WO2009115491A1 - Azolin-2-ylamino compounds for combating animal pests - Google Patents

Azolin-2-ylamino compounds for combating animal pests Download PDF

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WO2009115491A1
WO2009115491A1 PCT/EP2009/053079 EP2009053079W WO2009115491A1 WO 2009115491 A1 WO2009115491 A1 WO 2009115491A1 EP 2009053079 W EP2009053079 W EP 2009053079W WO 2009115491 A1 WO2009115491 A1 WO 2009115491A1
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alkyl
independently
another
halogen
cycloalkyl
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PCT/EP2009/053079
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French (fr)
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Ronan Le Vezouet
Markus Kordes
Christopher Koradin
Ernst Baumann
Deborah L. Culbertson
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/10—Anthelmintics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • A61P33/14—Ectoparasiticides, e.g. scabicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/04—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms
    • C07C275/20—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C275/24—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/10—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C335/12—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/44—Nitrogen atoms not forming part of a nitro radical
    • C07D233/48—Nitrogen atoms not forming part of a nitro radical with acyclic hydrocarbon or substituted acyclic hydrocarbon radicals, attached to said nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D277/18—Nitrogen atoms

Definitions

  • the present invention relates to azolin-2-ylamino compounds as well as to their precursor compounds, which are both useful for combating animal pests.
  • the invention also relates to a method for controlling animal pests by using these compounds, to seed and to an agricultural and veterinary composition comprising said compounds.
  • WO 2005/063724 describes 1 -(azolin-2-yl)amino-1 ,2-diphenylethane compounds of the general formulae C.1 and C.2,
  • WO 2008/138499 describes certain N-benzy-N-hydroxyethylthiourea compounds hav- ing insecticidal activity.
  • the invention relates to azolin-2-ylamino compounds of the general formula (I),
  • n 0, 1 , 2 or 3;
  • Ar is phenyl, which is unsubstituted or carries 1 , 2, 3, 4 or 5 substituents R Ar , wherein
  • R Ar is selected from halogen, CN, N 3 , NO 2 , d-Ce-alkyl, C 2 -C 6 -alkenyl and
  • each carbon atom in the aforementioned radicals in particular each radical of the group consisting of Ci-C ⁇ -alkyl, C2-C6-alkenyl and C2-C6-alkynyl is unsubstituted or may carry any combination of 1 , 2 or 3 substitiuents, independently of one another selected from halogen, CN,
  • R Ar may further be selected from cyclic radicals -Y-Cy or -Y-Ar 1 , wherein Ar 1 has one of the meanings given below,
  • Cy is C3-Ci2-cycloalkyl or a saturated or partially unsaturated 5, 6 or 7- membered heterocycle containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, wherein C3-Ci2-cycloalkyl and the heterocycle are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, halogen, CN, NO2, OH, SH, NH 2 , COOH, C-i-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and d-Ce-alkylthio,
  • X is S, O or N(R 10 );
  • R 7a , R 7b , R 7c and R 7d are selected independently from one another from hydrogen, halogen, Ci-C ⁇ -alkyl, d-C ⁇ -alkoxy, Ci-C ⁇ -alkylamino and C3-C6-cycloalkyl, wherein
  • B is a single bond or linear or branched Ci-C4-alkanediyl
  • R 3 , R 3 ', R b , R c , R d , R e , R f , Rs and R h independently of one another have one of the meanings given below;
  • Ci-C ⁇ -alkyl C 2 -C6-alkenyl, C 2 -C6-alkynyl and d-C ⁇ -haloalkyl, and
  • R a , R b , R c , R d , R e and Ar 10 have one of the meanings given below;
  • R a , R a ', R b , R c , R d , R e , R f , Rs and R h are each independently of one another selected from hydrogen, Ci-C ⁇ -alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, Cs-Cs-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S, N as ring members, and Ar 10 , wherein Ci-C ⁇ -alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl, Cs-Cs- cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen,
  • Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-C ⁇ -alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl and d-C ⁇ -haloalkyl; and
  • Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 are each independently of one another selected from phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heteroaryl, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein phenyl, naphtyl and hetaryl are unsubstituted or carry any combination of 1 to 5 substituents, independently of one another selected from halogen, CN, NO 2 , OH, d-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, d-Ce-haloalkyl, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, d-C ⁇ -alkylthio, d-C ⁇ -haloalkylthio,
  • the invention further relates to compounds of general formula
  • n, Ar, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently from one another have one of the meanings given for the compounds of formula I, and
  • A' is a radical of formula A 3 ,
  • W is halogen or -OR 11
  • R 7a , R 7b , R 7c , R 7d , R 8 , R 9 and X independently from one another have one of the meanings given for the compounds of formula I,
  • a particular embodiment of the invention relates to compounds of the formula Il and their salts, except for the compounds of the formula II, wherein R 1 is hydrogen, n is 1 , X is S, R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R 8 and R 9 ar hydrogen, W is OH and Ar is selected from phenyl, 2-fluorophenyl, 3-fluorophenyl and 4-fluorophenyl.
  • the invention further relates to agricultural composition containing at least one compound of formulae I or Il as defined above and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
  • the invention further relates to a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground, or cultivated plants, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formulae I or II, or a salt thereof, or with a pesticidally effective amount of an agricultural composition as defined above.
  • the invention further relates to seed, comprising at least one compound of formulae I or Il as defined above and/or an agriculturally acceptable salt thereof.
  • the invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of formulae I or II, or a veterinally acceptable salt thereof as defined above.
  • the invention further relates to use of a compound of formulae I or II, or a salt thereof as defined above for controlling animal pests.
  • the carbon atom which carries the radical Ar creates a center of chirality.
  • the compounds of formulae I and Il may be present in the form of different enantiomers or if another center of chirality is present, e.g. in any of the radicals R 2 to R 6 , it may exist in the form of diastereomers.
  • A is a radical of the formula A.1
  • the present invention relates to every possible stereoi- somer of the compounds of formulae I and II, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • Salts of the compounds of formulae I and Il are preferably agriculturally 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 formulae I or Il has a ba-sic functionality or by reacting an acidic compound of formulae I or Il 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-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of formulae I or Il 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 formulae I or Il containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for exam- pie 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 C n -Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particu- lar fluorine, chlorine or bromine.
  • Ci-C ⁇ -alkyl as used herein and in the alkyl moieties of d-C ⁇ -alkoxy, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, C-i-C ⁇ -alkylthio, d-C ⁇ -alkylcarbonyl,
  • Ci-C3-alkyl examples are methyl, ethyl, propyl and 1-methylethyl (isopropyl).
  • Ci-C ⁇ alkyl further encompass, butyl, 1-methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert-butyl), 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,
  • Ci-C ⁇ -haloalkyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C3-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, di- fluoromethyl, trifluoromethyl, chloro-fluoromethyl, dichlorofluoromethyl, chlorodifluoro- methyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethy
  • Exam- pies for Ci-C3-alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy) and OCH(CH3)2 (isopropoxy).
  • Ci-C ⁇ -alkoxy further encompass n-butoxy, OCH(CH3)C2H 5 (sec-butoxy), OCH 2 CH(CHs) 2 (isobutoxy), OC(CH 3 )S (tert-butoxy), n-pentoxy, 1 methyl- butoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1 methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy,
  • Ci-C ⁇ -haloalkoxy refers to a Ci-C6-alkoxy group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-C3-haloalkoxy groups i.e.
  • Ci-C3-alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chloro- difluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 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, pentafluoroeth- oxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoro
  • Ci-C ⁇ -haloalkoxy fur- ther encompass 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5 bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6 trichloro-1-hexoxy and dodecafluorohexoxy.
  • Particularly preferred are chloromethoxy, fluorometh-oxy, difluoromethoxy, trifluoro- methoxy, 2-fluoroethoxy, 2 chloroethoxy and 2,2,2-trifluoroethoxy.
  • Ci-C ⁇ -alkyl- carbonyl further encompass n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methyl- butylcarbonyl, 3-methylbutylcarbonyl, 1 ,1-dimethylpropylcarbonyl, 1 ,2-dimethylpropyl- carbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1-methyl- pentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentyl- carbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethylbutyl- carbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutyl- carbonyl, 1-ethylbutylcarbony
  • Ci-C4-alkoxycarbonyl examples include -C(O)OCH 3 , -C(O)OC 2 H 5 , -C(O)O-CH 2 -C 2 H 5 , -C(O)OCH(CHs) 2 , n-butoxycarbonyl, -C(O)OCH(CHs)-C 2 H 5 , -C(O)-OCH 2 CH(CHs) 2 and C(O)OC(CHs) 3 .
  • Ci-C ⁇ -alkoxycarbonyl further encompass 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-d
  • Examples for Ci-C3-alkylthio include methylthio, ethylthio, propylthio and 1 methylethylthio.
  • C-i-C ⁇ -alkylthio further encompass butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 ,1-dimethylethylthio.
  • Ci-C ⁇ -haloalkylthio refers to a d-C ⁇ -alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-C3-haloalkylthio groups i.e.
  • Ci-C3-alkylthio groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethyl- thio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoro- methylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2- difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-
  • C-i-C ⁇ -haloalkylthio further encompass 4-fluorobutylthio, 4-chlorobutylthio, 4 bromobutylthio, nonafluorobutylthio, 5-fluoro- 1-pentylthio, 5-chloro-1-pentylthio, 5 bromo-1-pentylthio, 5-iodo-1-pentylthio, 5,5,5-trichloro-1-pentylthio, undecafluoropentylthio, 6-fluoro-1-hexylthio, 6-chloro- 1-hexylthio, 6-bromo-1-hexylthio, 6-iodo-1-hexylthio, 6,6,6-trichloro-1-hexylthio and dodecafluorohexylthio.
  • chloromethyl-thio particularly preferred are chloromethyl-thio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio and 2,2,2-trifluoroethylthio.
  • Ci-C ⁇ -alkylamino refers to a secondary amino group carrying one alkyl group as defined above, e.g. me- thylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methyl- propylamino, 2-methylpropylamino, 1 ,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropyl- amino, 1-ethylpropylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropyl- amino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1
  • di(Ci-C6-alkyl)amino refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g.
  • C2-C6-alkenyloxy, C2-C6-alkenylamino and C2-C6-alkenylcarbonyl refers to a straight- chain or branched unsaturated hydrocarbon group having 2 to 6 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
  • C2-C6-alkenyloxy refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy and the like.
  • C2-C6-alkynyl as used herein and in the alkynyl moieties of C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio and C2-C6-alkynylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent- 1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl,
  • C2-C6-alkynyloxy refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, butyn-4-yloxy and the like.
  • monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • Phenyl fused to benzene is naphthyl.
  • Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl, 2,3-dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like.
  • heteroaryl (“mono or bicyclic 5- to 10-membered heteroaromatic ring”) as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyclic or heterocyclic 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the heter- aryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the carbocyclic or heterocyclic fused ring is se- lected from Cs-Cz-cycloalkyl, 5 to 7 membered heterocyclyl and phenyl.
  • 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.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
  • heterocycle (“saturated or partially unsaturated heterocycle”) comprises nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 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 pyr- rolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxa- zolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4-dioxanyl, thiopyranyl,
  • Ci-C ⁇ -alkanediyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms
  • Ci-C4-alkanediyl where one of the hydrogen atoms in these groups is replaced by a further bonding position.
  • Examples for linear C-i-C ⁇ -alkanediyl comprise methyldiyl, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl.
  • Examples for branched d-C ⁇ -alkanediyl comprise ethyl-1 ,1-diyl, propyl-1 ,1-diyl, butyl- 1 ,1-diyl, 1-methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1-ethylethane-1 ,2 diyl, 1-methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.
  • animal pests as used herein includes all invertebrate pests which may harm or damage plants, plant propagation material, or other non-living material.
  • animal pests as used herein includes in particular arthropods and nematodes.
  • “animal pests” are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
  • plant propagation material includes all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emer- gence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • cultivated plants as used herein includes plants which have been modified by breeding, mutagenesis or genetic engineering.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides), for example by glycosylation or polymer additions such as prenylated, acetylated or farne- sylated moieties or PEG moieties (e.g. as disclosed in Biotechnol Prog. 2001 JuI- Aug;17(4):720-8., Protein Eng. Des. SeI.
  • cultiva plants as used herein further includes plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO
  • specific classes of herbicides such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO
  • EP-A-0242236, EP-A-242246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • mutagenesis for example Clearfield ® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox.
  • cultiva plants as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus bacillus, particularly from bacil- lus thuringiensis, such as endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), Cry- IIA(b), CrylllA, CrylllB(bi ) or Cry ⁇ c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for exam- pie Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium or calcium channels
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ).
  • Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods insects, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
  • cultivars as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for exam- pie potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes for exam- pie potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g
  • cultiva plants as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil con- tent or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • cultiva plants as used herein further includes plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex- ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape).
  • cultiva plants as used herein further includes plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato).
  • recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato).
  • the group Ar preferably is phenyl, which carries 1 , 2 or 3 radicals R Ar , wherein R Ar is as defined above and wherein
  • R Ar bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2 3 or 4 substituents, independently of one another selected from halo- gen, CN, NO 2 , OH, SH, NH 2 , COOH, Ci-C 6 -alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyloxy,
  • radical R Ar is selected from halogen, CN, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, Ci-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy.
  • azolin-2-ylamino compounds of formula I wherein Ar is phenyl, which carries 2 radicals R Ar in the 2- and 3-postion, relative to the bonding position, and wherein R Ar has one of the meanings given before, in particular one of the preferred or more preferred meanings.
  • azolin-2-ylamino compounds of formula I wherein Ar is phenyl, which carries 2 radicals R Ar selected from halogen, CN, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and Ci-C6-haloalkoxy in the 2- and 3-position, relative to the bonding position of phenyl.
  • R Ar selected from halogen, CN, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and Ci-C6-haloalkoxy in the 2- and 3-position, relative to the bonding position of phenyl.
