of the invention relates to compounds of the for- mula I, wherein R ⁇ is phenyl, which is unsubstituted or substituted by 1 , 2 or 3 radicals R d as defined above, the radicals R d being preferably selected, independently of one another, from halogen, d-C 4 -alkyl, C r C 4 -alkoxy, C r C 4 -haloalkoxy, CrC-alkylthio and C r C 4 -haloalkyl, in particular from F 1 Cl, Br, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
  • Ar is preferably phenyl, which is unsubstituted or substituted by 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals R a as defined above, depending on the number k.
  • R 4 being different from hydrogen, the total number of radicals on phenyl is k+1 , or, if R 4 together with R 2 is the aformentioned bivalent radi- cal, the total number of substituents on phenyl is k.
  • radicals R a are selected, independently of one another, from halogen, CN, d-C 4 -alkyl, d-C 4 -alkoxy, Ci-C 4 -haloalkoxy and C r C 4 -haloalkyl, more preferably F 1 Cl, CN, CrC 3 -alkoxy, in particular methoxy, trifluoromethyl, di- fluoromethyl, trifluoromethoxy, difluoromethoxy and methyl.
  • R 2 and R 4 in formula I are monovalent radicals, i.e. R 2 and R 4 together do not form a bivalent radical.
  • R 2 is preferably selected from hydrogen, halogen, Ci-C 4 -alkyl, d-C 4 -alkoxy, C 1 - C 4 -haloalkoxy and d-C 4 -haloalkyl. More preferably R 2 is hydrogen, fluorine, chlorine bromine, methyl or ethyl.
  • R 4 is hydrogen or a radical R a as defined above.
  • R 4 is hydrogen or has one one of the preferred meanings of R a .
  • R 4 is 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 a as defined above.
  • Ar in formula I is phenyl, which is unsubstituted or substituted by 1, 2 or 3, in particular O, 1 or 2 radicals R a as defined above.
  • R b1 , R b2 , R b3 , R M and R b5 are preferably selected from hydrogen, d-C 4 -alkyl and d-C 4 -haloalkyl it being possible that R b2 and R b5 may also be selected from halogen.
  • R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 2 ⁇ are preferably selected independently from one another from hydrogen and d-C 4 -alkyl.
  • R c and R e are preferably selected, independently from another, from halogen, C r C 4 -alkyl, CN, NO 2 , OH 1 d-C ⁇ haloalkyl, d-C 4 -alkoxy and CrC-haloalkoxy.
  • the compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists.
  • O-alkylated hydroxylamines Il or their corresponding ammonium salts are known or can be prepared applying methods described e.g. in DE 3615473 or WO 95/04032 or in references cited therein.
  • aldehydes or ketones III can be obtained according to standard methods of organic synthesis, e.g. starting from benzaldehydes or het- eroaromatic aldehydes and aliphatic ketones or aldehydes (Organikum, Johann Am- brosius Barth Verlag, Heidelberg, 1996, pp. 493-495).
  • the compounds of the general formula I can be prepared by the method depicted in scheme 2. This method comprises reacting aldehydes or ketones of the formula III with hydroxylamine or its ammonium salts to form oximes IV which can be subsequently alkylated according to standard methods with compounds V to yield the compounds of the general formula I.
  • L is a conventional leaving group which can be replaced by O-nucleophiles, e.g. halogen, methylsulfonyloxy (mesylat), trifluormethylsulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesul- fonyloxy (tosylate)
  • O-nucleophiles e.g. halogen, methylsulfonyloxy (mesylat), trifluormethylsulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesul- fonyloxy (tosylate)
  • 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.
  • the compounds of the formula I and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids and insects as well as nematodes.
  • insects from the order of the lepidopterans 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, Den- drolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mel- lonella, Grapholitha funebrana, Grapholitha molesta, Heli
  • beetles Coldoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,
  • Leptinotarsa decemlineata Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta stholata, Popillia japonica, Sitona lineatus and Sito- philus granaria,
  • mosquitoes for example Aedes aegypti, Aedes albopictus, Aedes vex- ans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculat ⁇ s, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops dis- calis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sor- ghicola, Cordylobia anthropophaga, Culex pipiens, Culex nigripalpus, Cul
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • cockroaches e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
  • Hemiptera true bugs
  • Homoptera e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia tabaci, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfus
  • termites e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitenves flavipes, Reticulitermes lucifugus, Reticulitermes virginicus, Termes natalensis, and Coptotermes formosanus,
  • Hoplocampa minuta Hoplocampa testudinea, Monomorium pha- raonis, Solenopsis geminata, Solen
  • Vespula squamosa Paravespula vulgaris, Paraves- pula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,
  • crickets grasshoppers, locusts (Orthoptera), e.g Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina.
  • Orthoptera e.g Acheta domestica, Gryllotalpa gryllo- talpa, Locusta mi
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica
  • centipedes Chilopoda
  • Scutigera coleoptrata centipedes
  • milipedes e.g. Narceus spp.
  • earwigs e.g. forficula auricularia
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus h ⁇ manus corporis, Pthi- rus pubis, Haematopin ⁇ s e ⁇ rysternus, Haematopin ⁇ s suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • Nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- Kunststoffsis and other Globodera species; Heterodera avenae, Heterodera glycines, Het- erodera schachtii, Heterodera thfolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nema- todes
  • Arach- noidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, xodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Orni- thodorus turicata, Ornithonyssus bacoti
  • Arachnids e.g. of the
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panony- chus ulmi, Panonychus citri, and Oligonychus pratensis, Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa.
  • Compounds of the formula I are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Diptera and Homoptera.
  • 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.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexan
  • 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.
  • ground natural minerals e.g. kaolins, clays, talc, chalk
  • 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)
  • 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 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.
  • 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, e.g. 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
  • compounds I may be applied with other active ingredients, for example with 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.
  • Organo(thio)phosphates Acephate, Azamethiphos, Azinphos-methyl, Chlorpyrifos, Chlorpyrifos-methyl, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Me- thidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;
  • Pyrethroids Allethrin, Bifenthrin, Cyfluthrin, Cyhalothrin, Cyphenothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, zeta-Cypermethrin Deltamethrin, Esfenvaler- ate, Ethofenprox, Fenpropathrin, Fenvalerate, Imiprothrin, Lambda-Cyhalothrin, Perme- thrin, Prallethrin, Pyrethrin I and II, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tetrame- thrin, Tralomethrin, Transfluthrin;
  • Growth regulators a) chitin synthesis inhibitors: benzoylureas: Chlorfluazuron, Cyro- mazine, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, No- valuron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen, Spiromesifen;
  • Neonicotinoids Clothianidine, Dinotefuran, Imidacloprid, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Thiacloprid;
  • Pyrazole pesticides Acetoprole, Ethiprole, Fipronil, Tebufenpyrad, Tolfenpyrad, Va- niliprole; Various: Abamectin, Acequinocyl, Amidoflumet, Amidrazone, Amitraz, Azadirachtin, Benclothiaz, Bifenazate, Bistrifluron, Cartap, Chlorfenapyr, Chlordimeform, Cyflumeto- fen, Cyromazine, Diafenthiuron, Dimefluthrin, Diofenolan, Emamectin, Endosulfan, Fenazaquin, Flonicamid, Fluacyprim, Flubendiamide, Flufenerim, Flupyrazofos, For- metanate, Formetanate hydrochloride, Hydramethylnon, Indoxacarb, Lepimectin, Meta- flumizone, Milbemectin, NC 512,
  • R' is -CH 2 OCH 3 or H and R" is -CF 2 CF 2 CF 3
  • B 1 is hydrogen or a chlorine atom
  • B 2 is a bromine atom or CF 3
  • R B is d- C 6 -alkyl
  • 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. Ap- plication to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
  • compositions which are useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES)
  • 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 antifreeze 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 1 12, 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, polymethacry- lates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyl- eneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
  • 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, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethyl- formamide, 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.
  • 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 pesti- cidally 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 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.
  • 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 %.
  • Compounds of formula I and compositions comprising them may also be used for con- trolling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • Compounds of formula I and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
  • Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of formula I and compositions comprising them are suitable for sys- temic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
  • the compounds of formula I are especially useful for combating ectoparasites.
  • the compounds of formula I are especially useful for combating parasites of the follow- ing orders and species, respectively:
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, T ⁇ nga penetrans, and Nosopsyllus fasciatus,
  • cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta br ⁇ nnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
  • mosquitoes e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Ana- strepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, C ⁇ lex pipiens, Culex nigripalpus, Culex quinquefasciatus,
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • ticks and parasitic mites ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodo- rus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithon- yssus bacoti and Dermanyssus gallinae,
  • Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
  • Bots Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Tricho- dectes spp., and Felicola spp
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Roundworms Nematoda Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Xn- churidae; Trichuris spp., Capillaria spp,
  • Rhabditida e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
  • Strongylida e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp.
  • Cooperia spp. Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophago- stomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus den- tatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angio- strongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Diocto- phyma renale,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habro- nema spp.,
  • Thorny headed worms e.g. Acanthocephal ⁇ s spp., Macracanthor- hynchus hirudinaceus and Oncicola spp,
  • Planarians (Plathelminthes):
  • Flukes e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
  • Cercomeromorpha in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
  • the compounds of formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the compounds of formula I also are especially useful for combating endoparasites
  • Administration can be carried out both prophylactically and therapeutically.
  • Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the formula I compounds may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the formula I compounds may be formulated into an implant for subcutaneous administration.
  • the formula I compound may be transdermal ⁇ administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound.
  • the formula I compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound.
  • the formula I compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers.
  • the solutions are filtered and filled sterile.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation.
  • examples are polyvinylpyrrolidone, po- lyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
  • Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
  • Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
  • Solutions for use on the skin are prepared according to the state of the art and accor- ding to what is described above for injection solutions, sterile procedures not being necessary.
  • solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methyl- ethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether
  • ketons such as acetone, methyl- ethylketone
  • aromatic hydrocarbons such as acetone, methyl- ethylketone
  • vegetable and synthetic oils dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures
  • thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
  • Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results.
  • the thickeners employed are the thickeners given above.
  • Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
  • pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoti ⁇ g substances, antioxidants, light stabilizers, adhesives are added.
  • Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, pheno- xyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as N-methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, 2-pyrrolidone, 2,
  • Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
  • Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
  • Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
  • Suitable light stabilizers are, for example, novantisolic acid.
  • Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
  • Emulsions can be administered orally, dermally or as injections.
  • Emulsions are either of the water-in-oil type or of the oil-in-water type.
  • Suitable hydrophobic phases are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyc- eride mixture with vegetable fatty acids of the chain length C 8 -Ci 2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and di- glycerides of the C 8 -Ci 0 fatty acids,
  • fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length Ci 6 -C 18 , isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C 12 -C 18 , isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstea
  • Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
  • Suitable emulsifiers are:
  • non-ionic surfactants e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or leci- thin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
  • ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or leci- thin
  • anionic surfactants such as sodium lauryl sulfate, fatty alcohol ether sulfates,
  • Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
  • Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substan- ces, preservatives, antioxidants, light stabilizers.
  • auxiliaries such as wetting agents, colorants, bioabsorption-promoting substan- ces, preservatives, antioxidants, light stabilizers.
  • Liquid suspending agents are all homogeneous solvents and solvent mixtures.
  • Suitable wetting agents are the emulsifiers given above.
  • Other auxiliaries which may be mentioned are those given above.
  • Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
  • the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
  • Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
  • Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
  • auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula I.