  • the radical R 1 preferably is selected from hydrogen, halogen, Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-C ⁇ -cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of d-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-C ⁇ -cycloalkyl, is unsubsti- tuted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2,
  • R 1 is selected from hydrogen and Ci-C6-alkyl. Most preferably R 1 is hydrogen.
  • the radicals R 2 and R 3 preferably are independently of one another selected from hydrogen, halogen, Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-C ⁇ -cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, Ci-C ⁇ -haloalkoxy, C2-C6-alkenyloxy, C 2 -C 6 -alkynyloxy, NH 2 , Ci-Ce-alkylamino, di(Ci-C 6 -alkyl)amino
  • R 2 and R 3 are independently of one another selected from hydrogen, halogen and Ci-C6-alkyl. Most preferably the radicals R 2 and R 3 are hydrogen.
  • the number n of -C(R 2 )(R 3 )- groups preferably is 1 or 2. More preferably n is 1.
  • the group -[C(R 2 )(R 3 )] n - is methylene, i.e. the radicals R 2 and R 3 both are hydrogen and n is 1.
  • the radical R 4 preferably is selected from hydrogen, halogen, d-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy, C3-C8-cycloalkyl and Ar 5 , wherein Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy and Cs-Cs-cycloalkyl are unsubsti- tuted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected
  • the radical R 4 is selected from hydrogen, halogen, Ci-C ⁇ -alkyl and Ar 5 , wherein Ci-C ⁇ -alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, inde- pendently of one another selected from halogen, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Ar 6 , wherein Ar 5 and Ar 6 have one of the meanings given before.
  • the radical R 4 is selected from Ci-C ⁇ -alkyl and Ar 5 , wherein Ci-C ⁇ -alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 6 , wherein Ar 5 and Ar 6 have one of the meanings given before.
  • radicals Ar 5 and Ar 6 if present in the radicals R 4 are preferably independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and Ci-C ⁇ -haloalkoxy.
  • the radicals R 5 and R 6 preferably are selected independently of one another from hy- drogen, halogen, Ci-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkylnyl, C2-C6-alkynyloxy, Cs-Cs-cycloalkyl and Ar 8 , wherein Ci-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkylnyl, C2-C6-alkynyloxy and C3-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -OH, d-C ⁇ -alkoxy, Ci-C6-haloalkoxy, C2-C
  • R 5 and R 6 are selected independently of one another from hydrogen, halogen, Ci-C ⁇ -alkyl and Ar 8 , wherein Ci-C ⁇ -alkyl is unsubstituted or carries any com- bination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 9 , wherein Ar 8 and Ar 9 have one of the meanings given before.
  • radicals Ar 8 and Ar 9 if present in the radicals R 5 and R 6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy.
  • R 5 and R 6 are selected independently of one another from hydrogen and halogen. Particularly preferred are compounds of formulae I or Il wherein R 5 and R 6 both are hydrogen.
  • One particular embodiment of the invention relates to compounds of formulae I or II, wherein X is sulfur.
  • Another particular embodiment of the invention relates to compounds of formulae I or II, wherein X is oxygen.
  • X in formula I is oxygen
  • one of the radicals R 4 , R 5 and R 6 is different from hydrogen and d-C ⁇ -alkyl, if Ar is phenyl, that is unsubstituted or carries 1 , 2, 3 4 or 5 radicals R Ar .
  • Another particular embodiment of the invention relates to compounds of formulae I or Il wherein X is N(R 10 ).
  • X is O or S. More preferably X is S.
  • radicals R 7a , R 7b , R 7c , R 7d preferably are independently of one another selected from hydrogen, halogen, d-C ⁇ -alkyl and d-C ⁇ -haloalkyl. More preferably the radicals R 7a , R 7b , R 7c and R 7d are hydrogen.
  • the radicals R 8 , R 9 , R 10 preferably are selected independently of one another from hy- drogen, CN, NO 2 , d-C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl and C 3 -C 8 -cycloalkyl, wherein d-C ⁇ -alkyl, C 2 -C6-alkenyl, C 2 -C6-alkynyl and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2 or 3 or substituents, independently of one another selected from halogen, CN, NO 2 , -OH, Ci-C6-alkoxy, C 2 -C6-alkenyloxy, C 2 -C 6 -alkynyloxy, d-Ce-haloalkoxy, -SH, d-Ce-alkylthio, d-Ce-hal
  • R a , R b , R c , R d and R e independently of one another have one of the meanings given before.
  • the radicals R a , R a ', R b , R c , R d , R e , R f , Rs and R h preferably are selected each independently of one another from hydrogen, Ci-C ⁇ -alkyl and phenyl, wherein Ci-C ⁇ -alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, independ- ently of one another selected from halogen, CN, NO2, OH, Ci-C6-alkoxy, d-C ⁇ -haloalkoxy and d-C ⁇ -alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, Ci-C6-alkoxy and d-C ⁇ -haloalkoxy.
  • the radicals Ar 1 , Ar 2 , Ar 3 , Ar 4 , Ar 5 , Ar 6 , Ar 7 , Ar 8 , Ar 9 , Ar 10 and Ar 11 are preferably independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy.
  • the compounds of formula Il can be converted into compounds of formula I by means of a chemical reaction.
  • One specific embodiment relates to compounds of formula (II) wherein W a group - OR 11 .
  • the radical R 1 if present in the radical R 11 , preferably is selected from hydrogen, d-C ⁇ -alkyl, and Ar 12 , wherein d-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, C-i-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 13 , wherein Ar 12 and Ar 13 have one of the meanings given before.
  • radicals Ar 12 and Ar 13 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl and d-C ⁇ -haloalkoxy.
  • R 1 is selected from hydrogen, d-C ⁇ -alkyl, and Ar 12 , wherein d-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 13 , wherein
  • Ar 12 and Ar 13 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl and Ci-C ⁇ -haloalkoxy.
  • radical R 11 is selected from hydrogen and d-C ⁇ -alkylcarbonyl.
  • One specific embodiment of the invention relates to azolin-2-ylamino compounds of formula I, wherein
  • n is 1 or 2, preferably 1 ;
  • Ar is phenyl, which carries 1 , 2 or 3 radicals R Ar , wherein
  • R Ar bound to adjacent carbon atoms of the phenyl or naphtyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO 2 , OH, SH, NH2, COOH, d-Ce-alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, C-i-C ⁇ -haloalkoxy and d-C ⁇ -alkylthio; and wherein
  • R Ar is preferably selected from halogen, CN, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C-i-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy; and wherein R Ar is likewise preferably located in the 2- and 3-position, relative to the bonding position, relative to the bonding position of phenyl;
  • A is a radical of the formulae A 1 or A 2 as defined herein , wherein
  • X is S, O or N(R 10 ), preferably S or O, in particular S;
  • R 7a , R 7b , R 7c and R 7d are independently of one another selected from hydrogen, halogen, Ci-C ⁇ -alkyl and d-C ⁇ -haloalkyl, in particular hydrogen;
  • R 1 is selected from hydrogen, Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-C ⁇ -cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C ⁇ -alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, -SH and Ci-C ⁇ - alkylthio, and wherein Cs-
  • R 1 is preferably selected from hydrogen and Ci-C ⁇ -alkyl and more preferably is hydrogen;
  • R 2 and R 3 are selected independently of one another from hydrogen, Ci-C ⁇ -alkyl,
  • R 2 and R 3 are preferably selected from hydrogen and Ci-C ⁇ -alkyl and more preferably are hydrogen;
  • R 4 is selected from hydrogen, halogen, Ci-C ⁇ -alkyl and Ar 5 , wherein Ci-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkoxy, Ci-C ⁇ -haloalkoxy and Ar 6 , wherein
  • Ar 5 and Ar 6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, C-i-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy; and
  • R 5 and R 6 are selected each independently of one another from hydrogen, halogen,
  • Ci-C ⁇ -alkyl and Ar 8 wherein Ci-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 9 , wherein
  • Ar 8 and Ar 9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 sub- stituents, independently of one another selected from halogen, d-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, Ci-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy; and wherein
  • R 5 and R 6 preferably are hydrogen or halogen and most preferably hydrogen
  • Another specific embodiment of the invention relates to compounds of formula II, wherein
  • n is 1 or 2, preferably 1 ;
  • Ar is phenyl, which carries 1 , 2 or 3 radicals R Ar , wherein
  • R Ar bound to adjacent carbon atoms of the phenyl or naphtyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO 2 , OH, SH, NH 2 , COOH, d-Ce-alkyl, Ci-C 6 -alkoxy, C 2 -C 6 -alkenyloxy, C 2 -C 6 -alkynyloxy, d-C ⁇ -haloalkoxy and d-C ⁇ -alkylthio; and wherein
  • R Ar is preferably selected from halogen, CN, Ci-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy; and wherein R Ar is likewise preferably located in the 2- and 3-position, relative to the bonding position, relative to the bonding position of phenyl;
  • A is a radical of the formulae A 3 as defined herein, wherein
  • X is S, O or N(R 10 ), preferably S or O;
  • R 7a , R 7b , R 7c and R 7d are independently of one another selected from hydrogen, halogen, Ci-C ⁇ -alkyl and d-C ⁇ -haloalkyl, in particular hydrogen;
  • R 8 , R 9 and R 10 are hydrogen;
  • R 1 is selected from hydrogen, Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-C ⁇ -cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2- C ⁇ -alkynyloxy, NH2, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, -SH and C-i-C ⁇ - alkylthio, and wherein C
  • R 1 is preferably selected from hydrogen and Ci-C ⁇ -alkyl, and more preferably is hydrogen;
  • R 2 and R 3 are selected independently of one another from hydrogen, Ci-C ⁇ -alkyl,
  • C3-C6-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independ- ently of one another from d-C ⁇ -alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C-i-C ⁇ -haloalkyl; and wherein
  • R 2 and R 3 are preferably selected from hydrogen and d-C ⁇ -alkyl, and more pref- erably are hydrogen;
  • R 4 is selected from hydrogen, halogen, d-C ⁇ -alkyl and Ar 5 , wherein d-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, Ci-C6-haloalkoxy and Ar 6 , wherein
  • Ar 5 and Ar 6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy;
  • R 5 and R 6 are selected each independently of one another from hydrogen, halogen, d-C ⁇ -alkyl and Ar 8 , wherein d-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 9 , wherein
  • Ar 8 and Ar 9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, d-C ⁇ -alkoxy and d-C ⁇ -haloalkoxy; and wherein
  • R 5 and R 6 preferably are hydrogen or halogen and most preferably hydrogen
  • W is selected from halogen and -OR 11 and preferably is -OR 11 , wherein
  • R 1 is selected from hydrogen, d-C ⁇ -alkyl, and Ar 12 , wherein d-C ⁇ -alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independ- ently of one another selected from halogen, d-C ⁇ -alkoxy, d-C ⁇ -haloalkoxy and Ar 13 , wherein
  • Ar 12 and Ar 13 are independently of one another selected from phenyl and pyridyl, wherein phenyl and pyridyl are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl and d-C ⁇ -haloalkoxy; and wherein R 11 preferably is selected from hydrogen and Ci-C ⁇ -alkylcarbonyl;
  • Examples of preferred compounds of formula I are the compounds of formula I.A.1 , I.A.2, I.A.3 and I.A.4,
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of the following table 1 (compounds I .A.1 .1 to I .A.1 .1430, I .A.2.1 to I .A.2.1430, I .A.3.1 to I.A.3.1430 and I .A.4.1 to I .A.4.1430).
  • Table B Examples of preferred compounds of formula I are the compounds of formula I.B.1 , I.B.2, I.B.3 and I.B.4,
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds I.B.1.1 to I.B.1.1430, I.B.2.1 to I.B.2.1430, I.B.3.1 to I.B.3.1430 and I.B.4.1 to I.B.4.1430).
  • Table C Examples of preferred compounds of formula Il are the compounds of formula II. a and II. b,
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.a.1 to ll.a.1430 and ll.b.1 to ll.b.1430).
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.c.1 to II.C.1430 and ll.d.1 to ll.d.1430).
  • Table E Examples of preferred compounds of formula Il are the compounds of formula ll.e and ll.f,
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.e.1 to ll.e.1430 and ll.f.1 to ll.f.1430).
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.g.1 to ll.g.1430 and ll.h.1 to ll.h.1430).
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.i.1 to ll.i.1430 and ll.k.1 to ll.k.1430).
  • R 4 , R 5 and R 6 have the meanings corresponding to one line of table 1 (compounds ll.m.1 to ll.m.1430 and ll.n.1 to ll.n.1430).
  • the compounds of formulae I and Il can be obtained for example by the methods outlined in schemes 1 to 9.
  • n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R 8 , R 9 and Ar have one of the meanings given above.
  • a compound of formula I wherein R 8 or R 9 is hydrogen is treated with a suitable electrophile.
  • the compounds of the formula I wherein X is oxygen or sulfur can be prepared e.g. from the corresponding aminothiocarbonylaminoethanol compounds of formula II. a or from aminocarbonylaminoethanol compounds of formula II. b, respectively, as depicted in scheme 2.
  • n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d and Ar are as defined above.
  • the aminothiocarbonylaminoethanol compound II. a and the aminocarbonylaminoetha- nol compound ll.b, respectively, can be cyclized by conventional means thereby obtaining an azoline compound of the formula I. Cyclization of the compounds II. a and ll.b, respectively, can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters 1999, 40, 3125-3128) or as described in the preparation example 18.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d and Ar are as defined above.
  • An amine III or a salt thereof is converted to the corresponding iso(thio)cyanate IV by conventional means, e.g. by reacting III with (thio)phosgene, as described for example in the case of thiophosgene in Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter Nc, pp. 837-842, Georg Thieme Verlag 1983. It may be advantageous to carry out the reaction in the presence of a base.
  • the iso(thio)cyanate IV is then reacted with an aminoethanol V to form an amino(thio)carbonylaminoethanol compound.
  • the reaction of the aminoethanol V with iso(thio)cyanate IV can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Biochem. 56 (7), 1062-65 (1992).
  • n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R' and Ar are as defined above.
  • An aminoalkenyl compound III or a salt thereof can be converted to the corresponding aminothiocarbonylaminoethanol compound ILa, by reaction of the compound III with an isothiocyanate Vl and subsequent saponification as described in the preparation examples 1 and 2.
  • Suitable isothiocyanates can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117.
  • Aminoalkenyl compounds of formula III are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of amines and alkenes and as depicted e.g. in scheme 5 or shown in the preparation examples 1 and 38 to 40.
  • Suitable salts of aminoalkenyl compounds III are e.g. the acid addition salts formed by treating a compound of formula III with an inorganic or organic acid.
  • Anions of useful acids are e.g.
  • Ci-C4-alkanoic acids such as acetate, propionate, and the like.
  • magnesium halides VIII to appropriate imines VII followed by aqueous work up or acidic treatment can provide amines III as described in J. Org. Chem. 1983, 48, 289-294 or Tetrahedron 1999, 55, 8883-8904 or in the preparation example 39.
  • the alkene unit of the aminoalkenyl compounds III can also be prepared from carbonyl groups for example by reacting those carbonyl functions with carbon tetrabromide in the presence of triphenylphosphine according to the Corey-Fuchs method (cf. preparation example 41 ).
  • the carbonyls can be obtained for example by oxidation of the corre- sponding alcohols for example as described in J. Med. Chem. 2003, 46, 3539.
  • the alcohols are known in the art or can in general be prepared by methods familiar to an organic chemist and well known in the art for e.g. in Tetrahedron Letters 2004, 45,1503.
  • n R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d and Ar are as defined above.
  • An amine of formula III or a salt thereof can be converted to an azoline of formula I by reaction with a 2-chloroethylisothiocyanate or a 2-chloroethylisocyanate of formula IX e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22 and subsequent cycli- zation in the presence or absence of base.
  • 1-Chloro-2-isothiocyanatoethane CAS- reg.-no.: 6099-88-3
  • 2-chloro-ethyl-isocyanate CAS-reg.-no.: 1943-83-5
  • n R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R 9 and Ar are as defined above and LG is a leaving group.
  • n, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R 9 , R 10 and Ar are as defined above and LG is a leaving group.
  • the compounds of formula I wherein X is oxygen or sulfur and R 1 is hydrogen, can also be prepared starting from amines XII via aminothiazolines or ami- nooxazolines XIII, as outlined in scheme 9.
  • a further conversion with an alkylating or acylating reagent R 89 -LG can provide derivatised aminothiazolines or aminooxazolines XIV and/or XV.
  • Those can be subsequently alkylated with electrophiles of formula XVI , optionally followed by hydrolysis, as outlined in scheme 9 and in the preparation example 20.
  • n, R 2 , R 3 , R 4 , R 5 , R 6 , R 7a , R 7b , R 7c , R 7d , R 8 , R 9 and Ar are as defined above and LG and LG' are leaving groups, such as halogen.
  • radicals R 4 , R 5 and R 6 bound to the ethylenically unsaturated part of azoline compounds of formula I can be exchanged, for example by Heck reactions (see e.g. Synthesis 2002, 315-316 or Tetrahedron Lett. 2002, 43, 3401-3405 or the preparation example 21 ), to give further azoline compounds of formula I.
  • the compounds of formulae I and Il can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds of formulae I and Il or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formulae I and Il can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, metal catalyzed coupling reactions, oxidation and the like.
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colourless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
  • the compounds of formulae I and Il may be used for controlling animal pests. Accordingly, the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the mate- rials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or Il or a salt thereof or a composition as defined above.
  • the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the formula I or Il or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricul- tural composition as defined above and below.
  • the method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
  • animal pests are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
  • the invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of formula I or Il or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
  • compositions may contain a single active compound of formula I or Il or a salt thereof or a mixture of several active compounds of formulae I or Il or their salts according to the present invention.
  • the composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautom- ers or mixtures of tautomers.
  • the compounds of the formulae I and Il and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes.
  • Animal pests controlled by the compounds of formulae I and Il include for example:
  • 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, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heli
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtip
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycor
  • Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
  • homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melan
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Arachnids Acarina
  • Argasidae e.g. of the families Argas
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
  • Siphonatera e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
  • compositions and compounds of formula I are useful for the control of nematodes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
  • cyst-forming nematodes Globodera rostochiensis and other Globodera species
  • Het- erodera avenae Heterodera glycines, Heterodera schachtii, Heterodera trifolii, 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 nematodes Criconema species, Criconemella species, Criconemoides species, Mesocriconema species
  • Stem and bulb nematodes Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species
  • AwI nema- todes Dolichodor
  • the compounds of formula I are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina.
  • the com- pounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
  • the compounds of formulae I and Il or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pes- ticidally effective amount of compounds of formula I.
  • crop refers both to growing and harvested crops.
  • the compounds of formulae I and Il can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • auxiliaries suitable for the formulation of agrochemicals such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
  • solvents examples include water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral oil fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone, gamma-butyrolactone
  • pyrrolidones N
  • Suitable emulsifiers are non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
  • dispersants are lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sul- fonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, poly- oxyethylene octylphenol ether, ethoxylated isooctylphenol, octyl
  • Substances which are suitable for the preparation of directly sprayable solutions, emul- sions, 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, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or 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,
  • anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
  • Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
  • a suitable preservative is e.g. dichlorophen.
  • Seed treatment formulations may additionally comprise binders and optionally colorants.
  • Binders can be added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable binders are block copolymers, EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol ® , Polymin ® ), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , 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.
  • Examples of a gelling agent is carrageen (Satiagel ® ).
  • Powders, materials for spreading and dustable products 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 compounds to solid carriers.
  • solid carriers examples include 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, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s).
  • the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
  • the compounds of formula I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example 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; they are intended to ensure in each case the finest possible distribution of the active compound(s) 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 compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
  • the active compound(s) 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 compound, or even to apply the active compound without additives.
  • UUV ultra-low-volume process
  • Products for dilution with water for foliar applications may be applied to the seed diluted or undiluted.
  • the active compound(s) 10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.
  • Emulsions EW, EO, ES
  • 25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
  • an emulsifier machine e.g. Ultraturrax
  • 50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active com- pound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
  • 75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addi- tion of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained.
  • Products to be applied undiluted for foliar applications may be applied to the seed diluted or undiluted.
  • Dustable powders (DP, DS) 5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)
  • 0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound ⁇ ) is obtained.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
  • the compounds of formula I are also suitable for the treatment of plant propagation materials (such as seed).
  • Conventional seed treatment formulations include for exam- pie flowable concentrates FS, solutions LS, powders for dry treatment DS, water dis- persible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • compositions of compounds of formulae I or Il for seed treatment comprise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
  • oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
  • the compounds of formulae I and Il are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • com- pounds of formulae I and Il 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 formulae I or Il as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethylformamide, N-methylpyrrolidone, dimethyl sulphoxide, 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 formulae I or Il and their 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 sys- terns.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of formulae I or Il and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, non- wovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyre- throid not used for insect control such as ⁇ (+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)- enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eu
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and diethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of aliphatic acids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and diethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the active compounds of formulae I or Il or spray- ing them onto the nets.
  • seed treatment refers to all methods that bring plant propagation material, in particular seeds, and the compounds of formulae I or II, or a salt therof, into contact with each other
  • seed dressing to methods of seed treatment which provide the plant propagation material, in particular the seeds with an amount of the compounds of formulae I or II, i.e. which generate a plant propa- gation material, in particular a seed comprising the compound of formulae I or II.
  • the treatment can be applied to the plant propagation material, in particular to the seed at any time from the harvest of the plant propagation material, in particular of the seed to the sowing of the seed.
  • the plant propagation material, in particular the seed can be treated immediately before, or during, the planting of the plant propagation material, in particular of the seed, for example using the "planter's box" method.
  • the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
  • the treatment is applied to unsown plant propagation material, in particular unsown seed.
  • unsown seed is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
  • a procedure is followed in the treatment in which the plant propagation material, in particular the seed is mixed, in a suitable device, for example a mixing de- vice for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If ap-propriate, this is followed by a drying step.
  • the compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
  • a further object of the present invention is therefore to provide new methods for controlling parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
  • the invention also relates to compositions containing a parasiticidally effective amount of compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
  • the present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the present invention also provides a non-therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of for- mulae I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises including a parasiticidally effective amount of a compound of formula I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the invention relates further to the use of compounds of formula I for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
  • the invention relates also to the use of a compound of the formulae I or II, or a composition comprising it, for the manufacture of a medicament for the therapeutic treatment of animals against infections or infestions by parasites.
  • Compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling 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.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals
  • Compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof 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 formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
  • the compounds of formulae I or Il are especially useful for combating ectoparasites.
  • the compounds of formulae I or Il are especially useful for combating parasites of the following orders and species, respectively:
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
  • insects e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha 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, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Cul
  • 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, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g.
  • Orni- thonyssus bacoti and Dermanyssus gallinae actinedida (Prostigmata) and 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 Laminosiopte
  • 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
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trichinosis Trichosyringida
  • Trichinellidae Trichinella spp.
  • Trichuridae Trichuris spp.
  • Capillaria spp Trichinosis
  • 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., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp.,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascar
  • 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 Hab- ronema spp., Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus 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 formulae I or Il and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the compounds of formulae I or Il also are especially useful for combating endopara- sites (roundworms nematoda, thorny headed worms and planarians).
  • the compounds of formula I can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits).
  • the present invention relates to the therapeutic and the non-therapeutic use of compounds of formula I for controlling and/or combating parasites in and/or on animals.
  • the compounds of formula I may be used to protect the animals from attack or infestation by parasites by contacting them with a parasitically effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the parasite, e.g. also at it's locus, and optionally also administrating the compounds/composition directly on the animal) and indirect contact (applying the compounds/compositions to the locus of the parasite).
  • the contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of formula I.
  • “Locus” as defined above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests or parasites is expected.
  • the administration to the animal 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 compounds of formulae I and Il may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the compounds of formulae I 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 compounds of formeulae I and II, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the compounds of formulae I or Il may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds of formulae I or Il may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds of formulae I or Il may be formulated into an implant for subcutaneous administration.
  • the compounds of formulae I or Il 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 compounds of formulae I or II.
  • the compounds of formulae I or Il 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 compounds of formulae I or II.
  • the compounds of formulae I or Il 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 for oral or dermal administration; semi-solid preparations;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tab- lets, 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- methylpyrrolidone, 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, polyvinyl 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 according 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, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • alkyleneglycol alkylether e.g. dipropylenglycol monomethylether
  • ketons such as acetone, me- thylethylketone
  • aromatic hydrocarbons such as acetone, me- thylethylketone
  • vegetable and synthetic oils dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate,
  • 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-promoting substances, antioxidants, light stabilizers, adhesives are added.
  • Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene 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 methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N methylpyrroli- done
  • 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, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do 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 C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, is
  • 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 monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; 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.
  • non-ionic surfactants e.g. polyethoxy
  • 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 substances, preservatives, antioxidants, light stabilizers.
  • auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
  • Liquid suspending agents are all homogeneous solvents and solvent mixtures.
  • Suitable wetting agents are the emulsifiers 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.
  • 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.
  • 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.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compounds of formulae I or II.
  • the compounds of formulae I or Il 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 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
  • the preparations comprise the compounds of formulae I or Il against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
  • compositions comprising the compounds of formulae I or Il 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 formulae I or Il 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 compounds of formulae I or II.
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, 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.
  • agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds of formulae I or Il or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
  • Organo(thio)phosphates acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicro- tophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
  • Nicotinic receptor agonists/antagonists compounds acetamiprid, bensultap, car- tap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thio- cyclam, thiosultap-sodium and AKD1022.
  • GABA gated chloride channel antagonist compounds chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole
  • Chloride channel activators abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
  • METI I compounds fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
  • METI Il and III compounds acequinocyl, fluacyprim, hydramethylnon;
  • M.1 Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
  • Moulting disruptors cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
  • Mite growth inhibitors clofentezine, hexythiazox, etoxazole;
  • Lipid biosynthesis inhibitors spirodiclofen, spiromesifen, spirotetramat
  • Anthranilamides chloranthraniliprole,cyantraniliprole,
  • Anthranilamide derivatives of formula M24.1 have been described in WO 01/70671 , WO 04/067528 and WO 05/1 18552. Cyantraniliprole has been described in WO 01/70671 , WO 04/067528 and WO 05/118552.
  • the anthranilamides M 24.1 to M 24.6 have been described in WO 2008/72743 and WO 200872783.
  • the phthalamide M 21.1 is known from WO 2007/101540. Cyflumetofen and its preparation have been described in WO
  • the aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932.
  • Sulfoximine sulfoxaflor has been described in WO 2006/060029 and WO 2007/149134.
  • the alkynylether compound M22.1 is described e.g. in JP 2006131529.
  • Organic sulfur compounds have been described in WO 2007060839.
  • the carboxamide compound M 22.2 is known from WO 2007/83394.
  • the oxazoline compounds M 22.3 to M 22.6 have been described in WO 2007/074789.
  • the furanon compounds M 22.7 to M 22.16 have been described eg. in WO 2007/1 15644.
  • the pyripyropene derivative M 22.17 has been described in WO 2008/66153 and WO 2008/108491.
  • the pyridazin compound M 22.18 has been described in JP 2008/1 15155.
  • the malononitrile compounds have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.
  • Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole
  • the animal pest i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) of formulae I or Il or composition(s) containing them by any application method known in the art.
  • "contacting” includes both direct contact (applying the compounds/compositions di- rectly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
  • animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formulae I or II.
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • “Locus” means a habitat, breeding ground, cultivated plants, plant propagation material (such as 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 ef- fective 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 formulae I and Il and their compositions can be used for protecting wooden materials such as 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 the formulae I or Il 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, plywood, furniture, etc., wooden articles such as particle boards, half boards, 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 compounds of formulae I and Il can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formulae I and Il 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 formulae I or II.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and/or insecticide.
  • the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
  • the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the application rates of the active ingredients are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
  • HPLC High Performance Liquid Chromatography / mass spectroscopy
  • MS Quadrupol electrospray ionisation, 80 V (positive modus).