  • the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day , preferably 1 mg/kg to 50 mg/kg per day.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
  • the preparations comprise the compounds of formula I against endopara- sites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
  • compositions comprising the compounds of formula I them are applied dermally / topically.
  • the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the com- pounds of formula I.
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • the active compounds can also be used as a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
  • parasiticidally 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 parasiticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
  • HPLC column RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany).
  • THF tetrahydrofuran
  • DMF N.N-dimethylformamide
  • MS Quadrupol electrospray ionisation, 80 V (positiv modus)
  • the title product could be obtained by analogy to the method described in prepa- ration example 1.4 b) starting from 2-methyl-3-phenyl-propenal oxime.
  • the active compounds were formulated in 1 :3 DMSO : water. 10 to 15 eggs were placed into microtiterplates filled with 2% agar-agar in water and 300 ppm formaline. The eggs were sprayed with 20 ⁇ l of the test solution, the plates were sealed with pierced foils and kept at 24-26°C and 75-85% humidity with a day/night cycle for 3 to 5 days. Mortality was assessed on the basis of the remaining unhatched eggs or larvae on the agar surface and/or quantity and depth of the digging channels caused by the hatched larvae. Tests were replicated 2 times.
  • the active compounds were formulated in 1 :3 DMSO : water. 50 to 80 eggs were placed into microtiterplates filled with 0.5% agar-agar and 14 % diet in water. The eggs were sprayed with 5 ⁇ l of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility of the hatched larvae. Tests were replicated 2 times.
  • the active compounds were formulated in 1 :3 DMSO : water. 15 to 25 eggs were placed into microtiterplates filled with diet. The eggs were sprayed with 10 ⁇ l of the test solution, the plates were sealed with pierced foils and kept at 27-29 0 C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility and of comparative feeding of the hatched larvae. Tests were replicated 2 times.
  • the active compounds were formulated in 1 :3 DMSO : water.
  • Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm artworkTM.
  • the leaf disks were sprayed with 2.5 ⁇ l of the test solution and 5 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-24 0 C and 35-45% under fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Tests were replicated 2 times.

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Abstract

The present invention relates to a method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one 0-(phenyl/heterocyclyl)methyl oxime ether of the formula (I), and/or at least one agriculturally acceptable salt thereof, wherein is absent or a covalent bond; k is 0, 1, 2, 3 or 4; Ar is an aromatic ring selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl, and wherein Ra, R1, R2, R3, R4, R5 and R6 are as defined in the claims and in the specification.

Description

O-(Phenyl/heterocycly I) methyl Oxime Ether Compounds for Combating Animal Pests
The present invention relates to a method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one O-(phenyl/heterocyclyl) methyl oxime ether compound.
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.
EP-A 4754 discloses insecticidal oxime ether compounds of the formula
Ar
R NO-Q
wherein Ar is an aromatic radical, R is optionally substituted alkyl, alkenyl or cycloalkyl and Q is inter alia furylmethyl, thienylmethyl or benzyl.
EP-A 1 125931 describes biocidal alkyl-subsituted (hetero)aryl-ketoxime -O-ethers of the formula
Figure imgf000002_0001
wherein Ar1 and Ar2 independently of each other represent an optionally substituted aryl or hetaryl radical, m and n are independently 0, 1 , 2 or 3, X is O, S, SO, SO2, NH or NR with R being a lower alkyl group, Y is H, CN1 halogen, alkyl or alkoxy, Ra and Rb, independently of each other, might inter alia be hydrogen, halogen, alkyl, haloalkyl and the like and Rc is hydrogen, alkyl, aryl, hetaryl, alkenyl, alkynyl or acyl. The compounds are suggested to have herbicidal, fungicidal or insecticidal activity.
DE-A 4213149 discloses heteroaryl-alkyl-ketoxime-0-ethers of the formula
Figure imgf000003_0001
wherein Ar1 and Ar2 independently of each other represent an optionally substituted aryl or hetaryl radical, and R is an optionally substituted alkyl, alkenyl, alkynyl or cycloalkyl. The compounds are suggested to have acaricidal, nematicidal or insecticidal activity.
WO 02/081429 discloses oxime ether compounds of the formula
Figure imgf000003_0002
wherein A is substituted phenyl or heterocyclyl, B is H, alkyl or a radical C(O)R1, C(S)R1 or SO2R2 etc., with R1, R2 being inter alia alkyl or cycloalkyl, R represents alkyl, alkenyl, haloalkyl or phenylalkyl, and X is alkyl, cycloalkyl etc. The compounds are useful for combating insects or acarides.
However, the activity of the oxime ether compounds of prior art against harmful pests is not satisfactory.
Therefore, there is continuing need to provide compounds which are useful for combating animal pests such as insects, nematodes and arachnids.
It is an object of the present invention to provide further compounds having a good ac- tivity 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 by the agriculturally or veterinably acceptable salts thereof.
Therefore, the present invention relates to a method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one 0-(phenyl/heterocyclyl)methyl oxime ether of the formula I
Figure imgf000004_0001
and/or at least one agriculturally acceptable salt thereof, wherein
is absent or a covalent bond;
k is 0, 1 , 2, 3 or 4;
Ar is an aromatic ring selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl,
Ra independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, d-do-alkyl, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-Ci0- halocycloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, C1-C1CaIkOXy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-Ci0- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-do-alkylthio, C1- Cio-haloalkylthio, d-do-alkylsulfinyl, d-C10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-Cio-haloalkylsulfonyl, (Ci-Ci0-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (C1-Ci0-alkoxy)carbonyl, (CrC10-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR7R8, CO-NR7R8 and phenoxy, which itself may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substitu- ents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-do-alkyl, d-do-haloalkyl, C3-Ci0-cycloalkyl, C3- Cio-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, CrC10-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrCi0-alkylthio, C1- C10-haloalkylthio, d-do-alkylsulfinyl, d-do-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-C10-haloalkylsulfonyl, (d-do-alkyOcarbonyl, (Ci-C10- haloalkyl)carbonyl, (CrCio-alkoxyJcarbonyl, (CrCnj-haloalkoxyJcarbonyl, (C2-Ci0- alkenyloxy)carbonyl, (CrCio-haloalkenyloxyJcarbonyl, NR9R10 and CO-NR9R10;
R1 is hydrogen, d-do-alkyl, CrC10-haloalkyl, d-C10-cyanoalkyl, d-C10-hydroxy- alkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C3-C10-alkynyl or C2-C10-haloalkynyl, wherein the last 6 radicals may be substituted by cyano, nitro, hydroxy, d-do-alkoxy, d-do-haloalkoxy, CrC10-alkylthio, d-do-haloalkylthio, CrC10-alkylsulfonyl, CrC10-haloalkylsulfonyl, (C1-C10- alkyl)carbonyl, (d-C10-haloalkyl)carbonyl, (d-do-alkoxyjcarbonyl, (C1-C10- haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)- carbonyl, NR11R12 Or -CO-NR11R12;
R2 is hydrogen, halogen, cyano, d-Cio-alkyl, d-do-haloalkyl, C3-C10-cycloalkyl, C3- C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, C1-C1CaIkOXy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC10-alkylthio, C1- C10-haloalkylthio, hydroxy-d-C10-alkyl, d-do-alkoxy-d-do-alkyl, C1-C10- haloalkoxy-d-do-alkyl, (d-do-alkoxyjcarbonyl-d-do-alkyl, (C1-C10- haloalkoxy)carbonyl-d-C10-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C10-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, CrC10-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, CrC10-alkylthio, C^C^-haloalkylthio, CrC10-alkylsulfinyl, C1-C10- haloalkylsulfinyl, C^C^-alkylsulfonyl, C^C^-haloalkylsulfonyl, (C1-C10- alkyl)carbonyl, (CrC^-haloalkyOcarbonyl, (CrC10-alkoxy)carbonyl, (C1-C10- haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)- carbonyl, NR13R14 and -CO-R13R14;
R3 is hydrogen, halogen, cyano, Ci-CiO-alkyl, CrC10-haloalkyl, C3-C10-cycloalkyl, C3- C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, C^C^-alkoxy, d-Cnj-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, Crdo-alkylthio, C1- C10-haloalkylthio, hydroxy-Crdo-alkyl,
Figure imgf000005_0001
d-C10-alkoxy- d-du-haloalkyl, (CT-Cnj-alkoxyJcarbonyl-CrCKj-alkyl, d-C10-haloalkoxy- carbonyl-d-C10-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rβ, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, CrC10-alkyl, d-do-haloalkyl, C3- do-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, d-C10-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC10-alkylthio, d-C^-haloalkylthio, d-do-alkylsulfinyl, CT-C^-haloalkylsulfinyl, C1-C10- alkylsulfonyl, Crdo-haloalkylsulfonyl, (d-do-alkyOcarbonyl, (C1-C10- haloalkyl)carbonyl, (d-do-alkoxy)carbonyl, (d-do-haloalkoxy^arbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR15R16 and CO-NR15R16;
R4 is hydrogen, halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-do-haloalkyl, C3- C10-cycloalkyl, C3-Ci0-halocycloalkyl, C2-Ci0-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC10-alkylthio, d-C10-haloalkylthio, d-do-alkylsulfinyl, CrC10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-C10-haloalkylsulfonyl, (d-C10-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (CrC10-alkoxy)carbonyl, (C1-C10-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR17R18, CO-NR17R18 or phenoxy which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-do-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, d-C10-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-do-alkylthio, C1- C10-haloalkylthio, d-C10-alkylsulfinyl, CrC10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-C10-haloalkylsulfonyl, (CrC10-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (d-C10-alkoxy)carbonyl, (CrC10-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR19R20 and CO-NR19R20;
or if Ar is phenyl,
R2 and R4 together can also form a bivalent radical Z, which is selected from -O-, -S-, -S(O)-, S(O)2-, -N(Rb1)-, -O-C(O)-, -O-C(S)-, -O-CH(Rb2)-, -C(O)-N(R03)-, -C(S)-N(R")-, -C(H)=N-, -N(RM)-CH(Rb2)-, -S-CH(R"5)-, -S(O)-CH(R"5)-, -S(O)2-CH(R"5)-, thereby forming a 5- or 6-membered heterocyclic ring which is fused to Ar, wherein R"1, R"2, R"3, RM and Rb5 are selected, independently of one another, from the group consisting of d-do-alkyl, d-do-haloalkyl, C3-Ci0- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-C10-alkylsulfonyl, CrC^-haloalkylsulfonyl, (C1-C10- alkyl)carbonyl, (Crdo-haloalkyljcarbonyl, (d-C10-alkoxy)carbonyl, (C1-C10- haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)- carbonyl, NR21R22 and CO-NR21R22 and wherein R"2 and Rb5 may also be selected from halogen, cyano, or nitro;
R5 is hydrogen, d-C10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl or C3-C10- halocycloalkyl; R8 is a cyclic radical selected from phenyl and a saturated, unsaturated or aromatic 5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 heteroatoms as ring members which are selected, independently of one another, from oxygen, sulfur and nitrogen, and where the cyclic radical may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rd which are selected, independently of one another, from the group consisting of halogen, cyano, nitro, hydroxy, CrC10-alkyl, CrC10-haloalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2- Cio-alkynyl, C3-C10-haloalkynyl, Ci-Ci0-alkoxy, Ci-Cio-haloalkoxy, C2-Ci0- alkenyloxy, C2-Ci0-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, C1- do-alkylthio, d-do-haloalkylthio, d-do-alkylsulfϊnyl, d-C10-haloalkylsulfinyl, C1-
Cio-alkylsulfonyl, Ci-C10-haloalkylsulfonyl, d-do-alkylcarbonyl, C1-C10- haloalkylcarbonyl, (d-C10-alkoxy)carbonyl, (d-do-haloalkoxyjcarbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR23R24, CO-NR23R24, thienyl, furyl, pyridyl, phenyl, benzyl and phenoxy, wherein the aromatic ring of the 6 last mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re which, independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C10-alkyl, d-C10-haloalkyl, C3- C10-cycloalkyl, C3-Ci0-halocycloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-C10- alkynyl, C3-Ci0-haloalkynyl, d-do-alkoxy, CrCi0-haloalkoxy, C2-Ci0-alkenyloxy, C2-Ci0-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-C10-alkylthio,
Ci-Ci0-haloalkylthio, Ci-CiO-alkylsulfinyl, CrCi0-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-Ci0-haloalkylsulfonyl, (CrCi0-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (d-Ci0-alkoxy)carbonyl, (d-Ci0-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR25R26 and CO-R25R26;
R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25 and R26, are selected, independently of one another, from the group consisting of hydrogen, d-C10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, (C1-Ci0- alkyl)carbonyl, (Crdo-haloalkyljcarbonyl, phenyl, phenylcarbonyl or benzyl, wherein the phenyl ring of the 3 aromatic radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rβ, which, independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-Cio-haloalkyl, C3-C10-cycloalkyl, C3-Cio-halocycloalkyl, C2-C10-alkenyl, C2-C1O- haloalkenyl, d-do-alkoxy, d-C10-haloalkoxy, CrC10-alkylthio, C1-C10- haloalkylthio, Ci-C10-alkylsulfonyl, d-C10-haloalkylsulfonyl, (C1-C10- alkyl)carbonyl, (d-do-haloalky^carbonyl, (d-C10-alkoxy)carbonyl, (C1-Ci0- haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl and (C2-C10- haloalkenyloxy)carbonyl. Due to their excellent activity, the compounds of the general formula I can be used for controlling animal pests. The term "animal pest" is understood to include any pests that belong to the fauna, in particular arthropod pests such as insects and arachnids and also nemtodes. The compounds of the formula I are especially useful from combating insects.
The invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful pests, in particular 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 invention also provides a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a 0-(phenyl/heterocyclyl)methyl oxime ether of formula I as defined herein, or a vet- erinarily acceptable salt thereof. The parasites are preferably selected from insects, in particular from the Diptera, Siphonaptera and Ixodida orders.
Some of the compounds of the formula I have been described in the art for other pur- poses. However, compounds of the formula I, wherein R6 is an oxadiazolyl radical which may carry a radical Rd as defined above are new, except for 1-Benzofuran-2-yl- ethanone 0-(5-thiophen-2-yl-[1 ,3,4]oxadiazol-2-ylmethyl)-oxime. Therefore the invention also relates to compounds of the general formula I'
Figure imgf000008_0001
and to the agriculturally or veterinarily acceptable salt thereof, wherein Ar, k, Ra, R1, R2, R3, R4 and R5 are as defined above and wherein R6 is an oxadiazolyl radical which may carry a radical Rd as defined above are new, except for 1-benzofuran-2-yl- ethanone O-(5-thiophen-2-yl-[1 ,3,4]oxadiazol-2-ylmethyl)-oxime. 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.
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, the 0-N=C(R1) group and the CH(R5XR6) moiety. According to the present invention both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof can be used. The compounds of the general formula I may also exist in the form of different tautomers if R6 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 and veterinarily 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 Ci-C4-alkyl, CrC4-hydroxyalkyl, CrC4-alkoxy, CrC4-alkoxy-Cr C4-alkyl, hydroxy-CrC^alkoxy-d-C^alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(CrC4- alkyl)sulfonium, and sulfoxonium ions, preferably tri(CrC4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of CVC-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. 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.
By the term "veterinarily acceptable salts" is meant salts the anions of which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic 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-C01 indicates in each case the possible number of carbon atoms in the group.
"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.
The term "d-Cio-alkyl" as used herein (and also in d-C10-alkylsulfinyl 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 "d-do-haloalkyl" as used herein (and also in d-do-haloalkylsulfinyl and C1- C10-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 C1-C4- haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoro- methyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro- difluoromethyl, 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 d-C2-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-do-alkoxy" and "d-C10-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, at any bond in the alkyl group. Examples include C1-C4- alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, further d-C4-alkylthio such as methylthio, ethylthio, propylthio, isopro- pylthio, and n-butylthio.
Accordingly, the terms "d-C10-haloalkoxy" and " d-C10-haloalkylthio" refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond 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 -f luoroethoxy, 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, dichloro- fluoromethylthio, 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 C1-C2- fluoroalkoxy and d-C2-fluoroalkylthio refer to CrC2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
The term "C2-C10-alkenyr as used herein intends a branched or unbranched unsatu- rated 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-methyl-1-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-dimethyM-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-pentenyl1 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-Cio-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 linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.
Accordingly, the term "C2-Cio-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 linkages, respectively, at any bond 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-Ci0-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 linkages at any bond 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 at any bond in the alkynyl group, where some or all of the hydrogen atoms in this 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, cyclo- heptyl, cyclooctyl and cyclodecyl.
The term "C3-C10-halocycloalkyl" as used herein refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclo- hexyl, 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 "CrC^-alkylcarbonyl" as used herein refers to Crdo-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(CH3J2, n-butylcarbonyl, CO-CH(CH3)-C2H5> CO-CH2-CH(CH3)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-dimethylbutylcarbonyl, 2,2- dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1- ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2-trimethylpropylcarbonyl, 1 ,2,2- trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1-ethyl-2- methylpropylcarbonyl. The term "d-do-alkoxycarbonyl" as used herein refers to CrC10-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(CH3)2) CO-OC(CH3J3, 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 -methylpropoxycarbonyl or 1-ethyl-2- methylpropoxycarbonyl.
The term "halo-d-do-alkoxycarbonyl" as used herein refers to d-C10-haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.
The terms "hydroxy-d-do-alkyl", "d-Cio-alkoxy-d-do-alkyl", "halo-d-do-alkoxy-d- C10-alkyl", "d-do-alkoxycarbonyl-d-do-alkyl", "halo-d-do-alkoxycarbonyl-d-do- 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-do-alkoxy, C1-C10- haloalkoxy, CrC10-alkoxycarbonyl or d-do-haloalkoxycarbonyl.
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, pyr- rolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, di- oxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperaz- inyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihy- drothiopyranyl, 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 isoxa- zolyl.
With respect to the use according to the invention of the compounds of formula I, par- ticular preference is given to the following meanings of the substituents, in each case on their own or in combination:
R1 is preferably hydrogen, d-do-alkyl, d-C10-haloalkyl, more preferably hydrogen, C1- d-alkyl or d-C4-haloalkyl, and especially hydrogen. However, preference is also given to compounds I, wheren R1 is phenyl or pyridyl.
R2 is preferably selected from hydrogen, halogen, cyano and d-C4-alkyl, in particular from hydrogen, fluorine chlorine, bromine, cyano, methyl or ethyl.
R3 is preferably selected from hydrogen, halogen and d-C4-alkyl, with hydrogen being more preferred.
R5 is preferably selected from hydrogen and d-do-alkyl, in particular from hydrogen and Crd-alkyl.
Preference is given to compounds of formula I, wherein R8 in formula I is a cyclic radical selected from phenyl, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, oxadiazolyl or thiadiazolyl, and where the cyclic radical may be unsubstituted or substituted as de- scribed above. In particular the aformentioned radicals are unsubstituted or substituted by 1 , 2 or 3 radicals Rd as defined above.
Preferred radicals Rd comprise halogen, CN, d-d-alkyl, d-d-alkoxy, C1-C4- haloalkoxy, d-C4-alkylthio and d-C4-haloalkyl, in particular F, Cl, CN1 methyl, meth- oxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoro- methoxy and difluoromethoxy.
More preference is given to compounds of formula I, wherin R8 is a cyclic radical selected from phenyl, thienyl, furyl, isoxazolyl, pyrazolyl, oxadiazolyl, imidazolyl, pyraz- inyl, pyrimidyl and pyridyl, in particular from pyridyl, oxadiazolyl, thienyl and phenyl, where the cyclic radical may be substituted by 1 , 2 or 3 substuituents Rd which are as defined above and which are preferably selected, independently of one another, from halogen, CN, d-d-alkyl, d-C4-alkoxy, d-C4-haloalkoxy, CrC4-alkylthio and C1-C4- haloalkyl, in particular from F, Cl, CN, methyl, methoxy, ethoxy, methylthio, difluoro- methyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy. Examples of preferred radicals Rβ 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, 3-bromo-4,5-dimethylthien-2-yl, thien-3-yl, 2- chlorothien-4-yl; pyridin-2-yl, 6-methylthiopyridin-2-yl, 3-fluoropyridin-2-yl, 3-methoxypyridin-2-yl, 6-methylpyridin-2-yl, 5-nitropyridin-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-fluorophenyl, 2,4-difluorophenyl, 2,5- difluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3- dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 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-methylphenyl, 3-fluoro-4-methylphenyl, 2-methylphenyl, 3-methylphenyl, 4- methylphenyl, 2,6-dimethylphenyl, 2-(trifluoromethy I) phenyl, 3-
(trifluoromethyl)phenyl, 4-(trifluoromethyl)phenyl, 2-fluoro-4- (trifluoromethyl)phenyl, 3,5-bis(trifluoromethyl)phenyl, 4-tert.-butyl-phenyl, 2- methoxyphenyl, 3-methoxy phenyl, 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, 3-cyanophenyl, 4-cyanophenyl, 3-phenylphenyl, 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-methylisoxazol-5-yl, 3-(1-methylethyl)isoxazol-5-yl, 5- (chloromethyl)isoxazol-4-yl, 5-(hydroxymethyl)isoxazol-4-yl, 3-methylisoxazol-4- yl, 3-(1-methylethyl)isoxazol-4-yl, 5-(chloromethyl)isoxazol-3-yl, 5- (hydroxymethyl)isoxazol-3-yl, 1 ,3-bis(1 ,1 ,1-trifluoroeth-2-yl)pyrazol-4-yl, 1-methyl-3-(trifluoromethyl)pyrazol-5-yl, 1-methylimidazol-2-yl, 4-methylimididazol-5-yl, 4-amino-2-methylpyrimidin-2-yl, 6-hydroxy-2-methylpyrimidin-4-yl,
A very preferred embodiment of the invention relates to compounds of the formula I1 wherein R6 is thienyl, in particular 2-thienyl which is unsubstituted or substituted by 1 , 2 or 3 radicals Rd as defined above, the radicals Rd being preferably selected, independently of one another, from halogen, CrC4-alkyl, CrC-alkoxy, CrC4-alkylthio, C1-C4- haloalkoxy and Ci-C4-haloalkyl, in particular from F, Cl, Br, methyl, methoxy, difluoro- methyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
Another very preferred embodiment of the invention relates to compounds of the formula I, wherein R6 is furyl, in particular 2-furyl which is unsubstituted or substituted by 1 , 2 or 3 radicals Rd as defined above, the radicals Rd being preferably selected, inde- pendently of one another, from halogen, Ci-C4-alkyl, C1-C^aIkOXy, CrC^alkylthio, C1- C4-haloalkoxy and C1-C4-HaIOaIKyI, in particular from F, Cl, Br, methyl, methoxy, di- fluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy.
Another very preferred embodiment of the invention relates to compounds of the for- mula I, wherein R8 is pyridyl, in particular 2- or 3-pyridyl, more preferably 2-pyridyl which is unsubstituted or substituted by 1 , 2 or 3 radicals Rd as defined above, the radicals Rd being preferably selected, independently of one another, from halogen, C1- C4-alkyl, C1-C^aIkOXy, CrC^alkylthio, C^Crhaloalkoxy and Ci-C4-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 I1 wherein Rβ is oxadiazolyl, in particular 1 ,2,4-oxadiazol-3-yl, 1 ,2,4-oxadiazol-5-yl or 1 ,3,4-oxadiazol-2-yl, which is unsubstituted or carries a radical Rd as defined above, the radical Rd being preferably selected, from CrC4-alkyl, C3-Cβ-cycloalkyl and C1-C4- haloalkyl, in particular from methyl, ethyl, tert-butyl, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl and cyclopropyl.
A further very preferred embodiment of the invention relates to compounds of the for- mula I, wherein Rβ is phenyl, which is unsubstituted or substituted by 1 , 2 or 3 radicals Rd as defined above, the radicals Rd being preferably selected, independently of one another, from halogen, d-C4-alkyl, CrC4-alkoxy, CrC4-haloalkoxy, CrC-alkylthio and CrC4-haloalkyl, in particular from F1 Cl, Br, methyl, methoxy, ethoxy, methylthio, difluoromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, trifluoromethoxy and difluoromethoxy. Ar is preferably phenyl, which is unsubstituted or substituted by 1 , 2, 3 or 4, in particular 1 , 2 or 3 radicals Ra as defined above, depending on the number k. A skilled person will appreciate that in case of R4 being different from hydrogen, the total number of radicals on phenyl is k+1 , or, if R4 together with R2 is the aformentioned bivalent radi- cal, the total number of substituents on phenyl is k.
Preferably the radicals Ra (and likewise R4) are selected, independently of one another, from halogen, CN, d-C4-alkyl, d-C4-alkoxy, Ci-C4-haloalkoxy and CrC4-haloalkyl, more preferably F1 Cl, CN, CrC3-alkoxy, in particular methoxy, trifluoromethyl, di- fluoromethyl, trifluoromethoxy, difluoromethoxy and methyl.
In a preferred embodiment of the invention the radical R2 and R4 in formula I are monovalent radicals, i.e. R2 and R4 together do not form a bivalent radical. In this embodiment R2 is preferably selected from hydrogen, halogen, Ci-C4-alkyl, d-C4-alkoxy, C1- C4-haloalkoxy and d-C4-haloalkyl. More preferably R2 is hydrogen, fluorine, chlorine bromine, methyl or ethyl. In this embodiment R4 is hydrogen or a radical Ra as defined above. Preferably, R4 is hydrogen or has one one of the preferred meanings of Ra. In particular, R4 is 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 Ra as defined above.
Another embodiment of the invention relates to compounds of the formula I, wherein R4 together with R2 is a bivalent radical Z as defined above and which is preferably selected from O, S, CH=N, 0-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, S, and O-C(O), where in the last moiety 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 phenyl, which is unsubstituted or substituted by 1, 2 or 3, in particular O, 1 or 2 radicals Ra as defined above.
Apart from that, Rb1, Rb2, Rb3, RM and Rb5, if present, are preferably selected from hydrogen, d-C4-alkyl and d-C4-haloalkyl it being possible that Rb2 and Rb5 may also be selected from halogen.
If present, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25 and R2β are preferably selected independently from one another from hydrogen and d-C4-alkyl. If present, Rc and Re are preferably selected, independently from another, from halogen, CrC4-alkyl, CN, NO2, OH1 d-C^haloalkyl, d-C4-alkoxy and CrC-haloalkoxy.
A very preferred embodiment of the invention relates to compounds of the general for- mula Ia:
Figure imgf000019_0001
wherein k is O, 1 , 2 or 3, and wherein Ar, R1, R2, R3, R4, R5 and Ra are as defined above.
Examples of compounds Ia are given in the following tables 1 to 378.
Table 1 Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 2 Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H1 R4 is F and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 3 Compounds of the formula Ia in which R1 is H1 R2 is H1 R3 is H1 R4 is H and Ar-(Ra)k is 3-fluorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 4 Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 4-fluorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 5 Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H1 R4 is Cl and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 6
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 7
Compounds of the formula Ia in which R1 is H, R2 is H1 R3 is H, R4 is H and Ar-(Ra)k is 4-chlorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 8
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is Cl and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 9
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 3-difluoromethoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 10
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 11
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 12
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H1 R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 13
Compounds of the formula Ia in which R1 is H1 R2 is H1 R3 is H, R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 14
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 15
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 3-methoxyphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 16
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 4-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 17
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is CH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 18
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 19
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is CF3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 20
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 21
Compounds of the formula Ia in which R1 is H, R2 is H, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 22
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 23
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is F and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 24
Compounds of the formula Ia in which R1 is H, R2 is CN1 R3 is H, R4 is H and Ar-(Ra)k is 3-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 25
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 26
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is Cl and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 27
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 28
Compounds of the formula Ia in which R1 is H1 R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-chlorophenyl and the combination of R5 and Rθ for a compound corresponds in each case to one row of table A.
Table 29
Compounds of the formula Ia in which R1 is H1 R2 is CN, R3 is H, R4 is Cl and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 30
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 3-d ifluoromethoxy phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 31
Compounds of the formula Ia in which R1 is H1 R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 32
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 33
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 34
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 35
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 36
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is OCH3 and Ar-(Ra)k is 3-methoxyphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 37
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 4-trifluoromethylphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A
Table 38
Compounds of the formula Ia in which R1 is H, R2 is CN1 R3 is H, R4 is CH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 39
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 40
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is CF3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 41
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 42
Compounds of the formula Ia in which R1 is H, R2 is CN, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 43
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 44
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is F and Ar- (Ra)k is phenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 45
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)k is 3-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 46
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)κ is 4-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 47
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is Cl and Ar- (Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 48
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 49
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)k is 4-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 50
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is Cl and Ar- (Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 51
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)k is 3-difluoromethoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 52
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar- (Ra)κ is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 53
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and R6 for a com- pound corresponds in each case to one row of table A.
Table 54
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 55
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 56
Compounds of the formula Ia in which R1 is H, R2 is methyl H, R3 is H, R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 57
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is OCH3 and Ar-(Ra)k is 3-methoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 58
Compounds of the formula Ia in which R1 is H1 R2 is methyl, R3 is H, R4 is OCH3 and Ar-(Ra)k is 4-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 59
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H1 R4 is CH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 60
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 61
Compounds of the formula Ia in which R1 is H, R2 is methyl, R3 is H, R4 is CF3 and Ar-(Ra)k is phenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 62
Compounds of the formula Ia in which R1 is H1 R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 63
Compounds of the formula Ia in which R1 is H1 R2 is methyl, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 64
Compounds of the formula Ia in which R1 is H1 R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 65
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is F and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 66
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H1 R4 is H and Ar-(Ra)k is 3-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 67
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 4-fluorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 68
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is Cl and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 69
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 70
Compounds of the formula Ia in which R1 is H1 R2 is ethyl, R3 is H1 R4 is H and Ar-(Ra)k is 4-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 71
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is Cl and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 72
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 3-difluoromethoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 73
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 74
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 75
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H1 R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 76
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 77
Compounds of the formula Ia in which R1 is H1 R2 is ethyl H1 R3 is H1 R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 78
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is OCH3 and Ar- (Ra)κ is 3-methoxyphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 79
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is OCH3 and Ar- (Ra)κ is 4-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 80
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is CH3 and Ar- (Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 81
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 82
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is CF3 and Ar- (Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 83
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 84
Compounds of the formula Ia in which R1 is H, R2 is ethyl, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 85
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 86
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is F and Ar-(Ra)k is phenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 87
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 3-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 88
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 4-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 89
Compounds of the formula Ia in which R1 is H, R2 is Cl1 R3 is H, R4 is Cl and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 90
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 91
Compounds of the formula Ia in which R1 is H1 R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 4-chlorophenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 92
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H1 R4 is Cl and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 93
Compounds of the formula Ia in which R1 is H1 R2 is Cl1 R3 is H, R4 is H and Ar-(Ra)k is 3-difluoromethoxyphenyl and the combination of R5 and R8 for a compound corre- sponds in each case to one row of table A.
Table 94
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 95
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 96
Compounds of the formula Ia in which R1 is H1 R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 97
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 98
Compounds of the formula Ia in which R1 is H, R2 is Cl H, R3 is H, R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 99
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is OCH3 and Ar-(Ra)k is 3-methoxyphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 100
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is OCH3 and Ar-(Ra)k is 4-trifluoromethylphenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 101
Compounds of the formula Ia in which R1 is H1 R2 is Cl, R3 is H, R4 is CH3 and Ar-(Ra)k is phenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 102
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 103
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is CF3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 104
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 105
Compounds of the formula Ia in which R1 is H, R2 is Cl, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 106
Compounds of the formula Ia in which R1 is H, R2 is Br1 R3 is H, R4 is H and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 107
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is F and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 108
Compounds of the formula Ia in which R1 is H, R2 is Br1 R3 is H, R4 is H and Ar-(Ra)k is 3-fluorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 109
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 4-fluorophenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 110
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is Cl and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 111
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H1 R4 is H and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 112
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 4-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 113
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is Cl and Ar-(Ra)k is 3-chlorophenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 114
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 3-difluoromethoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 115
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 116
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 4-fluoro-3-trifluoromethylphenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 117
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H1 R4 is H and Ar-(Ra)k is 4-methoxy-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 118
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H1 R4 is H and Ar-(Ra)k is 4-methylthio-3-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 119
Compounds of the formula Ia in which R1 is H, R2 is Br H, R3 is H, R4 is OCH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 120
Compounds of the formula Ia in which R1 is H, R2 is Br1 R3 is H1 R4 is OCH3 and Ar-(Ra)k is 3-methoxyphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 121
Compounds of the formula Ia in which R1 is H1 R2 is Br, R3 is H, R4 is OCH3 and Ar-(Ra)k is 4-trifluoromethylphenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 122
Compounds of the formula Ia in which R1 is H, R2 is Br1 R3 is H, R4 is CH3 and Ar-(Ra)k is phenyl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 123
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is 3-methylphenyl and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 124
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is CF3 and Ar-(Ra)k is phenyl and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 125
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is fur-2-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 126
Compounds of the formula Ia in which R1 is H, R2 is Br, R3 is H, R4 is H and Ar-(Ra)k is pyrid-3-yl and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Tables 127 to 252
Compounds of the formula Ia in which R2, R3, R4 and Ar-(Ra)k are as defined in one of the tables 1 to 126, and the combination of R5 and R6 for a compound corresponds in each case to one row of table A and R1 is methyl instead of hydrogen.
Tables 253 to 378
Compounds of the formula Ia in which R2, R3, R4 and Ar-(Ra)k are as defined in one of the tables 1 to 126, and the combination of R5 and R6 for a compound corresponds in each case to one row of table A and R1 is ethyl instead of hydrogen.
Table A:
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_0002
Another very preferred embodiment of the invention relates to compounds of the general formula Ib:
Figure imgf000045_0001
wherein k is 0, 1 , 2 or 3, and wherein R1, R3, R5, R6 and Ra are as defined above and Z is as defined above. Amongst the compounds Ib those are preferred, wherein Z is O, S or OC(O) and wherein R1, R3 , Ra and k have the meanings given as preferred.