  • Example 2 Preparation of 1-[1-(2,3-dimethylphenyl)-3-phenylbut-3-enyl]-3-(2-hydroxy- ethyl)thiourea
  • a mixture of acetic acid 2- ⁇ 3-[1-(2,3-dimethylphenyl)-3-phenylbut-3-enyl]- thioureido ⁇ ethyl ester (142 mg, 0.36 mmol, 1 eq, cf. example 1 )
  • lithium hydroxide monohydrate 34 mg, 0.80 mmol, 2.3 eq
  • water 0.5 ml
  • tetrahydrofuran 4.3 ml
  • Urea compounds i. e. compounds of formula II, wherein X is O
  • Urea compounds can be prepared by anology to the method outlined in preparation example 1 by using isocyanato compounds instead of isothiocyanato compounds.
  • Diisopropylethylamine (74 mg, 0.57 mmol, 1.6 eq) and cyanomethyl-trimethyl- phosphonium iodide (175 mg, 0.72 mmol, 2 eq, cf. Tetrahedron 2001 , 57, 5451 ) were subsequently added to a solution of 1-[1-(2,3-dimethylphenyl)-3-phenylbut- 3-enyl]-3-(2-hydroxyethyl)thiourea (127 mg, 0.36 mmol, 1 eq, cf. example 2) in propionitrile (16 ml).
  • Solution B was added dropwise to solution A at -78 0 C and the mixture was stirred for 2.5 h.
  • a saturated solution of aqueous ammonium chloride was then added and the mixture was extracted with ethyl acetate (x 3).
  • the combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo.
  • the residue was purified by column chromatography to yield 2-[1-(2,3-dichloro- phenyl)-3-methyl-but-3-enylimino]thiazolidin-3-ylcarboxylic acid tert-butyl ester.
  • N-(4,5-dihydrothiazol-2-yl)-N-[1 -(2,3-dichlorophenyl)but-3-enyl]amine (500 mg, 1.66 mmol, 1 eq, cf. example 23) were subsequently added to a mixture of palla- dium(ll) acetate (18.7 mg, 0.08 mmol, 0.05 eq) and triphenylphosphine (43.5 mg, 0.17 mmol, 0.1 eq) in acetonitrile (10 ml) under an argon atmosphere. After re- fluxing for 10 h, a 1 M aqueous solution of hydrochloric acid was added at 0 0 C until the pH reached 6.5.
  • Phenylboronic acid (332 mg, 2.72 mmol, 1.06 eq) was added to a mixture of N-[1-(2,3-dimethylphenyl)-3-iodobut-3-enyl]carbamic acid tert-butyl ester (1.00 g, 2.49 mmol, 1 eq, cf. example 38.1 ), tetrakis(triphenylphosphine)palladium(0)
  • Chlorotrimethylsilane (176 g, 1.62 mol, 5 eq) and water (14.5 ml, 808 mmol, 2.5 eq) were subsequently added over 5 minutes each to a mixture of sodium iodide (242 g, 1.62 mmol, 5 eq) in acetonitrile (1.4 I).
  • 1-(2,3- dichlorophenyl)-but-3-ynylamine (56 g, 324 mmol, 1 eq) was added over 15 min- utes and the mixture stirred at 70 0 C for 2 h.
  • the active compounds were formulated in 50 : 50 acetone : water and 100 ppm Ki- netic ® surfactant.
  • Cotton plants in the cotyledon stage (variety 'Delta Pine') are infested with approximately 100 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The cotyledons of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days. In this test, the compounds of examples 3, 13, 18, 20, 21 , 23, 25, 27, 30, 31 , 32, 35, 36, 37, 38 and 39 at 300 ppm showed over 70 % mortality in comparison with untreated controls.
  • the active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic ® surfactant.
  • Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') are infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The leaves of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
  • Cowpea aphid (Aphis craccivora)
  • the active compounds were formulated in 50:50 acetone : water and 100 ppm Kinetic ® surfactant.
  • Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population has been recorded. Population reduction was recorded after 24, 72, and 120 hours.
  • the active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® surfactant.
  • Selected cotton plants were grown to the cotyledon state (one plant per pot).
  • the cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry.
  • Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced.
  • the insects were colleted using an aspirator and a 0.6 cm, non-toxic Tygon® tubing (R- 3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • the cups were covered with a re-usable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 0 C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.

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Abstract

The present invention relates to azolin-2-ylamino compounds of formulae (I) and (II), wherein n is 0 to 3; Ar is phenyl; A is a radical of formulae A1 or A2, wherein * indicates the point of attachment; X is S, O or N(R10); R7a-d are H, halogen, C1-C6-alkyl, C1-C6-alkoxy, C1-C6-alkylamino or C3-C6-cycloalkyl; R8-10 are H, CN, NO2, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, Ar3, -B-C(=O)Ra, -B-C(=S)Ra, -B-C(=NRf)Ra, etc., wherein B is a single bond or C1-C4-alkanediyl; R1 is H, halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, phenyl or benzyl; R2,3 are H, halogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, phenyl or benzyl; R4 is H, halogen, CN, N3, NO2, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, a heterocycle, Ar5, -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, etc.; or R4 and R5 together form a carbocycle or heterocycle; R5,6 are H, halogen, CN, N3, NO2, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, heterocycle, Ar8, -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, etc.; or R5 and R6 together form a carbocycle or heterocycle; Ra-h are H, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, heterocycles or Ar10; Ar1 to 11 are phenyl, naphthyl or heteroaryl; and A' is a radical of formula A3, wherein W is halogen or OR11; R11 is H or -C(=O)-Ri; Ri is H, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, heterocycle or Ar12; and Ar12 is phenyl, naphthyl or heteroaryl; as well as to agricultural composition containing such compounds, the use of such compounds for controlling animal pests, seed, comprising such compounds, a method for controlling animal pests and a method for treating or protecting an animal from infestation or infection by parasites.

Description

Azolin-2-ylamino compounds for combating animal pests
The present invention relates to azolin-2-ylamino compounds as well as to their precursor compounds, which are both useful for combating animal pests. The invention also relates to a method for controlling animal pests by using these compounds, to seed and to an agricultural and veterinary composition comprising said compounds.
Animal pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwellings and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating insects, arachnids and nematodes. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different animal pests, especially against difficult to control insects, arachnids and nematodes.
Jennings et al. Pesticide Biochemistry and Physiology 30, 1988, p. 190-197, describe several 2-phenylamino oxazolines and 2-benzylamino oxazolines which have insecti- cidal activity. Biosci. Biotech. Biochem. 1992, 56 (7), 1062-1065, discloses phenyl-, benzyl- und phenethyl thiazolines having insecticidal activity. However, these compounds are limited in their activity or with regard to the breadth of their activity spectrum.
WO 2005/063724 describes 1 -(azolin-2-yl)amino-1 ,2-diphenylethane compounds of the general formulae C.1 and C.2,
Figure imgf000003_0001
(C.1 ) (C.2) wherein X is sulfur or oxygen, which are useful for combating insects, arachnids and nematodes. WO 2008/119506 and WO 2008/119511 describe certain 2-(N-benzylimino)- oxazolidines having insecticidal activity.
WO 2008/138499 describes certain N-benzy-N-hydroxyethylthiourea compounds hav- ing insecticidal activity.
It is an object of the present invention to provide compounds that have a good pesti- cidal activity, in particular insecticidal activity, and show a broad activity spectrum against a large number of different animal pests, especially against difficult to control insects.
It has been found that these objectives can be achieved by compounds of the formula I below.
Therefore, in a first aspect the invention relates to azolin-2-ylamino compounds of the general formula (I),
Figure imgf000004_0001
wherein
n is 0, 1 , 2 or 3;
Ar is phenyl, which is unsubstituted or carries 1 , 2, 3, 4 or 5 substituents RAr, wherein
RAr is selected from halogen, CN, N3, NO2, d-Ce-alkyl, C2-C6-alkenyl and
C2-C6-alkynyl, wherein each carbon atom in the aforementioned radicals, in particular each radical of the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl and C2-C6-alkynyl is unsubstituted or may carry any combination of 1 , 2 or 3 substitiuents, independently of one another selected from halogen, CN,
NO2, NH2, OH, SH, COOH, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, Ci-Cβ-haloalkoxy and Ci-Cβ-alkylthio, and
RAr may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra,
-C(=NRf)ORb, -C(=NRf)NRcRd, -C(=NRf)SRe, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra, -O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe, -SRe, -S(=O)Re, -S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb, -NRf-C(=O)NRcRd, -N=CR3R3', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein R3, R3', Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below, and
RAr may further be selected from cyclic radicals -Y-Cy or -Y-Ar1, wherein Ar1 has one of the meanings given below,
Y is a single bond, d-Cβ-alkandiyl, Ci-C6-alkandiyloxy, -C(=O)-,
-C(=S)-, -C(=NRf)-, -C(=NRf)O-, -C(=NRf)S-, -C(=NRf)NRc, -C(=O)O-, -C(=O)NRS -C(=O)S-, -C(=S)O-, -C(=S)NRC-, -C(=S)S-, -O-,
-O-C(=O)-, -O-C(=O)O-, -O-C(=O)-NRC-, -O-C(=O)S-, -S-, -S(=O)-, -S(=O)2-, -S(=O)2O-, -S(=O)2NRS -NRC-, -NRf-C(=O)-, -NRf-C(=O)O-, -NRf-C(=O)NRc-, -N=CR3-, -NRf-NRc-, -NRf-C(=O)S-, -NRf-C(=S)NRc-, wherein R3, Rb, Rc and Rf independently of one another have one of the meanings given below,
Cy is C3-Ci2-cycloalkyl or a saturated or partially unsaturated 5, 6 or 7- membered heterocycle containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, wherein C3-Ci2-cycloalkyl and the heterocycle are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, halogen, CN, NO2, OH, SH, NH2, COOH, C-i-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and d-Ce-alkylthio,
and/or two radicals RAr bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5-, 6- or 7-membered carbocycle or a fused 5-, 6- or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy and d-Cβ-alkylthio; dical of the formulae A1 or A2,
Figure imgf000006_0001
wherein
* indicates the point of attachment to the remaining part of the compound;
X is S, O or N(R10);
R7a, R7b, R7c and R7d are selected independently from one another from hydrogen, halogen, Ci-Cβ-alkyl, d-Cβ-alkoxy, Ci-Cβ-alkylamino and C3-C6-cycloalkyl, wherein
each carbon atom of the aforementioned radicals, in particular each radical of the group consisting of Ci-Cβ-alkyl, C-i-Cβ-alkoxy, Ci-Cβ-alkylamino and C3-C6-cycloalkyl, may be unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -SRe, -NRcRd, C(=O)-Ra, C(=O)ORb and Ar2, wherein Ar2, Ra, Rb, Rc, Rd and Re have one of the meanings given below and wherein C3- Cβ-cycloalkyl additionally may carry any combination of 1 , 2 or 3 substituents of one another selected from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-Cβ-haloalkyl,
R8, R9 and R10 are selected each independently from one another from hydrogen, CN, NO2, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl and Ar3, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=O)Ra, -C(=O)ORb, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, -Ar4, -O-Ar4, -S-Ar4 or -CH2-Ar4, wherein Ar3, Ar4, Ra, Rb, Rc, Rd, Re and Rf have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry any combination of 1 , 2 or 3 or substituents, independently of one another selected from Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, and
R8, R9 and R10 may further be selected from -B-C(=O)Ra, -B-C(=S)Ra, -B-C(=NRf)Ra, -B-C(=NRf)ORb, -B-C(=NRf)NRcRd, -B-C(=NRf)SRe, -B-C(=O)ORb, -B-C(=O)NRcRd, -B-C(=O)SRe, -B-C(=S)ORb, -B-C(=S)NRcRd, -B-C(=S)SRe, -B-ORb, -B-O-C(=O)Ra, -B-O-C(=O)ORb, -B-O-C(=O)-NRcRd, -B-O-C(=O)SRe, -B-SRe, -B-NRcRd, -B-NRf-C(=O)Ra, -B-NRf-C(=O)ORb, -B-NRf-C(=O)NRcRd, -B-N=CR3R3', -B-NRf-NRcRd, -B-NRf-C(=O)SRe, -B-NRf-C(=S)NRcRd, -B-S(=O)Re, -B-S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -P(=O)RsRh and P(=S)R9Rh, wherein
B is a single bond or linear or branched Ci-C4-alkanediyl, and
R3, R3', Rb, Rc, Rd, Re, Rf, Rs and Rh independently of one another have one of the meanings given below;
R1 is selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, phenyl and benzyl, wherein each carbon atom of the aforementioned radicals, in particular each radical of the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cβ-cycloalkyl, phenyl and benzyl, is unsubsti- tuted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -ORb, NRcRd, -SRe, -C(=0)R3 and - C(=O)ORb, wherein R3, Rb, Rc, Rd and Re have one of the meanings given below, and wherein Cs-Cβ-cycloalkyl, phenyl and benzyl additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-Cβ- alkenyl, C2-C6-alkynyl and C-i-Cβ-haloalkyl;
R2 and R3 are selected each independently of one another from hydrogen, halogen Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cβ-cycloalkyl, phenyl and benzyl, wherein each carbon atom of the aforementioned radicals, in particular each radical of the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6- cycloalkyl, phenyl and benzyl, is unsubstituted or carries any combination of 1 , 2 or 3 radicals selected independently of one another from the group consisting of halogen, CN, NO2, -ORb, NRcRd, -SRe -C(=0)R3 and -C(=O)ORb, wherein R3, Rb, Rc, Rd and Re have one of the meanings given above, and wherein C3-C6- cycloalkyl, phenyl and benzyl additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-Cβ- alkynyl and d-Cβ-haloalkyl;
R4 is selected from hydrogen, halogen, CN, N3, NO2, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, saturated or partially unsaturated 5, 6 or 7- membered heterocycle containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members, and Ar5, wherein d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycle are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=0)R3, -C(=O)ORb, Ar6, -CH2-Ar6, -O-Ar6, and -S-Ar6, wherein Rb, Rc, Rd Re, Ar5 and Ar6 have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycle additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-Cβ-haloalkyl, and
R4 may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, -C(=NRf)ORb, -C(=NRf)NRcRd, -C(=NRf)SRe, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra, -O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe, -SRe, -S(=O)Re, -S(=O)2Re, - S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb,
-NRf-C(=O)NRcRd, -N=CRaRa', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein Ra, Ra', Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below; or
R4 and R5 together with the carbon atoms to which they are bound form a partially unsaturated 5, 6 or 7-membered carbocycle or a partially unsaturated 5, 6 or 7-membered heterocycle, wherein the heterocycle contains 1 , 2, 3 or 4 het- eroatoms selected independently from one another from S, O and N as ring members, and wherein each carbocycle or heterocycle may be unsubstituted or may carry 1 or 2 substituents, independently of one another selected from halogen, CN, NO2, -ORb -SRe, -NRcRd, -C(=O)Ra, -C(=O)ORb, Ci-C6-alkyl, C-2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ar7, -CH2-Ar7, -O-Ar7, -S-Ar7, wherein Ra, Rb, Rc, Rd, Re and Ar7 have one of the meanings given below;
R5 and R6 are selected each independently of one another from hydrogen, halogen, CN, N3, NO2, C-i-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, and Ar8, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=O)Ra, -C(=O)ORb, Ar9, -CH2-Ar9, -O-Ar9 and -S-Ar9, wherein Ra, Rb, Rc, Rd, Re, Ar8 and Ar9 have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from
Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cβ-haloalkyl, and
R5 or R6 may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, -C(=NRf)ORb, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra, -O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe,
-SRe, -S(=O)Re, -S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb, -NRf-C(=O)NRcRd, -N=CRaRa', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein Ra, Ra\ Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below, or
R5 and R6 together with the carbon atom to which they are bound form a 5, 6 or 7-membered carbocycle or 5, 6 or 7-membered heterocycle, wherein the hetero- cycle contains 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, and wherein each carbocycle or heterocycle may be unsubstituted or may carry 1 or 2 substituents, independently of one another selected from halogen, CN, NO2, -ORb -SRe, -NRcRd, -C(=O)Ra, -C(=O)ORb, d-Ce-alkyl, C-2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ar10,
-CH2-Ar10, -O-Ar10, and -S-Ar10, wherein Ra, Rb, Rc, Rd, Re and Ar10 have one of the meanings given below;
Ra, Ra', Rb, Rc, Rd, Re, Rf, Rs and Rh are each independently of one another selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S, N as ring members, and Ar10, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs- cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen,
CN, NO2, OH, d-Ce-alkoxy, d-Ce-haloalkoxy, d-Ce-alkylthio, Ci-C6- haloalkylthio, d-Cβ-alkylcarbonyl, d-Cβ-haloalkylcarbonyl, d-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Cs-Ce-cycloalkyl, C3-C6-halocycloalkyl, Ar11, -CH2-Ar11, -O-Ar11 and -S-Ar11, wherein Ar10 and Ar11 have one of the meanings given below, and wherein
Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cβ-haloalkyl; and
Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10 and Ar11 are each independently of one another selected from phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heteroaryl, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein phenyl, naphtyl and hetaryl are unsubstituted or carry any combination of 1 to 5 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, d-Ce-haloalkyl, d-Cβ-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Cβ-haloalkylthio, Ci-Cβ-alkylcarbonyl, d-Cβ-haloalkylcarbonyl, d-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, C3-C6-cycloalkyl, Cs-Cβ-halocycloalkyl, unsubstituted phenyl and phenyl carrying 1 , 2, 3, 4 or 5 substituent selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and Ci-C6-haloalkoxy; or the enantiomers, diastereomers or salts thereof.