Examples of compounds Ib are given in the following tables 379 to 396:
Table 379
Compounds of the formula Ib in which R1 is H, R3 is H, Z is O, (Ra)k is H and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 380
Compounds of the formula Ib in which R1 is H, R3 is H, Z is O, (Ra)k is 5-CH3 and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 381
Compounds of the formula Ib in which R1 is H, R3 is H, Z is O, (Ra)k is 5-CI and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 382
Compounds of the formula Ib in which R1 is H, R3 is H, Z is S, (Ra)k is H and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 383
Compounds of the formula Ib in which R1 is H, R3 is H, Z is S, (Ra)k is 5-CH3 and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 384
Compounds of the formula Ib in which R1 is H, R3 is H, Z is S, (Ra)k is 5-CI and the combination of R5 and R8 for a compound corresponds in each case to one row of table A.
Table 385
Compounds of the formula Ib in which R1 is H, R3 is H, Z is OC(O), (Ra)k is H and the combination of R5 and R8 for a compound corresponds in each case to one row of table A. Table 386
Compounds of the formula Ib in which R1 is H, R3 is H, Z is OC(O), (Ra)k is 5-CH3 and the combination of R5 and R6 for a compound corresponds in each case to one row of table A.
Table 387
Compounds of the formula Ib in which R1 is H, R3 is H, Z is OC(O)1 (Ra)k is 5-CI and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 388
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is O, (Ra)k is H and the combination of R^ and R6 for a compound corresponds in each case to one row of table
A.
Table 389
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is O, (Ra)k is 5-CH3 and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 390
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is O, (Ra)k is 5-CI and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 391
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is S, (Ra)k is H and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 392
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is S, (Ra)k is 5-CH3 and the combination of R5 and R8 for a compound corresponds in each case to one row of table
A.
Table 393
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is S1 (Ra)k is 5-CI and the combination of R5 and Rβ for a compound corresponds in each case to one row of table
A. Table 394
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is OC(O)1 (Ra)k is H and the combination of R5 and R6 for a compound corresponds in each case to one row of table
A.
Table 395
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is OC(O), (Ra)κ is 5-CH3 and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
Table 396
Compounds of the formula Ib in which R1 is CH3, R3 is H, Z is OC(O), (Ra)k is 5-CI and the combination of R5 and Rβ for a compound corresponds in each case to one row of table A.
The compounds of the formula I may be readily synthesized using techniques generally known by synthetic organic chemists.
Compounds of the formula I can be prepared applying synthesis methods described for example in WO 00/031024 and EP 579124. For instance, suitable O-alkylated hy- droxylamines Il or their corresponding ammonium salts can be reacted with aldehydes or ketones III to form compounds of the fomrula I as shown in scheme 1 :
Scheme 1 :
Figure imgf000048_0001
Il III I
O-alkylated hydroxylamines Il or their corresponding ammonium salts are known or can be prepared applying methods described e.g. in DE 3615473 or WO 95/04032 or in references cited therein.
If not commercially available, aldehydes or ketones III can be obtained according to standard methods of organic synthesis, e.g. starting from benzaldehydes or het- eroaromatic aldehydes and aliphatic ketones or aldehydes (Organikum, Johann Am- brosius Barth Verlag, Heidelberg, 1996, pp. 493-495). Alternatively, the compounds of the general formula I can be prepared by the method depicted in scheme 2. This method comprises reacting aldehydes or ketones of the formula III with hydroxylamine or its ammonium salts to form oximes IV which can be subsequently alkylated according to standard methods with compounds V to yield the compounds of the general formula I. In scheme 2 L is a conventional leaving group which can be replaced by O-nucleophiles, e.g. halogen, methylsulfonyloxy (mesylat), trifluormethylsulfonyloxy or arylsulfonyloxy such as benzenesulfonyloxy or toluenesul- fonyloxy (tosylate)
Scheme 2:
Figure imgf000049_0001
I
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.
The compounds of the formula I and their salts are in particular suitable for efficiently controlling arthropodal pests such as arachnids and insects as well as nematodes.
In particular, they are suitable for controlling insect pests, such as
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, Den- drolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mel- lonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hypo- nomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, MaIa- cosoma neustria, Mamestra brassicae, Orgyia pseudotsυgata, Ostrinia nubilalis, Pano- Hs flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthori- maea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sito- troga cerealella, Sparganothis pilleriana, Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,
beetles (Coleoptera) for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,
Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata , Diabrotica 12-punctata, Diabrotica virgifera, Diabrotica speciosa, EpHa- chna 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, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta stholata, Popillia japonica, Sitona lineatus and Sito- philus granaria,
flies, mosquitoes (Diptera), for example Aedes aegypti, Aedes albopictus, Aedes vex- ans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatυs, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops dis- calis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sor- ghicola, Cordylobia anthropophaga, Culex pipiens, Culex nigripalpus, Culex quinque- fasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachin- oides, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina,
Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia tilillanus, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Os- cinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora dis- color, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa,
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
true bugs (Hemiptera), e.g. 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, SoIu bea insularis and Thyanta perditor,
Homoptera, e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia tabaci, Bemisia 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 pyή, Empoasca fabae, Hyalopterus prυni, Hyperomyzus lactucae, Macrosiphυm avenae, Macrosiphum euphorbiae, Mac- rosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis- nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon hυmuli, Psylla mali, Psylla pin, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vapo- rariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus,
termites (Isoptera) , e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitenves flavipes, Reticulitermes lucifugus, Reticulitermes virginicus, Termes natalensis, and Coptotermes formosanus,
ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, AUa cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Monomorium pha- raonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasy- mutilla occidentalis, Bombus spp. Vespula squamosa, Paravespula vulgaris, Paraves- pula pennsylvanica, Paravespula germanica, Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile,
crickets, grasshoppers, locusts (Orthoptera), e.g Acheta domestica, Gryllotalpa gryllo- talpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina.
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,
centipedes (Chilopoda), e.g. Scutigera coleoptrata,
milipedes (Diplopoda), e.g. Narceus spp., earwigs (Dermaptera), e.g. forficula auricularia, and
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus hυmanus corporis, Pthi- rus pubis, Haematopinυs eυrysternus, Haematopinυs suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
They are also suitable for controlling Nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- chiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Het- erodera schachtii, Heterodera thfolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nema- todes, Criconema species, Criconemella species, Criconemoides species, Mesocri- conema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dip- saci and other Ditylenchus species; AwI nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longi- dorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nema- todes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhyn- chus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode spe- cies.
The compounds of the formula I and their salts are also useful for controlling Arach- noidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sar- coptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, xodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Orni- thodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Pso- roptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Rhipicephalus san- guineus, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyl- locoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panony- chus ulmi, Panonychus citri, and Oligonychus pratensis, Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa.
Compounds of the formula I are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Diptera and Homoptera.
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, FG1 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, e.g. 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.
In the method of this invention compounds I may be applied with other active ingredients, for example with 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.
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:
Organo(thio)phosphates: Acephate, Azamethiphos, Azinphos-methyl, Chlorpyrifos, Chlorpyrifos-methyl, Chlorfenvinphos, Diazinon, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Me- thidathion, 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: Allethrin, Bifenthrin, Cyfluthrin, Cyhalothrin, Cyphenothrin, Cypermethrin, alpha-Cypermethrin, beta-Cypermethrin, zeta-Cypermethrin Deltamethrin, Esfenvaler- ate, Ethofenprox, Fenpropathrin, Fenvalerate, Imiprothrin, Lambda-Cyhalothrin, Perme- thrin, Prallethrin, Pyrethrin I and II, Silafluofen, Tau-Fluvalinate, Tefluthrin, Tetrame- thrin, Tralomethrin, Transfluthrin;
Growth regulators: a) chitin synthesis inhibitors: benzoylureas: Chlorfluazuron, Cyro- mazine, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, No- valuron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen, Spiromesifen;
Neonicotinoids: Clothianidine, Dinotefuran, Imidacloprid, Thiamethoxam, Nitenpyram, Nithiazine, Acetamiprid, Thiacloprid;
Pyrazole pesticides: Acetoprole, Ethiprole, Fipronil, Tebufenpyrad, Tolfenpyrad, Va- niliprole; Various: Abamectin, Acequinocyl, Amidoflumet, Amidrazone, Amitraz, Azadirachtin, Benclothiaz, Bifenazate, Bistrifluron, Cartap, Chlorfenapyr, Chlordimeform, Cyflumeto- fen, Cyromazine, Diafenthiuron, Dimefluthrin, Diofenolan, Emamectin, Endosulfan, Fenazaquin, Flonicamid, Fluacyprim, Flubendiamide, Flufenerim, Flupyrazofos, For- metanate, Formetanate hydrochloride, Hydramethylnon, Indoxacarb, Lepimectin, Meta- flumizone, Milbemectin, NC 512, Piperonylbutoxide, Profluthrin, Pyridaben, Pyridalyl, Pymetrozine, Pyrafluprole, Pyriprole, Spinosad, Sulfur, Tebufenpyrad, Thiocyclam, Tolfenpyrad; and the pesticide of the following formula as described in WO 98/05638
Figure imgf000059_0001
aminoisothiazole compound of formula r
Figure imgf000059_0002
wherein R' is -CH2OCH3 or H and R" is -CF2CF2CF3
anthranilamide compounds of formula F3
Figure imgf000059_0003
wherein B1 is hydrogen or a chlorine atom, B2 is a bromine atom or CF3, and RB is d- C6-alkyl, and
compounds of the formulae
Figure imgf000060_0001
and malononitrile compounds as described in JP 2002 284608, WO 02/89579, WO 02/90320, WO 02/90321, WO 04/06677, WO 04/20399, or JP 2004 99597.
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. Ap- plication to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.
Compositions which are useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS) D Emulsions (EW, 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, SP1 WS)
H Dustable powders (DP, DS)
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 antifreeze 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 1 12, 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, polymethacry- lates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyl- eneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.
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, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 0C, dimethyl- formamide, 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.
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 pesti- cidally 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).
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.
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 %.
Compounds of formula I and compositions comprising them may also be used for con- trolling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Compounds of formula I and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of formula I and compositions comprising them are suitable for sys- temic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development. The compounds of formula I are especially useful for combating ectoparasites.
The compounds of formula I are especially useful for combating parasites of the follow- ing orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tυnga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brυnnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Ana- strepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Cυlex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus inte- stinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoi- des, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectora- //s, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarco- phaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Ta- banus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodo- rus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithon- yssus bacoti and Dermanyssus gallinae,
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Tricho- dectes spp., and Felicola spp,
Roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Xn- churidae; Trichuris spp., Capillaria spp,
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophago- stomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus den- tatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angio- strongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Diocto- phyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habro- nema spp.,
Thorny headed worms (Acanthocephala), e.g. Acanthocephalυs spp., Macracanthor- hynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp. The compounds of formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of the compounds of formula I and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula I and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formula I and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula I and compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of formula I also are especially useful for combating endoparasites
(roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the formula I compounds may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the formula I compounds may be formulated into an implant for subcutaneous administration. In addition the formula I compound may be transdermal^ administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound. The formula I compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound. In addition, the formula I compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:
- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
- Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
- Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
- Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, po- lyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol. Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and accor- ding to what is described above for injection solutions, sterile procedures not being necessary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methyl- ethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promotiπg substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, pheno- xyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as N-methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, 2-pyrrolidone, 2,2- dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosi- ty-enhancing substances.
Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyc- eride mixture with vegetable fatty acids of the chain length C8-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and di- glycerides of the C8-Ci0 fatty acids,
- fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length Ci6-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and - mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are:
- non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or leci- thin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substan- ces, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above. Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of formula I.
Generally it is favorable to apply the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day , preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds of formula I against endopara- sites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formula I them are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the com- pounds of formula I. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
The active compounds can also be used as a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
In general, "parasiticidally 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 parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The present invention is now illustrated in further detail by the following examples.
I Preparation examples of compounds I 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 + 0.1% (TFA) 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 DMF: N.N-dimethylformamide MS: Quadrupol electrospray ionisation, 80 V (positiv modus)
1.1 Preparation example 1 : 3-phenyl-propenal O-4-methylbenzyl-oxime
A mixture of 52 mg (0.4 mmol) of cinnamic aldehyde and 54 mg (0.4 mmol) of O-4-methylbenzyl hydroxylamine in 4 ml toluene and 126 mg of pyridine (1.6 mmol) was heated to reflux in the presence of molecular sieve (4 A) over night. After cooling to room temperature and evaporation of volatile materials in vacuo
113 mg (0.4 mmol, 100 %) of the desired product were obtained. (HPLC/MS: RT = 4.318 min, m/z = 252 [M+H]+).
1.2 Preparation example 2: 3-(4-fluorophenyl)-2-methyl propenal 0-5-chlorothien-3- ylmethyl-oxime
A mixture of 66 mg (0.4 mmol) of 3-(4-fluorophenyl)-2-methyl propenal and 80 mg of (0.4 mmol) 0-5-chlorothien-3-ylmethyl hydroxylamine in 4 ml of toluene and 126 mg of pyridine (1.6 mmol) was heated to reflux in the presence of molecular sieve (4 A) over night. After cooling to room temperature and evaporation of volatile materials in vacuo 112 mg (0.36 mmol, 90 %) of the desired product were obtained. (HPLC/MS: RT = 4.637 min, m/z = 311 [M+H]+).
1.3 Preparation example 3: 4-(4-fluoro-phenyl)-but-3-en-2-one O-benzyl-oxime
a) Preparation of 4-(4-fluoro-phenyl)-but-3-en-2-one oxime: A mixture of 3.28 g (20 mmol) of 4-(4-fluoro-phenyl)-but-3-en-2-one and 1.67 g (24 mmol) of hydroxylamine hydrochlorid in 100 ml of dichloromethane/methanol 4:1 was stirred at room temperature overnight. After evaporation of the solvent the crude product was dissolved in 150 ml dichloromethane. The solution was extracted with 50 ml of acetic acid/sodium acetate buffer (pH 4.65) and subsequently with 50 ml of a saturated K2CO3 solution. The organic phase was dried over magnesium sulfate and concentrated in vacuo yielding 2.97 g (16.6 mmol, 83%) of the desired product as a mixture of E and Z isomers. The compound was sufficiently pure for subsequent reactions (> 95% according to HPLC/MS; RT = 2.497 min and 2.606 min, m/z = 180 [IvHH]+)-
b) Preparation of 4-(4-fluoro-phenyl)-but-3-en-2-one O-benzyl-oxime: A mixture of 90 mg (0.5 mmol) of 4-(4-fluoro-phenyl)-but-3-en-2-one oxime, 86 mg (0.5 mmol) of benzyl bromide and 326 mg (1 mmol) of cesium carbonate in 2.5 ml of DMF was heated to 500C for 25 min in a microwave oven (max. 250 W). After cooling to room temperature the mixture was filtered over Celite and concentrated in vacuo. The crude product was dissolved in 4 ml dichloromethane, washed two times with 2 ml of water and dried over magnesium sulfate. After evaporation of the solvent 116 mg (0.43 mmol, 86%) of the desired product were obtained as a mixture of E and Z isomers (RT = 4.104 min and 4.209 min, m/z = 270 [IvRH]+).
1.4 Preparation example 4: 2-methyl-3-pyridin-3-yl-propenal O-benzyl-oxime
a) Preparation of 2-methyl-3-pyridin-3-yl-propenal oxime
A mixture of 2.94 g (20 mmol) of 2-methyl-3-pyridin-3-yl-propenal and 1.39 g (20 mmol) of hydroxylamine hydrochlorid in 20 ml methanol and 2.77 ml (20 mmol) of triethylamine was heated to reflux for 3 hours. After cooling to room temperature and evaporation of the solvent the crude product was dissolved in 200 ml of dichloromethane. The solution was extracted with 75 ml of acetic acid/sodium acetate buffer (pH 4.65) and subsequently with 75 ml of water. The solution was dried over magnesium sulfate and concentrated in vacuo yielding 0.38 g (2.4 mmol, 12%) of the desired product as a mixture of E and Z isomers. The compound was sufficiently pure for subsequent reactions (> 95% according to HPLC/MS; RT = 0.608 min and 0.772 min, m/z = 163 [M+H]+).
b) Preparation of 2-methyl-3-pyridin-3-yl-propenal O-benzyl-oxime: A mixture of 41 mg (0.25 mmol) of 2-methyl-3-pyridin-3-yl-propenal oxime, 43 mg
(0.25 mmol) of benzyl bromide and 163 mg (0.5 mmol) cesium carbonate in 1.25 ml of DMF was heated to 50°C for 25 min in a microwave oven (max. 250 W). After cooling to room temperature the mixture was filtered over Celite and concentrated in vacuo. The crude product was dissolved in 2 ml of dichloromethane, washed two times with 2 ml of water and dried over magnesium sulfate. After evaporation of the solvent 63 mg (0.25 mmol, 100%) of the desired product were obtained (RT = 2.439 min, m/z = 253 [M+H]+).
1.4 Preparation example 5: 2-methyl-3-phenyl-propenal O-benzyl-oxime
a) Preparation of 2-methyl-3-phenyl-propenal oxime
A mixture of 2.92 g (20 mmol) of 2-methyl-3-phenyl-propenal and 1.39 g (20 mmol) of hydroxylamine hydrochlorid in 20 ml of methanol and 2.77 ml (20 mmol) of triethylamine was heated to reflux for 3 hours. After cooling to room temperature and evaporation of the solvent the crude product was dissolved in
200 ml of dichloromethane and extracted with 75 ml of acetic acid/sodium acetate buffer (pH 4.65) and subsequently with 75 ml of water. The solution was dried over magnesium sulfate. After evaporation of the solvent 2.82 g (17.5 mmol, 88%) of the desired product were obtained. The compound was sufficiently pure for subsequent reactions (> 95% according to HPLC/MS; RT =
2.885 min, m/z = 162 [IvHH]+).
b) Preparation of 2-methyl-3-phenyl-propenal O-benzyl-oxime
The title product could be obtained by analogy to the method described in prepa- ration example 1.4 b) starting from 2-methyl-3-phenyl-propenal oxime.
Likewise the compounds A1 to A127, B1 to B30 and C1 to C7 given in following tables can be prepared.
Figure imgf000077_0001
-«
Figure imgf000077_0002
-
Figure imgf000078_0001
0
Figure imgf000079_0001
(
Figure imgf000080_0001
C
Figure imgf000081_0001
Figure imgf000082_0001
0
Figure imgf000083_0001
I
Figure imgf000084_0001
0
Figure imgf000084_0002
Figure imgf000085_0001
Figure imgf000086_0001
0 U
Figure imgf000087_0001
Figure imgf000087_0002
The action of the compounds of the formula I against pests was demonstrated by the following experiments:
I Activity against insects
1. Activity against Boll weevil (Anthonomus prandis)
The active compounds were formulated in 1 :3 DMSO : water. 10 to 15 eggs were placed into microtiterplates filled with 2% agar-agar in water and 300 ppm formaline. The eggs were sprayed with 20 μl of the test solution, the plates were sealed with pierced foils and kept at 24-26°C and 75-85% humidity with a day/night cycle for 3 to 5 days. Mortality was assessed on the basis of the remaining unhatched eggs or larvae on the agar surface and/or quantity and depth of the digging channels caused by the hatched larvae. Tests were replicated 2 times.
In this test, e.g. compounds A4, A5, A7, A9, A10, A12, A19, A24, A32, A34, A35, A36, A38, A41 , A45, A51 , A67, A94, A95, A97, A98, A99, A100, A101 , A103, A107, A108, A109, A110, A112, A114, A115, A119, A124, A126, A127, B5, B6, B7, B10, C5 and C7 at 2500 ppm showed over 75 % mortality compared to untreated controls.
2. Activity against Mediterranean fruitflv {Ceratitis capitate)
The active compounds were formulated in 1 :3 DMSO : water. 50 to 80 eggs were placed into microtiterplates filled with 0.5% agar-agar and 14 % diet in water. The eggs were sprayed with 5 μl of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility of the hatched larvae. Tests were replicated 2 times.
In this test, e.g. compounds A3, A8, A20, A21 , A22, A26, A37, A46, A49 and A63 at 2500 ppm showed over 75 % mortality compared to untreated controls.
3. Activity against Tobacco budworm (Heliothis virescens)
The active compounds were formulated in 1 :3 DMSO : water. 15 to 25 eggs were placed into microtiterplates filled with diet. The eggs were sprayed with 10 μl of the test solution, the plates were sealed with pierced foils and kept at 27-290C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility and of comparative feeding of the hatched larvae. Tests were replicated 2 times.
In this test, e.g. compounds A93 and B14 at 2500 ppm showed over 75 % mortality compared to untreated controls.
4. Activity against Vetch aphid (Meaoura viciae)
The active compounds were formulated in 1 :3 DMSO : water. Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm opus™. The leaf disks were sprayed with 2.5 μl of the test solution and 5 to 8 adult aphids were placed into the microtiterplates which were then closed and kept at 22-240C and 35-45% under fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Tests were replicated 2 times.
In this test, e.g. compounds A6, A17, A39, A48, A50, A52, A64, A68 and A1 17 at 2500 ppm showed over 75 % mortality compared to untreated controls.
5. Activity against house fly (Musca domestica) via glass contact
Glass vials were treated with 0.5 ml of a solution of active ingredient in acetone and allowed to dry. Insects were placed into each vial together with some food and moisture supply. The vials were kept at 22 0C and were observed for treatment effects at various time intervals.
In this test, e.g. compound A44 at 10 ppm showed over 50 % mortality compared to untreated controls.
6. Activity against vellowfever mosguito (Aedes aegyptii) adults via glass contact
Glass vials were treated with 0.5 ml of a solution of active ingredient in acetone and allowed to dry. Insects were placed into each vial together with some food and moisture supply. The vials were kept at 22 0C and were observed for treatment effects at various time intervals.
In this test, e.g. compounds A11 and A43 at 10 ppm showed over 75 % mortality compared to untreated controls. 7. Activity against vellowfever mosquito (Aedes aeavotii) larvae via water treatment
Well plates were used as test arenas. The active ingredient was dissolved in acetone and diluted with water to obtain the concentrations needed. The final solutions contain- ing appr. 1% acetone were placed into each well. Approximately 10 mosquito larvae (^-instars) in 1 ml water were added to each well. Larvae were fed one drop of liver powder each day. The dishes were covered and maintained at 22°C. Mortality was recorded daily and dead larvae and live or dead pupae were removed daily. At the end of the test remaining live larvae were recorded and percent mortality was calculated.
In this test, e.g. compound A44 at 10 ppm showed over 75 % mortality compared to untreated controls.
8. Activity against acrobat ant (Crematogaster spp.) via glass contact
Glass vials were treated with 0.5 ml of a solution of active ingredient in acetone and allowed to dry. Insects were placed into each vial together with some food and moisture supply. The vials were kept at 22 0C and were observed for treatment effects at various time intervals.
In this test, e.g. compound A11 at 100 ppm showed over 75 % mortality compared to untreated controls.