The invention further relates to compounds of general formula
Figure imgf000010_0001
wherein n, Ar, R1, R2, R3, R4, R5 and R6 independently from one another have one of the meanings given for the compounds of formula I, and
A' is a radical of formula A3,
Figure imgf000010_0002
wherein W is halogen or -OR11,
R7a, R7b, R7c, R7d, R8, R9 and X independently from one another have one of the meanings given for the compounds of formula I,
* indicates the point of attachment to the remaining part of the compound; and
R11 is selected from hydrogen and -C(=O)-R', wherein R1 is selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members, and Ar12, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, OH, Ci-Cβ-alkoxy, C-i-Cβ-haloalkoxy, C-i-Cβ-alkylthio, C-i-Cβ-haloalkylthio, d-Cβ-alkylcarbonyl, Ci-Cβ-haloalkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Cs-Cβ-cycloalkyl, Cs-Cβ-halo- cycloalkyl, Ar13, -CH2-Ar11, -O-Ar11 and -S-Ar11, wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C-i-Cβ-haloalkyl; and wherein Ar12 and Ar13 are independently of one another selected from phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heteroaryl, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein phenyl, naphtyl and hetaryl are unsubstituted or carry any combination of 1 to 5 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, d-Ce-haloalkoxy, Ci-C6-alkylthio, d-Ce-haloalkylthio, C-i-Cβ-alkylcarbonyl, d-Cβ-haloalkylcarbonyl, d-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, d-Cβ-alkylamino, di(Ci-C6-alkyl)amino,
C3-C6-cycloalkyl, Cs-Cβ-halocycloalkyl, unsubstituted phenyl and phenyl carrying 1 , 2, 3, 4 or 5 substituent selected from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy;
or the enantiomers, diastereomers or salts thereof.
A particular embodiment of the invention relates to compounds of the formula Il and their salts, except for the compounds of the formula II, wherein R1 is hydrogen, n is 1 , X is S, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R8 and R9 ar hydrogen, W is OH and Ar is selected from phenyl, 2-fluorophenyl, 3-fluorophenyl and 4-fluorophenyl.
The invention further relates to agricultural composition containing at least one compound of formulae I or Il as defined above and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
The invention further relates to a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground, or cultivated plants, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formulae I or II, or a salt thereof, or with a pesticidally effective amount of an agricultural composition as defined above.
The invention further relates to seed, comprising at least one compound of formulae I or Il as defined above and/or an agriculturally acceptable salt thereof.
The invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of formulae I or II, or a veterinally acceptable salt thereof as defined above. The invention further relates to use of a compound of formulae I or II, or a salt thereof as defined above for controlling animal pests.
In the compounds of formulae I and II, the carbon atom which carries the radical Ar creates a center of chirality. Thus, the compounds of formulae I and Il may be present in the form of different enantiomers or if another center of chirality is present, e.g. in any of the radicals R2 to R6, it may exist in the form of diastereomers. In case that A is a radical of the formula A.1 , the compound I may also exist as a cis- or trans-isomer with respect to the N=C axis. The present invention relates to every possible stereoi- somer of the compounds of formulae I and II, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
Salts of the compounds of formulae I and Il are preferably agriculturally 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 formulae I or Il has a ba-sic functionality or by reacting an acidic compound of formulae I or Il 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, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of formulae I or Il 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 of those cations or anions 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 formulae I or Il containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for exam- pie 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-Cm indicates in each case the possible number of carbon atoms in the group.
The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particu- lar fluorine, chlorine or bromine.
Examples of other meanings are:
The term "Ci-Cβ-alkyl" as used herein and in the alkyl moieties of d-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, C-i-Cβ-alkylthio, d-Cβ-alkylcarbonyl,
Ci-Cβ-alkoxycarbonyl, Ci-Cβ-alkylaminocarbonyl and di(Ci-C6-alkyl)aminocarbonyl refers to a saturated straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 3 carbon groups (= Ci-C3-alkyl). Examples for Ci-C3-alkyl are methyl, ethyl, propyl and 1-methylethyl (isopropyl). Examples for Ci-Cβ alkyl further encompass, butyl, 1-methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethylethyl (tert-butyl), 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.
The term "Ci-Cβ-haloalkyl" as used herein and in the haloalkyl moieties of C-i-Cβ-haloalkoxy, C-i-Cβ-haloalkylthio, Ci-Cβ-haloalkylcarbonyl and Ci-Cβ-haloalkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C3-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, di- fluoromethyl, trifluoromethyl, chloro-fluoromethyl, dichlorofluoromethyl, chlorodifluoro- methyl, 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 "Ci-Cβ-alkoxy" as used herein and in the term Ci-Cβ-alkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (= Ci-C3-alkoxy) which is attached via an oxygen atom. Exam- pies for Ci-C3-alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy) and OCH(CH3)2 (isopropoxy). Examples for Ci-Cβ-alkoxy further encompass n-butoxy, OCH(CH3)C2H5 (sec-butoxy), OCH2CH(CHs)2 (isobutoxy), OC(CH3)S (tert-butoxy), n-pentoxy, 1 methyl- butoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, n-hexoxy, 1 methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy,
1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2 trimethylpropoxy, 1-ethyl- 1-methylpropoxy, 1-ethyl-2-methylpropoxy and the like.
The term "Ci-Cβ-haloalkoxy" as used herein and in the term C-i-Cβ-haloalkoxycarbonyl refers to a Ci-C6-alkoxy group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are Ci-C3-haloalkoxy groups, i.e. Ci-C3-alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chloro- difluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 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, pentafluoroeth- oxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3 trichloropropoxy, 2,2,3,3,3-penta- fluoropropoxy, heptafluoropropoxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2- chloroethoxy and 1 (bromomethyl)-2-bromoethoxy. Examples for Ci-Cβ-haloalkoxy fur- ther encompass 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5 bromo-1-pentoxy, 5-iodo-1-pentoxy, 5,5,5-trichloro-1-pentoxy, undecafluoropentoxy, 6-fluoro-1-hexoxy, 6-chloro-1-hexoxy, 6-bromo-1-hexoxy, 6-iodo-1-hexoxy, 6,6,6 trichloro-1-hexoxy and dodecafluorohexoxy. Particularly preferred are chloromethoxy, fluorometh-oxy, difluoromethoxy, trifluoro- methoxy, 2-fluoroethoxy, 2 chloroethoxy and 2,2,2-trifluoroethoxy.
The term "Ci-Cβ-alkylcarbonyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylcarbonyl) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group. Examples for Ci-C4-alkylcarbonyl include C(=O)CH3, C(O)C2H5, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 ,1-dimethylethylcarbonyl. Examples for Ci-Cβ-alkyl- carbonyl further encompass n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methyl- butylcarbonyl, 3-methylbutylcarbonyl, 1 ,1-dimethylpropylcarbonyl, 1 ,2-dimethylpropyl- carbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1-methyl- pentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentyl- carbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethylbutyl- carbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutyl- carbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2 trimethylpropylcarbonyl, 1 ,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1 -ethyl-2-methyl- propylcarbonyl and the like.
The term "Ci-Cβ-alkoxycarbonyl" as used herein refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkoxycarbonyl) attached via the carbon atom of a carbonyl group to the remainder of the molecule (R-O-C(O)-; R = alkyl). Examples for Ci-C4-alkoxycarbonyl include -C(O)OCH3, -C(O)OC2H5, -C(O)O-CH2-C2H5, -C(O)OCH(CHs)2, n-butoxycarbonyl, -C(O)OCH(CHs)-C2H5, -C(O)-OCH2CH(CHs)2 and C(O)OC(CHs)3. Examples for Ci-Cβ-alkoxycarbonyl further encompass 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 "d-Ce-alkylthio "(Ci-C6-alkylsulfanyl: Ci-C6-alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, prefera- bly 1 to 3 carbon atoms (= Ci-C3-alkylthio) which is attached via a sulfur atom. Examples for Ci-C3-alkylthio include methylthio, ethylthio, propylthio and 1 methylethylthio. Examples for C-i-Cβ-alkylthio further encompass butylthio, 1-methylpropylthio, 2-methylpropylthio and 1 ,1-dimethylethylthio. n-pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1 ,1-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1-dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3-dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1 -ethyl-1 -methylpropylthio and 1-ethyl-2-methylpropylthio. The term "Ci-Cβ-haloalkylthio" as used herein refers to a d-Cε-alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are Ci-C3-haloalkylthio groups, i.e. Ci-C3-alkylthio groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethyl- thio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoro- methylthio, 2-fluoroethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 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, pentafluoroethyl- thio, 2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio, 2-chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-fluoroethylthio, 1-(chloromethyl)-2-chloroethylthio or
1-(bromomethyl)-2-bromoethylthio. Examples for C-i-Cε-haloalkylthio further encompass 4-fluorobutylthio, 4-chlorobutylthio, 4 bromobutylthio, nonafluorobutylthio, 5-fluoro- 1-pentylthio, 5-chloro-1-pentylthio, 5 bromo-1-pentylthio, 5-iodo-1-pentylthio, 5,5,5-trichloro-1-pentylthio, undecafluoropentylthio, 6-fluoro-1-hexylthio, 6-chloro- 1-hexylthio, 6-bromo-1-hexylthio, 6-iodo-1-hexylthio, 6,6,6-trichloro-1-hexylthio and dodecafluorohexylthio. Particularly preferred are chloromethyl-thio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2-fluoroethylthio, 2-chloroethylthio and 2,2,2-trifluoroethylthio.
The term "Ci-Cβ-alkylamino" as used herein and in the term Ci-Cβ-alkylaminocarbonyl refers to a secondary amino group carrying one alkyl group as defined above, e.g. me- thylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methyl- propylamino, 2-methylpropylamino, 1 ,1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropyl- amino, 1-ethylpropylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropyl- amino, 1-methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1-dimethylbutylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2-trimethyl- propylamino, 1 ,2,2-trimethylpropylamino, 1-ethyl-1-methylpropylamino or 1 -ethyl-2- methylpropylamino.
The term "di(Ci-C6-alkyl)amino" as used herein and in the term di(Ci-C6-alkylamino- carbonyl refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g. dimethylamino, diethylamino, di-n-propylamino, diiso-propylamino, N-ethyl-N- methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)-N- methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)-N- methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)-N ethylamino, N-(isopropyl)-N- ethylamino, N-(n-butyl)-N-ethylamino, N-(n-pentyl)-N ethylamino, N-(2-butyl)-N- ethylamino, N-(isobutyl)-N-ethylamino and the like.
The term "C2-C6-alkenyl" as used herein and in the alkenyl moieties of
C2-C6-alkenyloxy, C2-C6-alkenylamino and C2-C6-alkenylcarbonyl refers to a straight- chain or branched unsaturated hydrocarbon group having 2 to 6 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-dimethyl-1 -propenyl, 1 ,2-dimethyl-2- propenyl, 1-ethyl-1 -propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1- butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3- dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1- butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3 dimethyl-1 -butenyl, 3,3- dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1 ethyl-3-butenyl, 2-ethyl-1- butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2 trimethyl-2-propenyl, 1 -ethyl-1 - methyl-2-propenyl, 1-ethyl-2-methyl-1 -propenyl and 1-ethyl-2-methyl-2-propenyl.
The term, "C2-C6-alkenyloxy" as used herein refers to a straight-chain or branched alkenyl group having 2 to 6 carbon atoms which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy and the like.
The term "C2-C6-alkynyl" as used herein and in the alkynyl moieties of C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio and C2-C6-alkynylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent- 1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent- 2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1- yl, n-hex-1-yn-3-yl, n-hex-1 yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3 methylpent-1-yn-3-yl, 3-methylpent-1 -yn-4-yl, 3-methylpent-1- yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2 -yn-4-yl or 4-methylpent-2-yn-5-yl and the like. The term, "C2-C6-alkynyloxy" as used herein refers to a straight-chain or branched al- kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, butyn-4-yloxy and the like.
The term "C3-Ci2-cycloalkyl" as used herein refers to a mono- or bi- or polycyclic hydrocarbon radical having 3 to 12 (= C3-Ci2-cycloalkyl), frequently 3 to 8 carbon atoms (= C3-C8-cycloalkyl), in particular 3 to 6 carbon atoms (= Cs-Cβ-cycloalkyl). Examples of monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
Phenyl fused to benzene is naphthyl.
Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl, 2,3-dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like. Examples for phenyl fused to a 5- or 6-membered aromatic heterocyclic ring (= fused to a 5- or 6-membered heteroaromatic ring) are given below.
The term "heteroaryl" ("mono or bicyclic 5- to 10-membered heteroaromatic ring") as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyclic or heterocyclic 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heter- aryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The carbocyclic or heterocyclic fused ring is se- lected from Cs-Cz-cycloalkyl, 5 to 7 membered heterocyclyl and phenyl.
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.
Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring (or for benzene fused to a 5- to 6-membered heteroaromatic ring) are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl. Examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
The term "heterocycle" ("saturated or partially unsaturated heterocycle") comprises nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 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 pyr- rolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxa- zolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4-dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin- 2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.
The term "linear or branched Ci-Cβ-alkanediyl" as used herein and in the term d-Cβ-alkanediyloxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms
(= Ci-C4-alkanediyl), where one of the hydrogen atoms in these groups is replaced by a further bonding position. Examples for linear C-i-Cβ-alkanediyl comprise methyldiyl, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl. Examples for branched d-Cβ-alkanediyl comprise ethyl-1 ,1-diyl, propyl-1 ,1-diyl, butyl- 1 ,1-diyl, 1-methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1-ethylethane-1 ,2 diyl, 1-methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.
The term "animal pests" as used herein includes all invertebrate pests which may harm or damage plants, plant propagation material, or other non-living material. The term "animal pests" as used herein includes in particular arthropods and nematodes. In the sense of the present invention, "animal pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
The term "plant propagation material" as used herein includes all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emer- gence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. The term "cultivated plants" as used herein includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides), for example by glycosylation or polymer additions such as prenylated, acetylated or farne- sylated moieties or PEG moieties (e.g. as disclosed in Biotechnol Prog. 2001 JuI- Aug;17(4):720-8., Protein Eng. Des. SeI. 2004 Jan;17(1 ):57-66, Nat. Protoc. 2007;2(5):1225-35., Curr. Opin. Chem. Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1):1 13- 21 ).
The term "cultivated plants" as used herein further includes plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO
00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
The term "cultivated plants" as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus bacillus, particularly from bacil- lus thuringiensis, such as endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), Cry- IIA(b), CrylllA, CrylllB(bi ) or Cryθc; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for exam- pie Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods insects, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
The term "cultivated plants" as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for exam- pie potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are de- scribed, for example, in the publications mentioned above.
The term "cultivated plants" as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil con- tent or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants. The term "cultivated plants" as used herein further includes plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex- ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
The term "cultivated plants" as used herein further includes plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato). The remarks made below concerning preferred embodiments of the variables of the compounds of formulae I and II, of the features of the use and method according to the invention and of the composition of the invention are valid on their own as well as pref- erably in combination with each other.
The group Ar preferably is phenyl, which carries 1 , 2 or 3 radicals RAr, wherein RAr is as defined above and wherein
RAr preferably is selected from halogen, CN, Ci-Cβ-alkyl, Cs-Cs-cycloalkyl, formyl, C-i-Ce-alkylcarbonyl, -C(=O)OH, d-Ce-alkoxycarbonyl, -C(=O)NH2, Ci-Cβ-alkylaminocarbonyl, di(Ci-C6-alkyl)aminocarbonyl, -OH, Ci-Cβ-alkoxy, -SH, C-i-Cε-alkylthio, -NH2, Ci-Cβ-alkylamino and di(Ci-C6-alkyl)amino, wherein each of the aforementioned radicals, in particular each of the akyl and cycloalkyl moieties in the aforementioned radicals, may carry any combination of 1 , 2 or 3 substitu- ents, independently of one another selected from halogen, CN, NO2, OH, C-i-Cβ- alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, and/or
two radicals RAr bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2 3 or 4 substituents, independently of one another selected from halo- gen, CN, NO2, OH, SH, NH2, COOH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy,
C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy and d-Cβ-alkylthio.
More preferably the radical RAr is selected from halogen, CN, Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, Ci-Cβ-alkoxy and d-Cβ-haloalkoxy.
Likewise preferred are azolin-2-ylamino compounds of formula I, wherein Ar is phenyl, which carries 2 radicals RAr in the 2- and 3-postion, relative to the bonding position, and wherein RAr has one of the meanings given before, in particular one of the preferred or more preferred meanings.
More preferred are azolin-2-ylamino compounds of formula I, wherein Ar is phenyl, which carries 2 radicals RAr selected from halogen, CN, d-Cε-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and Ci-C6-haloalkoxy in the 2- and 3-position, relative to the bonding position of phenyl.
The radical R1 preferably is selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, is unsubsti- tuted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2,
Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and d-Cβ-alkylthio, and wherein C3-C6-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl.
More preferably the radical R1 is selected from hydrogen and Ci-C6-alkyl. Most preferably R1 is hydrogen.
The radicals R2 and R3 preferably are independently of one another selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, Ci-Cβ-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-Ce-alkylamino, di(Ci-C6-alkyl)amino, -SH and d-Ce-alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Ce-haloalkyl.
More preferably R2 and R3 are independently of one another selected from hydrogen, halogen and Ci-C6-alkyl. Most preferably the radicals R2 and R3 are hydrogen.
The number n of -C(R2)(R3)- groups preferably is 1 or 2. More preferably n is 1.
According to one preferred embodiment of the invention the group -[C(R2)(R3)]n- is methylene, i.e. the radicals R2 and R3 both are hydrogen and n is 1. The radical R4 preferably is selected from hydrogen, halogen, d-Cε-alkyl, d-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy, C3-C8-cycloalkyl and Ar5, wherein Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy and Cs-Cs-cycloalkyl are unsubsti- tuted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, -SH, d-Cβ-alkylthio, Ar6, -CH2-Ar6, -O-Ar6 and -S-Ar6, wherein Ar5 and Ar6 have one of the meanings given before, and wherein Cs-Cs-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl.
More preferably the radical R4 is selected from hydrogen, halogen, Ci-Cβ-alkyl and Ar5, wherein Ci-Cβ-alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, inde- pendently of one another selected from halogen, Ci-C6-alkoxy, Ci-C6-haloalkoxy and Ar6, wherein Ar5 and Ar6 have one of the meanings given before.
Most preferably the radical R4 is selected from Ci-Cβ-alkyl and Ar5, wherein Ci-Cβ-alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar6, wherein Ar5 and Ar6 have one of the meanings given before.
The radicals Ar5 and Ar6 if present in the radicals R4, as defined above, are preferably independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and Ci-Cβ-haloalkoxy.
The radicals R5 and R6 preferably are selected independently of one another from hy- drogen, halogen, Ci-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkylnyl, C2-C6-alkynyloxy, Cs-Cs-cycloalkyl and Ar8, wherein Ci-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkylnyl, C2-C6-alkynyloxy and C3-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -OH, d-Cβ-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, d-Ce-alkylamino, di(Ci-C6-alkyl)amino, -SH, d-Ce-alkylthio, Ar9, -CH2-Ar9, -O-Ar9 and -S-Ar9, wherein Ar8 and Ar9 have one of the meanings given before, and wherein C3-Cs-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl.
More preferably R5 and R6 are selected independently of one another from hydrogen, halogen, Ci-Cβ-alkyl and Ar8, wherein Ci-Cβ-alkyl is unsubstituted or carries any com- bination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar9, wherein Ar8 and Ar9 have one of the meanings given before.
The radicals Ar8 and Ar9 if present in the radicals R5 and R6, as defined before, are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, Ci-Cβ-alkoxy and d-Cβ-haloalkoxy.
Most preferably R5 and R6 are selected independently of one another from hydrogen and halogen. Particularly preferred are compounds of formulae I or Il wherein R5 and R6 both are hydrogen.
One particular embodiment of the invention relates to compounds of formulae I or II, wherein X is sulfur.
Another particular embodiment of the invention relates to compounds of formulae I or II, wherein X is oxygen.
In this particular embodiment wherein X in formula I is oxygen, preferably one of the radicals R4, R5 and R6 is different from hydrogen and d-Cβ-alkyl, if Ar is phenyl, that is unsubstituted or carries 1 , 2, 3 4 or 5 radicals RAr.
Another particular embodiment of the invention relates to compounds of formulae I or Il wherein X is N(R10).
Preferably X is O or S. More preferably X is S.
The radicals R7a, R7b, R7c, R7d preferably are independently of one another selected from hydrogen, halogen, d-Cβ-alkyl and d-Cβ-haloalkyl. More preferably the radicals R7a, R7b, R7c and R7d are hydrogen.
The radicals R8, R9, R10 preferably are selected independently of one another from hy- drogen, CN, NO2, d-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C8-cycloalkyl, wherein d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2 or 3 or substituents, independently of one another selected from halogen, CN, NO2, -OH, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Ce-haloalkoxy, -SH, d-Ce-alkylthio, d-Ce-haloalkylthio, -C(=O)H, Ci-Cβ-alkylcarbonyl, Ci-C6-haloalkylcarbonyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S, N as ring members, -Ar4 or -CH2-Ar4, wherein Ar4 has one of the meanings given before, and wherein Cs-Cs-cycloalkyl additionally may carry any combination of 1 , 2 or 3 or substituents, independently of one another selected from Ci-Cβ-alkyl, d-Cβ-haloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, and
likewise preferred R8, R9, R10 may further be selected from -B-C(=O)Ra, -B-C(=O)ORb, -B-C(=O)SRe, -B-C(=S)ORb, -B-C(=S)NRcRd, -B-C(=S)SRe, -B-ORb, -B-SRe, -S(=O)Re, B-NRcRd, -S(=O)2Re and -S(=O)2ORb, wherein
B is a single bond or -CH2-, and wherein Ra, Rb, Rc, Rd and Re independently of one another have one of the meanings given before.
More preferably the radicals R8, R9 and R10 are independently of one another selected from hydrogen, CN, d-Ce-alkyl, -C(=O)Ra, -C(=O)ORb, -ORb and -B-NRcRd, wherein Ra, Rb Rc and Rd are selected independently of one another from hydrogen, C-i-Cε-alkyl and phenyl, wherein Ci-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C6-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy. Most pref- erably the radicals R8, R9 and R10 are hydrogen.
The radicals Ra, Ra', Rb, Rc, Rd, Re, Rf, Rs and Rh preferably are selected each independently of one another from hydrogen, Ci-Cβ-alkyl and phenyl, wherein Ci-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, independ- ently of one another selected from halogen, CN, NO2, OH, Ci-C6-alkoxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, Ci-C6-alkoxy and d-Cβ-haloalkoxy.
The radicals Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10 and Ar11 are preferably independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy.
The compounds of formula Il can be converted into compounds of formula I by means of a chemical reaction. Thus, the definitions given hereinbefore for Ar, RAr, R1, R2, R3, R4, R5, R6, X, R7a, R7b, R7c, R7d, R8, R9, R10, B, Ra, Ra', Rb, Rc, Rd, Re, Rf, Rs, Rh, Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10 and Ar11 apply for compounds of formula I as well as for the compounds of formula II. In both cases the remarks made hereinbefore concerning preferred meanings of those variables are valid on their own as well as preferably in combination with each other. For the compounds of formula Il the remarks made hereinbefore concerning preferred meanings of those variables are further pref- erably valid in combination with the preferred meanings given for the radicals R11, R1, Ar12 or Ar13.
One specific embodiment relates to compounds of formula (II) wherein W a group - OR11.
The radical R1, if present in the radical R11, preferably is selected from hydrogen, d-Cβ-alkyl, and Ar12, wherein d-Cε-alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, C-i-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar13, wherein Ar12 and Ar13 have one of the meanings given before.
The radicals Ar12 and Ar13, if present in the radical R1, are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl and d-Cβ-haloalkoxy.
The radical R11 preferably is selected from hydrogen and -C(=O)-R', wherein
R1 is selected from hydrogen, d-Cβ-alkyl, and Ar12, wherein d-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar13, wherein
Ar12 and Ar13 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl and Ci-Cβ-haloalkoxy.
More preferably the radical R11 is selected from hydrogen and d-Cβ-alkylcarbonyl.