Claims

We claim:
1. A method of combating animal pests which comprises contacting the animal pest, their habit, 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 animal attack or infestation, with a pesticidally effective amount of at least one O-(phenyl/heterocyclyl)methyl oxime ether of the formula I
Figure imgf000091_0001
and/or at least one agriculturally acceptable salt thereof, wherein
is absent or a covalent bond;
k is O, 1 , 2, 3 or 4;
Ar is an aromatic ring selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl,
Ra independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-CiO-alkyl, CrC^-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, CrC^-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, C^C^-alkylthio, CrC1o-haloalkylthio, C^C^-alkylsulfinyl,
CrCnj-haloalkylsulfinyl, CrC1o-alkylsulfonyl, Ci-C1o-haloalkylsulfonyl, (C1- Cio-alkyl)carbonyl, (d-C^-haloalky^carbonyl, (CT-C^-alkoxyJcarbonyl, (C1- C1o-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR7R8, CO-NR7R8 and phenoxy, which itself may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C10-alkyl, d-Cnrhaloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, d-C10-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-do-alkylthio,
CrC10-haloalkylthio, Crdo-alkylsulfinyl, CrC10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, (d-C10-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (CrC10-alkoxy)carbonyl, (d-C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR9R10 and CO-NR9R10;
R1 is hydrogen, d-do-alkyl, Ci-C10-haloalkyl, d-C1o-cyanoalkyl, C1-C10- hydroxyalkyl, C3-C10-cycloalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2- do-haloalkenyl, C3-C10-alkynyl or C2-C10-haloalkynyl, wherein the last 6 radicals may be substituted by cyano, nitro, hydroxy, d-C10-alkoxy, C1-C10- haloalkoxy, d-C10-alkylthio, d-C10-haloalkylthio, d-C10-alkylsulfonyl, C1-
C1o-haloalkylsulfonyl, (d-do-alkyljcarbonyl, (CrC10-haloalkyl)carbonyl, (C1-C10-alkoxy)carbonyl, (d-C1o-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR11R12 Or -CO-NR11R12;
R2 is hydrogen, halogen, cyano, d-C10-alkyl, d-do-haloalkyl, C3-C10- cycloalkyl, Ca-do-halocycloalkyl, C2-C10-alkenyl, C2-C1o-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC1o-alkoxy, d-do-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C1 o-alkynyloxy, C3-C10- haloalkynyloxy, CrC1o-alkylthio, d-C1o-haloalkylthio, hydroxy-d-C1o-alkyl, d-do-alkoxy-d-do-alkyl, d-do-haloalkoxy-d-do-alkyl, (C1-C10- alkoxy)carbonyl-d-do-alkyl, (d-do-haloalkoxyjcarbonyl-d-do-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C1o-alkyl, CrC1o-haloalkyl, C3-C10- cycloalkyl, d-do-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, CrCTo-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C1o-alkynyloxy, C3-C10- haloalkynyloxy, d-C1o-alkylthio, CrC^-haloalkylthio, d-do-alkylsulfinyl, CrC1o-haloalkylsulfinyl, d-C1o-alkylsulfonyl,
Figure imgf000092_0001
(C1-
C1o-alkyl)carbonyl, (C^do-haloalkyljcarbonyl, (CrC^-alkoxyJcarbonyl, (C1- C10-haloalkoxy)carbonyl, (C2-C1o-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR13R14 and -CO-R13R14;
R3 is hydrogen, halogen, cyano, d-C1o-alkyl, CrC10-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl,
Figure imgf000092_0002
C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, CrC1o-alkylthio, d-C1o-haloalkylthio, hydroxy-d-C1o-alkyl, d-do-alkoxy-d-do-alkyl, CTC^-alkoxy-Crdo-haloalkyl, (C1-C10- alkoxyJcarbonyl-d-Cio-alkyl, d-do-haloalkoxycarbonyl-d-do-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, CrC10-alkyl, d-C10-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, Ci-C10-haloalkoxy, C2-C10- alkenyloxy, C2-C1o-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, d-C1o-alkylthio, d-C10-haloalkylthio, CrC1o-alkylsulfinyl, d-do-haloalkylsulfinyl, CrC10-alkylsulfonyl, d-C1o-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (d-do-haloalkyOcarbonyl, (d-do-alkoxyjcarbonyl, (C1-
C1o-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR15R16 and CO-NR15R16;
R4 is hydrogen, halogen, cyano, nitro, hydroxy, d-do-alkyl, d-C1o-haloalkyl, C3-C10-cycloalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl,
C2-C10-alkynyl, C3-C1o-haloalkynyl, d-C1o-alkoxy, d-C1o-haloalkoxy, C2- C1o-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, d-C1o-alkylthio, d-C1o-haloalkylthio, CrC1o-alkylsulfinyl, d-C1o-haloalkylsulfinyl, d-do-alkylsulfonyl, CrC10-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (CrC^-haloalky^carbonyl, (C^C^-alkoxyJcarbonyl, (C1-
C1o-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR17R18, CO-NR17R18 or phenoxy which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C1o-alkyl, d-C1o-haloalkyl, C3-C10-cycloalkyl, C3-Ci0- halocycloalkyl, C2-Ci0-alkenyl, C2-C1o-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, C^C^-alkoxy, d-do-haloalkoxy, C2-C1o-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC^-alkylthio,
Figure imgf000093_0001
CrC1o-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC1o-haloalkylsulfonyl, (d-C1o-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (Ci-do-alkoxy)carbonyl, (d-do-haloalkoxyjcarbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR19R20 and CO-NR19R20;
or if Ar is phenyl,
R2 and R4 together can also form a bivalent radical Z, which is selected from -0-, -S-, -S(O)-, S(O)2-, -N(Rb1)-, -O-C(O)-, -O-C(S)-, -O-CH(Rb2)-, -C(O)-N(R")-, -C(S)-N(R")-, -C(H)=N-, -N(RM)-CH(Rb2)-, -S-CH(R"5)-, -S(O)-CH(Rb5)-, -S(O)2-CH(R05)-, thereby forming a 5- or 6-membered heterocyclic ring which is fused to Ar, wherein Rb1, Rb2, Rb3, RM and Rb5 are selected, independently of one another, from the group consisting of CrCi0-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-Cio-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, d-C10-alkylsulfonyl, C1-C10- haloalkylsulfonyl, (d-C10-alkyl)carbonyl, (d-do-haloalkyOcarbonyl, (C1-C10- alkoxy)carbonyl, (d-C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR21R22 and CO-NR21R22 and wherein Rb2 and Rb5 may also be selected from halogen, cyano or nitro;
R5 is hydrogen, CrC10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl or C3-C10- halocycloalkyl;
R6 is a cyclic radical selected from phenyl and a saturated, unsaturated or aromatic 5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 hetero- atoms as ring members which are selected, independently of one another, from oxygen, sulfur and nitrogen, and where the cyclic radical may be un- substituted or may carry 1 , 2, 3, 4 or 5 substituents Rd which are selected, independently of one another, from the group consisting of halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, d-C10-alkoxy, d-C10-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, d-C10-alkylthio, d-do-haloalkylthio, d-C10-alkylsulfinyl, Ci-C10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-C10-haloalkylsulfonyl, d-do-alkylcarbonyl, C1-C10- haloalkylcarbonyl, (d-C10-alkoxy)carbonyl, (d-C10-haloalkoxy)carbonyl,
(C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR23R24, CO-NR23R24, thienyl, furyl, pyridyl, phenyl, benzyl and phenoxy, wherein the aromatic ring of the 6 last mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or substituents Re which, independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, C1-
C10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10- alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, C1-C10- alkoxy, CrC10-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2- C10-alkynyloxy, C3-C10-haloalkynyloxy, d-C10-alkylthio, d-C10-haloalkylthio, d-C10-alkylsulfinyl, d-C10-haloalkylsulfinyl, d-C10-alkylsulfonyl, C1-C10- haloalkylsulfonyl, (d-do-alkyOcarbonyl, (d-C10-haloalkyl)carbonyl, (C1- C10-alkoxy)carbonyl, (d-C10-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR25R26 and -CO-R25R26; R 7 , D
Figure imgf000095_0001
I X11 , D i \12 , D I x18 , Dr\22 , DIΛ23 , Γ D\24 ,
R25 and R2β, are selected, independently of one another, from the group consisting of hydrogen, d-Cio-alkyl, Ci-Ci0-haloalkyl, C3-C10-cycloalkyl, C3- Cio-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3- Cio-haloalkynyl, (Ci-Cio-alkyl)carbonyl, (Ci-Ci0-haloalkyl)carbonyl, phenyl, phenylcarbonyl or benzyl, wherein the phenyl ring of the 3 aromatic radicals may be unsubstituted or may carry 1, 2, 3, 4 or 5 substituents Re, which, independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-C10-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C1-C10- alkoxy, d-dϋ-haloalkoxy, d-C10-alkylthio, CrC^-haloalkylthio, C1-C10- alkylsulfonyl, C^C^-haloalkylsulfonyl, (CrC10-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (d-C^-alkoxyJcarbonyl, (CrC10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl and (C2-C10-haloalkenyloxy)carbonyl.
2. The method as claimed in claim 1 , wherein Ar in formula I is phenyl,
3 The method as claimed in claim 1 , wherein k in formula I is 1 , 2 or 3.
4 The method as claimed in claim 1, wherein Ra, independently of one another, are selected from the group consisting of cyano, fluorine, chlorine, bromine, methyl, methoxy or trifluoromethyl.
5. The method as claimed in claim 1 , wherein R1 is hydrogen, Ci-C10-alkyl or C1- do-haloalkyl.
6. The method as claimed in claim 1 , wherein R2 is hydrogen, halogen or C1-C4- alkyl.
7. The method as claimed in claim 1 , wherein R3 is hydrogen, halogen or C1-C4- alkyl.
8. The method as claimed in claim 1 , wherein Ar is phenyl and wherein R2 and R4 together are oxygen thereby forming a furan ring, which may carry a substituent R3 as defined in claim 1.
9. The method as claimed in claim 1 , wherein R5 is hydrogen or d-C10-alkyl.
10. The method as claimed in claim 1 , wherein R6 in formula I is phenyl, thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, pyrazolyl, imidazolyl, pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, oxadiazolyl or thiadiazolyl, where the cyclic radical may be substituted by 1 , 2, 3, 4 or 5 substituents Rd as defined in claim 1.
11. The method as claimed in claim 1 , wherein the pests are insects, arachnids or nematodes.
12. A method for protecting crops from attack or infestation by animal pests which comprises contacting a crop with a pesticidally effective amount of at least one 0-(phenyl/heterocyclyl)methyl oxime ether of formula I and/or at least one agri- culturally acceptable salt thereof as defined in claim 1.
13. The method as claimed in claim 12, wherein the pests are insects, arachnids or nematodes.
14. A method for protecting non-living materials from attack or infestation by animal pests, the method comprising contacting the non-living material with a pesticidally effective amount of at least one 0-(phenyl/heterocyclyl)methyl oxime ether of formula I and/or with an agriculturally acceptable salt thereof, as defined in claim 1.
15. The method as claimed in claim 14, wherein the pests are insects, arachnids or nematodes.
16. A method for treating, controlling, preventing or protecting animals against infes- tation or infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a O- (phenyl/heterocyclyl)methyl oxime ether of formula I as defined in claim 1 , or a veterinarily acceptable salt thereof.
17. The method as claimed in claim 16, wherein the parasites are selected from the Diptera, Siphonaptera and Ixodida orders.