One specific embodiment of the invention relates to azolin-2-ylamino compounds of formula I, wherein
n is 1 or 2, preferably 1 ;
Ar is phenyl, which carries 1 , 2 or 3 radicals RAr, wherein
RAr is selected from halogen, CN, d-Cβ-alkyl, Cs-Cs-cycloalkyl, formyl, d-Ce-alkylcarbonyl, -C(=O)OH, d-Ce-alkoxycarbonyl, -C(=O)NH2, d-Cβ-alkylaminocarbonyl, di(d-C6-alkyl)aminocarbonyl, -OH, d-Ce-alkoxy, -SH, d-C6-alkylthio, -NH2, d-Ce-alkylamino and di(Ci-C6-alkyl)amino, wherein each carbon atom of the aforementioned radicals, in particular each of the alkyl or alkoxy moieties in the aforementioned radicals, is unsubstituted or may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, and/or
two radicals RAr bound to adjacent carbon atoms of the phenyl or naphtyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C-i-Cβ-haloalkoxy and d-Cβ-alkylthio; and wherein
RAr is preferably selected from halogen, CN, Ci-Cβ-alkyl, d-Cβ-haloalkyl, C-i-Cβ-alkoxy and d-Cβ-haloalkoxy; and wherein RAr is likewise preferably located in the 2- and 3-position, relative to the bonding position, relative to the bonding position of phenyl;
A is a radical of the formulae A1 or A2 as defined herein , wherein
X is S, O or N(R10), preferably S or O, in particular S;
R7a, R7b, R7c and R7d are independently of one another selected from hydrogen, halogen, Ci-Cβ-alkyl and d-Cβ-haloalkyl, in particular hydrogen;
R8, R9 and R10 are independently of one another selected from hydrogen, CN, d-Ce-alkyl, -C(=O)Ra, -C(=O)ORb and -0Rb, wherein Ra and Rb are se- lected independently of one another from hydrogen, Ci-Cβ-alkyl and phenyl, wherein Ci-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkoxy, Ci-Ce-haloalkoxy and d-Ce-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C6-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy; in particular R8, R9 and R10 are hydrogen;
R1 is selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-Cβ-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-C6-alkylamino, di(Ci-C6-alkyl)amino, -SH and Ci-Cβ- alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substitu- ents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-
Cβ-alkynyl and Ci-C6-haloalkyl; and wherein
R1 is preferably selected from hydrogen and Ci-Cβ-alkyl and more preferably is hydrogen;
R2 and R3 are selected independently of one another from hydrogen, Ci-Cβ-alkyl,
C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of d-Cε-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-Cβ-alkoxy, Ci-Cβ- haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-C6-alkylamino, di(Ci-C6- alkyl)amino, -SH and Ci-C6-alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci- Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cβ-haloalkyl; and wherein
R2 and R3 are preferably selected from hydrogen and Ci-Cβ-alkyl and more preferably are hydrogen;
R4 is selected from hydrogen, halogen, Ci-Cβ-alkyl and Ar5, wherein Ci-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkoxy, Ci-Cβ-haloalkoxy and Ar6, wherein
Ar5 and Ar6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, Ci-Cβ-haloalkyl, C-i-Cβ-alkoxy and d-Cβ-haloalkoxy; and
R5 and R6 are selected each independently of one another from hydrogen, halogen,
Ci-Cβ-alkyl and Ar8, wherein Ci-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar9, wherein
Ar8 and Ar9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 sub- stituents, independently of one another selected from halogen, d-Cε-alkyl, C-i-Cε-haloalkyl, Ci-Cβ-alkoxy and d-Cβ-haloalkoxy; and wherein
R5 and R6 preferably are hydrogen or halogen and most preferably hydrogen;
or the enantiomers, diastereomers or salts thereof.
Another specific embodiment of the invention relates to compounds of formula II, wherein
n is 1 or 2, preferably 1 ;
Ar is phenyl, which carries 1 , 2 or 3 radicals RAr, wherein
RAr is selected from halogen, CN, Ci-Cβ-alkyl, Cs-Cs-cycloalkyl, formyl, d-Ce-alkylcarbonyl, -C(=O)OH, d-Ce-alkoxycarbonyl, -C(=O)NH2, d-Cβ-alkylaminocarbonyl, di(d-C6-alkyl)aminocarbonyl, -OH, d-Ce-alkoxy, -SH, d-C6-alkylthio, -NH2, d-Ce-alkylamino and di(d-C6-alkyl)amino, wherein each carbon atom of the aforementioned radicals, in particular each of the alkyl or alkoxy moieties in the aforementioned radicals, is unsubstituted or may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, and/or
two radicals RAr bound to adjacent carbon atoms of the phenyl or naphtyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, d-Ce-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio; and wherein
RAr is preferably selected from halogen, CN, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy; and wherein RAr is likewise preferably located in the 2- and 3-position, relative to the bonding position, relative to the bonding position of phenyl; A is a radical of the formulae A3 as defined herein, wherein
X is S, O or N(R10), preferably S or O;
R7a, R7b, R7c and R7d are independently of one another selected from hydrogen, halogen, Ci-Cβ-alkyl and d-Cβ-haloalkyl, in particular hydrogen;
R8, R9 and R10 are independently of one another selected from hydrogen, CN, d-Ce-alkyl, -C(=O)Ra, -C(=O)ORb and -0Rb, wherein Ra and Rb are se- lected independently of one another from hydrogen, Ci-Cβ-alkyl and phenyl, wherein Ci-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkoxy, Ci-C6-haloalkoxy and Ci-C6-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl,
C-i-Cβ-alkoxy and d-Cβ-haloalkoxy; in particular R8, R9 and R10 are hydrogen;
R1 is selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2- Cβ-alkynyloxy, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and C-i-Cβ- alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2- Cβ-alkynyl and d-Cβ-haloalkyl; and wherein
R1 is preferably selected from hydrogen and Ci-Cβ-alkyl, and more preferably is hydrogen;
R2 and R3 are selected independently of one another from hydrogen, Ci-Cβ-alkyl,
C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals, in particular each of the radicals selected from the group consisting of Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, C1-C6- haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-C6-alkylamino, di(Ci-C6- alkyl)amino, -SH and Ci-C6-alkylthio, and wherein
C3-C6-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independ- ently of one another from d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C-i-Cε-haloalkyl; and wherein
R2 and R3 are preferably selected from hydrogen and d-Cβ-alkyl, and more pref- erably are hydrogen;
R4 is selected from hydrogen, halogen, d-Cβ-alkyl and Ar5, wherein d-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, Ci-C6-haloalkoxy and Ar6, wherein
Ar5 and Ar6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkyl, C-i-Cε-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy;
R5 and R6 are selected each independently of one another from hydrogen, halogen, d-Cβ-alkyl and Ar8, wherein d-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar9, wherein
Ar8 and Ar9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy; and wherein
R5 and R6 preferably are hydrogen or halogen and most preferably hydrogen; and
W is selected from halogen and -OR11 and preferably is -OR11, wherein
R11 is selected from hydrogen and -C(=O)-R', wherein
R1 is selected from hydrogen, d-Cβ-alkyl, and Ar12, wherein d-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independ- ently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar13, wherein
Ar12 and Ar13 are independently of one another selected from phenyl and pyridyl, wherein phenyl and pyridyl are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl and d-Cβ-haloalkoxy; and wherein R11 preferably is selected from hydrogen and Ci-Cβ-alkylcarbonyl;
or the enantiomers, diastereomers or salts thereof.
In the particular embodiment of the compounds of the formula II, wherein X in formula I is sulfur, preferably one of the radicals R4, R5 and R6 is different from hydrogen and Ci- Cβ-alkyl, if Ar is phenyl, that is unsubstituted or carries 1 , 2, 3 4 or 5 radicals RAr.
Examples of particularly preferred compounds of the general formulae I and Il are the compounds compiled in Tables A to H below. Moreover, the meanings mentioned for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table A: Examples of preferred compounds of formula I are the compounds of formula I.A.1 , I.A.2, I.A.3 and I.A.4,
Figure imgf000033_0001
wherein R4, R5 and R6 have the meanings corresponding to one line of the following table 1 (compounds I .A.1 .1 to I .A.1 .1430, I .A.2.1 to I .A.2.1430, I .A.3.1 to I.A.3.1430 and I .A.4.1 to I .A.4.1430).
Table 1
Figure imgf000033_0002
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0003
Table B: Examples of preferred compounds of formula I are the compounds of formula I.B.1 , I.B.2, I.B.3 and I.B.4,
Figure imgf000067_0001
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds I.B.1.1 to I.B.1.1430, I.B.2.1 to I.B.2.1430, I.B.3.1 to I.B.3.1430 and I.B.4.1 to I.B.4.1430).
Table C: Examples of preferred compounds of formula Il are the compounds of formula II. a and II. b,
Figure imgf000067_0002
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.a.1 to ll.a.1430 and ll.b.1 to ll.b.1430).
Table D: Examples of preferred compounds of formula Il are the compounds of formula
Figure imgf000068_0001
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.c.1 to II.C.1430 and ll.d.1 to ll.d.1430).
Table E: Examples of preferred compounds of formula Il are the compounds of formula ll.e and ll.f,
Figure imgf000068_0002
.f)
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.e.1 to ll.e.1430 and ll.f.1 to ll.f.1430).
Table F Examples of preferred compounds of formula Il are the compounds of formula ll.g and ll.h,
Figure imgf000069_0001
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.g.1 to ll.g.1430 and ll.h.1 to ll.h.1430).
Table G: Examples of preferred compounds of formula Il are the compounds of formula
Figure imgf000069_0002
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.i.1 to ll.i.1430 and ll.k.1 to ll.k.1430).
Table H: Examples of preferred compounds of formula Il are the compounds of formula
Figure imgf000069_0003
wherein R4, R5 and R6 have the meanings corresponding to one line of table 1 (compounds ll.m.1 to ll.m.1430 and ll.n.1 to ll.n.1430). The compounds of formulae I and Il can be obtained for example by the methods outlined in schemes 1 to 9.
Compounds of the formula I wherein R8 and R9 both have a meaning different from hydrogen, can be obtained as outlined in scheme 1.
Scheme 1 :
Figure imgf000070_0001
In scheme 1 , n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R8, R9 and Ar have one of the meanings given above. A compound of formula I wherein R8 or R9 is hydrogen is treated with a suitable electrophile. Suitable electrophiles are e.g. alkylating or acylat- ing agents R89-LG (LG = leaving group) as described e.g. in WO 2005063724.
The compounds of the formula I wherein X is oxygen or sulfur can be prepared e.g. from the corresponding aminothiocarbonylaminoethanol compounds of formula II. a or from aminocarbonylaminoethanol compounds of formula II. b, respectively, as depicted in scheme 2.
Scheme 2:
Figure imgf000070_0002
(!!'bj- χ = o (I) wherein R9 is H
In scheme 2, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d and Ar are as defined above. The aminothiocarbonylaminoethanol compound II. a and the aminocarbonylaminoetha- nol compound ll.b, respectively, can be cyclized by conventional means thereby obtaining an azoline compound of the formula I. Cyclization of the compounds II. a and ll.b, respectively, can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters 1999, 40, 3125-3128) or as described in the preparation example 18.
Compounds of the formula 11. a and ll.b, respectively, can be prepared as depicted in schemes 3 and 4 below.
Scheme 3:
Figure imgf000071_0001
(III) or a salt thereof (IV)
Figure imgf000071_0002
In scheme 3, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d and Ar are as defined above. An amine III or a salt thereof is converted to the corresponding iso(thio)cyanate IV by conventional means, e.g. by reacting III with (thio)phosgene, as described for example in the case of thiophosgene in Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter Nc, pp. 837-842, Georg Thieme Verlag 1983. It may be advantageous to carry out the reaction in the presence of a base. The iso(thio)cyanate IV is then reacted with an aminoethanol V to form an amino(thio)carbonylaminoethanol compound. The reaction of the aminoethanol V with iso(thio)cyanate IV can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Biochem. 56 (7), 1062-65 (1992).
A further route to compounds II, wherein X is S is shown in scheme 4. Scheme 4:
Figure imgf000072_0001
(III) or a salt thereof (ILa)'
Figure imgf000072_0002
(ILa)
In scheme 4, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R' and Ar are as defined above.
An aminoalkenyl compound III or a salt thereof can be converted to the corresponding aminothiocarbonylaminoethanol compound ILa, by reaction of the compound III with an isothiocyanate Vl and subsequent saponification as described in the preparation examples 1 and 2. Suitable isothiocyanates can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117.
Aminoalkenyl compounds of formula III are known in the art or can be prepared by methods familiar to an organic chemist, for instance by application of general methods for the synthesis of amines and alkenes and as depicted e.g. in scheme 5 or shown in the preparation examples 1 and 38 to 40. Suitable salts of aminoalkenyl compounds III are e.g. the acid addition salts formed by treating a compound of formula III with an inorganic or organic acid. Anions of useful acids are e.g. sulfate, hydrogensulfate, phosphate, dihydrogenphosphate, hydrogenphosphate, nitrate, bicarbonate, carbonate, chloride, bromide, p-toluene sulfonate, and the anions of Ci-C4-alkanoic acids such as acetate, propionate, and the like.
Scheme 5:
Figure imgf000073_0001
of
In scheme 5, n, R1, R2, R3, R4, R5, R6 and Ar are as defined above and Z is for example SiMe3 or S(=O)-tert-butyl and X is a halogen.
The addition of magnesium halides VIII to appropriate imines VII followed by aqueous work up or acidic treatment can provide amines III as described in J. Org. Chem. 1983, 48, 289-294 or Tetrahedron 1999, 55, 8883-8904 or in the preparation example 39.
Compounds of formula III wherein R4 is halogen can be obtained from the corresponding alkynes as outlined in J. Org. Chem. 2000, 65, 7475-7478 or in the preparation example 40. The alkyne themselves can be introduced by addition of appropriate nucleo- philes (see e.g. J. Org. Chem. 1989, 54, 5198-5198) to suitable imines (cf. preparation example 40).