18. The use of 0-(phenyl/heterocyclyl)methyl oxime ethers of formula I and of their agriculturally acceptable salts, as defined in claim 1 , for combating animal pests.
19. The use of O-(phenyl/heterocyclyl)methyl oxime ethers of formula I and of their agriculturally acceptable salts, as defined in claim 1 , for protecting crops from attack or infestation by animal pests.
20. The use of O-(phenyl/heterocyclyl)methyl oxime ethers of formula I1 as defined in claim 1 , and of their veterinarily acceptable salts, as defined in claim 1 , for combating parasites in and on animals.
21. An O-(phenyl/heterocyclyl)methyl oxime ether of the formula I1
Figure imgf000097_0001
and the agriculturally or veterinarily acceptable salt thereof, wherein
is absent or a covalent bond;
k is O, 1 , 2, 3 or 4;
Ar is an aromatic ring selected from phenyl, pyridyl, pyrimidyl, furyl and thienyl,
Ra independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-C10-alkyl, CrC10-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC1o-alkoxy, CrC1o-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, CrC^-alkylthio, CrC10-haloalkylthio, CrC1o-alkylsulfinyl, CrC10-haloalkylsulfinyl, CTC^-alkylsulfonyl, CrC1o-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (CrC1o-haloalkyl)carbonyl, (CrCϊo-alkoxy^arbonyl, (C1-
C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR7R8, CO-NR7R8 and phenoxy, which itself may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, CrC1o-alkyl, CrC^-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C1o-alkynyl, C3-Ci0- haloalkynyl, d-C^-alkoxy, CrC1o-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, Ci-C1o-alkylthio, CrC^-haloalkylthio, d-Cw-alkylsulfinyl, CrC10-haloalkylsulfinyl, C1-C10- alkylsulfonyl, d-Cm-haloalkylsulfonyl, (CrCKj-alkyOcarbonyl, (C1-C10- haloalkyl)carbonyl, (CrC10-alkoxy)carbonyl, (C^C^-haloalkoxyJcarbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR9R10 and CO-NR9R10;
R1 is hydrogen, d-Cio-alkyl, d-do-haloalkyl, CrCio-cyanoalkyl, C1-C10- hydroxyalkyl, C3-Ci0-cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl, C2-
Cio-haloalkenyl, C3-Ci0-alkynyl or C2-C10-haloalkynyl, wherein the last 6 radicals may be substituted by cyano, nitro, hydroxy, d-do-alkoxy, C1-C10- haloalkoxy, CrC10-alkylthio, d-C10-haloalkylthio, d-do-alkylsulfonyl, C1- C10-haloalkylsulfonyl, (d-do-alkyOcarbonyl, (CrC10-haloalkyl)carbonyl, (d-do-alkoxyjcarbonyl, (CrCi0-haloalkoxy)carbonyl, (C2-C10- alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR11R12 Or -CO-NR11R12;
R2 is hydrogen, halogen, cyano, Ci-Cio-alkyl, Ci-C10-haloalkyl, C3-C10- cycloalkyl, Cs-do-halocycloalkyl, C2-C1o-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-C10-alkoxy, CrC1o-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C1o-alkynyloxy, C3-C10- haloalkynyloxy, d-do-alkylthio, d-C1o-haloalkylthio, hydroxy-d-C10-alkyl, Ci-Cio-alkoxy-CrCio-alkyl, d-C10-haloalkoxy-Ci-do-alkyl, (C1-C10- alkoxy)carbonyl-d-C1o-alkyl, (d-C^-haloalkoxyJcarbonyl-CrC^-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-C10-haloalkyl, C3-C10- cycloalkyl, C3-C1o-halocycloalkyl, C2-C10-alkenyl, C2-C1o-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, Crdo-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C1o-alkynyloxy, C3-C10- haloalkynyloxy, CrC^-alkylthio, d-do-haloalkylthio, CrC1o-alkylsulfinyl, Crdo-haloalkylsulfinyl, CrC1o-alkylsulfonyl, C^C^-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (CrCTo-haloalky^carbonyl, (C^do-alkoxyjcarbonyl, (C1- C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR13R14 and -CO-R13R14;
R3 is hydrogen, halogen, cyano, d-C10-alkyl, CrC10-haloalkyl, C3-C10- cycloalkyl, Cs-do-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-C10-alkoxy, d-C10-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, Crdo-alkylthio, CrC^-haloalkylthio, hydroxy-d-C10-alkyl, d-do-alkoxy-d-do-alkyl, d-CKj-alkoxy-CrCuj-haloalkyl, (C1-C10- alkoxy)carbonyl-CrC1o-alkyl, Crdo-haloalkoxycarbonyl-d-CTo-alkyl or phenyl which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rβ, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, CVdo-alkyl, CrCio-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10- alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, d-d0-haloalkoxy, C2-C10- alkeηyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, d-do-alkylthio, d-do-haloalkylthio, d-do-alkylsulfinyl, d-do-haloalkylsulfinyl, d-do-alkylsulfonyl, CrC10-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (d-do-haloalkyljcarbonyl, (d-C10-alkoxy)carbonyl, (C1- C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR15R16 and CO-NR15R16;
R4 is hydrogen, halogen, cyano, nitro, hydroxy, d-do-alkyl, d-do-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10-haloalkynyl, CrC10-alkoxy, CrC10-haloalkoxy, C2- C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, CrC10-alkylthio, d-do-haloalkylthio, d-do-alkylsulfinyl, d-C10-haloalkylsulfinyl, d-C10-alkylsulfonyl, d-do-haloalkylsulfonyl, (C1- C10-alkyl)carbonyl, (d-C10-haloalkyl)carbonyl, (d-C10-alkoxy)carbonyl, (C1- C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR17R18, CO-NR17R18 or phenoxy which may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Rc, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, d-C10-alkyl, d-do-haloalkyl, C3-C10-cycloalkyl, C3-C10- halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl, C3-C10- haloalkynyl, d-C10-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10- haloalkenyloxy, C2-C10-alkynyloxy, C3-C10-haloalkynyloxy, CrC10-alkylthio, CrC^-haloalkylthio, d-C10-alkylsulfinyl, CT-Cm-haloalkylsulfinyl, C1-C10- alkylsulfonyl, CrC^-haloalkylsulfonyl, (d-C10-alkyl)carbonyl, (C1-C10- haloalkyl)carbonyl, (d-Cm-alkoxyJcarbonyl, (CTCm-haloalkoxyJcarbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR19R20 and
CO-NR19R20;
or if Ar is phenyl,
R2 and R4 together can also form a bivalent radical Z, which is selected from -0-,
-S-, -S(O)-, S(O)2-, -N(Rb1)-, -O-C(O)-, -O-C(S)-, -O-CH(Rb2)-, -C(O)-N(R03)-, -C(S)-N(R"3)-, -C=N-, -N(RM)-CH(Rb2)-, -S-CH(Rb5)-, -S(O)-CH(R"5)-, -S(O)2-CH(R05)-, thereby forming a 5- or 6-membered heterocyclic ring which is fused to Ar, wherein Rb1, Rb2, Rb3, RM and Rb5 are selected, inde- pendently of one another, from the group consisting of d-do-alkyl, C1-C10- haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10- haloalkenyl, C2-C10-alkynyl, C3-Ci0-haloalkynyl, CrCi0-alkylsulfonyl, C1-C10- haloalkylsulfonyl, (d-do-alky^carbonyl, (CrC10-haloalkyl)carbonyl, (C1-C10- alkoxy)carbonyl, (Ci-C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10-haloalkenyloxy)carbonyl, NR21R22 and CO-NR21R22 and wherein Rb2 and Rb5 may also be selected from halogen, cyano or nitro;
R5 is hydrogen, d-do-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl or C3-C10- halocycloalkyl;
R6 is an oxadiazol radical, which may be substituted by Rd, selected from the group consisting of cyano, nitro, hydroxy, d-C10-alkyl, d-C10-haloalkyl, C3- C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2- C10-alkynyl, C3-C10-haloalkynyl, d-do-alkoxy, Ci-do-haloalkoxy, C2-C10- alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-C10- haloalkynyloxy, d-do-alkylthio, d-do-haloalkylthio, d-do-alkylsulfinyl, d-C10-haloalkylsulfinyl, d-do-alkylsulfonyl, d-C10-haloalkylsulfonyl, C1- C10-alkylcarbonyl, d-do-haloalkylcarbonyl, (d-C10-alkoxy)carbonyl, (C1- C10-haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR23R24, CO-NR23R24, thienyl, furyl, pyridyl, phenyl, benzyl and phenoxy, wherein the ring of the 6 aromatic radicals may be partially or completely substituted by substituents Re which, independently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, d-do-alkyl, CrC10-haloalkyl, C3-C10-cycloalkyl, C3-C10-halocycloalkyl, C2-C10-alkenyl, C2-C10-haloalkenyl, C2-C10-alkynyl,
C3-C10-haloalkynyl, d-do-alkoxy, d-do-haloalkoxy, C2-C10-alkenyloxy, C2-C10-haloalkenyloxy, C2-C10-alkynyloxy, C3-Ci0-haloalkynyloxy, C1-C10- alkylthio, C^C^-haloalkylthio, Crdo-alkylsulfinyl, d-C10-haloalkylsulfinyl, CrCuj-alkylsulfonyl, d-C10-haloalkylsulfonyl, (d-C10-alkyl)carbonyl, (C1- C10-haloalkyl)carbonyl, (CrC10-alkoxy)carbonyl, (C1-C10- haloalkoxy)carbonyl, (C2-C10-alkenyloxy)carbonyl, (C2-C10- haloalkenyloxy)carbonyl, NR25R26 and CO-NR25R26;
R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21, R22, R23, R24, R25 and R26, are selected, independently of one another, from the group consisting of hydrogen, CrC10-alkyl, d-C10-haloalkyl, C3-C10-cycloalkyl, C3- do-halocycloalkyl, C2-C10-alkenyl, C2-Ci0-haloalkenyl, C2-C10-alkynyl, C3- C10-haloalkynyl, (d-C10-alkyl)carbonyl, (Crdo-haloalkyOcarbonyl, phenyl, phenylcarbonyl or benzyl, wherein the phenyl ring of the 3 aromatic radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents Re, which, in- dependently of one another, are selected from the group consisting of halogen, cyano, nitro, hydroxy, Ci-CiO-alkyl, CrC10-haloalkyl, C3-C10- cycloalkyl, C3-C10-halocycloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C1-C10- alkoxy, C^C^-haloalkoxy, d-do-alkylthio, d-do-haloalkylthio, C1-C10- alkylsulfonyl, CrC10-haloalkylsulfonyl, (CrCm-alkylJcarbonyl, (C1-C10- haloalkyl)carbonyl, (d-C^-alkoxyJcarbonyl, (d-CnrhaloalkoxyJcarbonyl, (C2-C10-alkenyloxy)carbonyl and (C2-C10-haloalkenyloxy)carbonyl.
with the exception of 1 -benzofuran-2-yl-ethanone O-(5-thiophen-2-yl- [1 ,3,4]oxadiazol-2-ylmethyl)-oxime.
22. An agricultural composition comprising such an amount of at least one O-
(phenyl/heterocyclyl)methyl oxime ether of the formula I" or an agricultural useful salt of I' as defined in claim 21, and at least one inert liquid and/or solid agronomically acceptable carrier that it has a pesticidal action and, if desired, at least one surfactant.
PCT/EP2006/004982 2005-05-25 2006-05-24 O-(phenyl/heterocyclyl)methyl oxime ether compounds for combating animal pests Ceased WO2006125637A1 (en)

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