Compounds of formula III wherein R4 and/or R5 and/or R6 are halogen can be used for further derivatisation of the alkene unit by cross coupling reactions such as Suzuki for example like in J. Org. Chem. 2000, 65, 7475-7478 or Ace. Chem. Res. 2007, 40, 275- 286 or the preparation example 38.2.
The alkene unit of the aminoalkenyl compounds III can also be prepared from carbonyl groups for example by reacting those carbonyl functions with carbon tetrabromide in the presence of triphenylphosphine according to the Corey-Fuchs method (cf. preparation example 41 ). The carbonyls can be obtained for example by oxidation of the corre- sponding alcohols for example as described in J. Med. Chem. 2003, 46, 3539. The alcohols are known in the art or can in general be prepared by methods familiar to an organic chemist and well known in the art for e.g. in Tetrahedron Letters 2004, 45,1503.
Alternatively, the compounds of the formula I according to the invention wherein X is O or S can be prepared by the method shown in scheme 6.
Scheme 6:
Figure imgf000074_0001
(III) or a salt thereof (I) wherein R9 is H
In scheme 6, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d and Ar are as defined above.
An amine of formula III or a salt thereof can be converted to an azoline of formula I by reaction with a 2-chloroethylisothiocyanate or a 2-chloroethylisocyanate of formula IX e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22 and subsequent cycli- zation in the presence or absence of base. 1-Chloro-2-isothiocyanatoethane (CAS- reg.-no.: 6099-88-3) and 2-chloro-ethyl-isocyanate (CAS-reg.-no.: 1943-83-5) are commercially available.
Compounds of the formula I according to the invention wherein X is S may be prepared by the method shown in scheme 7.
Scheme 7:
Figure imgf000074_0002
(III) or a salt thereof (I) wherein R9 is H and X is S
In scheme 7, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R9 and Ar are as defined above and LG is a leaving group.
Compounds of the formula I may be obtained by reacting an amine III or a salt thereof with a 2-substituted thiazoline of formula X, for example 2-(p-tolyloxy)-2-thiazoline, as shown in preparation example 19.
Compounds of the formula I wherein X is NR10 may be prepared by the method shown in scheme 8. Scheme 8:
Figure imgf000075_0001
(III) or a salt thereof (I), wherein
R9 = H and X = NR10
In scheme 8, n, R1, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R9, R10 and Ar are as defined above and LG is a leaving group.
Compounds of the formula I may be obtained by reacting an appropriate substituted amine III or a salt thereof with a 2-substituted imidazoline Xl in an appropriate solvent. This reaction can be carried out, for example by analogy to the methods described in US 5,130,441 or EP 0389765.
Alternatively, the compounds of formula I, wherein X is oxygen or sulfur and R1 is hydrogen, can also be prepared starting from amines XII via aminothiazolines or ami- nooxazolines XIII, as outlined in scheme 9. A further conversion with an alkylating or acylating reagent R89-LG can provide derivatised aminothiazolines or aminooxazolines XIV and/or XV. Those can be subsequently alkylated with electrophiles of formula XVI , optionally followed by hydrolysis, as outlined in scheme 9 and in the preparation example 20.
Scheme 9:
Figure imgf000075_0002
(IX) wherein (XIII) X = S or O
Figure imgf000076_0001
(XV)
In scheme 9, n, R2, R3, R4, R5, R6, R7a, R7b, R7c, R7d, R8, R9 and Ar are as defined above and LG and LG' are leaving groups, such as halogen.
As a further alternative, the radicals R4, R5 and R6 bound to the ethylenically unsaturated part of azoline compounds of formula I can be exchanged, for example by Heck reactions (see e.g. Synthesis 2002, 315-316 or Tetrahedron Lett. 2002, 43, 3401-3405 or the preparation example 21 ), to give further azoline compounds of formula I.
As a rule, the compounds of formulae I and Il can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds of formulae I and Il or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formulae I and Il can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, metal catalyzed coupling reactions, oxidation and the like.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colourless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
Due to their excellent activity, the compounds of formulae I and Il may be used for controlling animal pests. Accordingly, the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the mate- rials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or Il or a salt thereof or a composition as defined above.
Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the formula I or Il or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricul- tural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
In the sense of the present invention, "animal pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
The invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of formula I or Il or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may contain a single active compound of formula I or Il or a salt thereof or a mixture of several active compounds of formulae I or Il or their salts according to the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautom- ers or mixtures of tautomers.
The compounds of the formulae I and Il and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes. Animal pests controlled by the compounds of formulae I and Il include for example:
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, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destruc- tor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa; thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;
hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, NiIa- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furcifera Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata 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 kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
Siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
The compositions and compounds of formula I are useful for the control of nematodes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Het- erodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, 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 nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; AwI nema- todes, 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 Longidorus species; Pin nematodes, Paratylen- chus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other 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 species.
In a preferred embodiment of the invention the compounds of formula I are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina. The com- pounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
The compounds of formulae I and Il or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pes- ticidally effective amount of compounds of formula I. The term "crop" refers both to growing and harvested crops.
The compounds of formulae I and Il can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and
Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publish- ers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
Suitable emulsifiers are non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose. Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sul- fonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, poly- oxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide conden- sates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emul- sions, 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, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
A suitable preservative is e.g. dichlorophen.
Seed treatment formulations may additionally comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers, EO/PO surfactants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , 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.
Examples of a gelling agent is carrageen (Satiagel®).
Powders, materials for spreading and dustable products 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 compounds 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 compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
The compounds of formula I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example 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; they are intended to ensure in each case the finest possible distribution of the active compound(s) 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. However, it is also 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 compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
The active compound(s) 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 compound, or even to apply the active compound without additives.
The following are examples of formulations:
1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A) Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.
B) Dispersible concentrates (DC)
20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xy- lene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active com- pound(s), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addi- tion of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
I) Dustable powders (DP, DS) 5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)
J) Granules (GR, FG, GG, MG)
0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound^) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV solutions (UL)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.
The compounds of formula I are also suitable for the treatment of plant propagation materials (such as seed). Conventional seed treatment formulations include for exam- pie flowable concentrates FS, solutions LS, powders for dry treatment DS, water dis- persible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Other preferred FS formulations of compounds of formulae I or Il for seed treatment comprise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1. The compounds of formulae I and Il are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, com- pounds of formulae I and Il 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 formulae I or Il as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 2500C, dimethylformamide, N-methylpyrrolidone, dimethyl sulphoxide, 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 formulae I or Il and their 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 sys- terns.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formulae I or Il and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, non- wovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyre- throid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)- enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and diethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the active compounds of formulae I or Il or spray- ing them onto the nets.
Methods which can be employed for treating the plant propagation material, in particular seedm are, in principle, all suitable seed treatment and especially seed dressing techniques known in the art, such as seed coating (e.g. seed pelleting), seed dusting and seed imbibition (e.g. seed soaking). Here, "seed treatment" refers to all methods that bring plant propagation material, in particular seeds, and the compounds of formulae I or II, or a salt therof, into contact with each other, and "seed dressing" to methods of seed treatment which provide the plant propagation material, in particular the seeds with an amount of the compounds of formulae I or II, i.e. which generate a plant propa- gation material, in particular a seed comprising the compound of formulae I or II. In principle, the treatment can be applied to the plant propagation material, in particular to the seed at any time from the harvest of the plant propagation material, in particular of the seed to the sowing of the seed. The plant propagation material, in particular the seed can be treated immediately before, or during, the planting of the plant propagation material, in particular of the seed, for example using the "planter's box" method. However, the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
Expediently, the treatment is applied to unsown plant propagation material, in particular unsown seed. As used herein, the term "unsown seed" is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Specifically, a procedure is followed in the treatment in which the plant propagation material, in particular the seed is mixed, in a suitable device, for example a mixing de- vice for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If ap-propriate, this is followed by a drying step.
The compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
A further object of the present invention is therefore to provide new methods for controlling parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions containing a parasiticidally effective amount of compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
The present invention also provides a non-therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of for- mulae I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises including a parasiticidally effective amount of a compound of formula I or Il or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
The invention relates further to the use of compounds of formula I for treating, controlling, preventing or protecting animals against infestation or infection by parasites. The invention relates also to the use of a compound of the formulae I or II, or a composition comprising it, for the manufacture of a medicament for the therapeutic treatment of animals against infections or infestions by parasites.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, nonemetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly, it has been found that compounds of formulae I or Il are suitable for combating endo- and ectoparasites in and on animals.
Compounds of formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling 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 formulae I or Il or the enantiomers or veterinarily acceptable salts thereof 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 formulae I or Il or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non- systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of formulae I or Il are especially useful for combating ectoparasites.
The compounds of formulae I or Il are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha 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, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intes- tinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Lep- toconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar- gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sar- cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus 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, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae, actinedida (Prostigmata) and 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., Trichodectes spp., and Felicola spp,
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) 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., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris 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 Hab- ronema spp., Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus 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 formulae I or Il and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of compounds of formulae I or Il and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formulae I or Il and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formulae I or Il and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formulae I or Il and of the compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of formulae I or Il also are especially useful for combating endopara- sites (roundworms nematoda, thorny headed worms and planarians).
The compounds of formula I can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits).
The present invention relates to the therapeutic and the non-therapeutic use of compounds of formula I for controlling and/or combating parasites in and/or on animals.
The compounds of formula I may be used to protect the animals from attack or infestation by parasites by contacting them with a parasitically effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the parasite, e.g. also at it's locus, and optionally also administrating the compounds/composition directly on the animal) and indirect contact (applying the compounds/compositions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of formula I.
"Locus" as defined above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal. The compounds of the invention can also be applied preventively to places at which occurrence of the pests or parasites is expected.
The administration to the animal 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 compounds of formulae I and Il may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addi-tion, the compounds of formulae I 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 compounds of formeulae I and II, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of formulae I or Il may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formulae I or Il may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formulae I or Il may be formulated into an implant for subcutaneous administration. In addition the compounds of formulae I or Il 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 compounds of formulae I or II.
The compounds of formulae I or Il 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 applica-tion, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of formulae I or II. In addition, the compounds of formulae I or Il 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, tab- lets, 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- methylpyrrolidone, 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, polyvinyl 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 according 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, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, 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-promoting substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene 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 methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N methylpyrroli- done, 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, viscosity-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, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do 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 C16-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-octyl- dodecanol, 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 monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; 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 substances, 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.
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 compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compounds of formulae I or II.
Generally, it is favorable to apply the compounds of formulae I or Il 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 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
Furthermore, the preparations comprise the compounds of formulae I or Il against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formulae I or Il 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 formulae I or Il 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 compounds of formulae I or II. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
Compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
These agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds of formulae I or Il or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
The following list M of pesticides together with which the compounds according to the invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation:
M.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicro- tophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phor- ate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirim- fos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamido- thion;
M.2. Carbamates: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxy- carboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, pro- poxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
M.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flu- cythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, teflu- thrin, tetramethrin, tralomethrin, transfluthrin;
M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, car- tap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thio- cyclam, thiosultap-sodium and AKD1022.
M.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole
M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
M.9. METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
M.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
M.13. Synergists: piperonyl butoxide, tribufos;
M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone; M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;
M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;
M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;
M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, te- flubenzuron, triflumuron;
M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
M.20. Octapaminergic agonsits: amitraz;
M.21. Ryanodine receptor modulators: flubendiamide, (R)-, (S)- 3- Chlor-N1-{2-methyl- 4-[1 ,2,2,2 - tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2- methylsulfonylethyl)phthalamid (M21.1 );
M.22. Various: aluminium phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor , 4-But-2-ynyloxy-6-(3,5-dimethyl- piperidin-1-yl)-2-fluoro-pyrimidine (M22.1 ), 3-Benzoylamino-N-[2,6-dimethyl-4-(1 , 2,2,2- tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide (M22.2), 4-[5-(3,5- Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2- ylmethyl-benzamide (M22.3),4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoro-ethyl)-benzamide (M22.4),4-[5-(3,5-Dichloro- phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-thiazol-2-ylmethyl- benzamide (M22.5), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3- yl]-2-methyl-N-(tetrahydro-furan-2-ylmethyl)-benzamide (M22.6), 4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.7), 4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on(M22.8), 4-{[(2-Chloro1 ,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.9), 4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.10), 4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on(M22.11 ), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on(M22.12), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on(M22.13), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on(M22.14), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on(M22.15), 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on(M22.16), Cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2- cyclopropylacetyl)oxy]methyl]-1 ,3,4 ,4a, 5,6,6a, 12, 12a, 12b-decahydro-12-hydroxy- 4,6a,12b-trimethyl-1 1-oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1-b]pyrano[3,4-e]pyran- 3,6-diyl] ester(M22.17), 8-(2-Cyclopropylmethoxy-4-methyl-phenoxy)-3-(6-methyl-pyridazin-3-yl)-3-aza- bicyclo[3.2.1]octane(M22.18),
M.23. N-R'-2,2-dihalo-1-R"cyclo-propanecarboxamide-2-(2,6-dichloro-α ,α ,α -trifluoro- p-tolyl)hydrazone or N-R'-2,2-di(R'")propionamide-2-(2,6-dichloro-α ,α ,α -trifluoro-p- tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl;
M.24. Anthranilamides: chloranthraniliprole,cyantraniliprole,
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 - cyclopropyl-ethylcarbamoyO-θ-methyl-phenylJ-amide (M24.1 ),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1 - cyclopropyl-ethylcarbamoyO-phenylJ-amide (M24.2),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6-
(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M24.3), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6-
(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M24.4),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1 - cyclopropyl-ethylcarbamoyO-phenyO-amide (M24.5),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2-(1 - cyclopropyl-ethylcarbamoyO-θ-methyl-phenylJ-amide (M24.6),
M.25. Malononitrile compounds: CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF3, (2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoro-propyl)malononitrile), CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF2CF3 (2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2- (3,3,4,4,4-pentafluorobutyl)-malonodinitrile);
M.26. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
The commercially available compounds of the group M may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.
Thioamides of formula M6.1 and their preparation have been described in WO 98/28279. Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Benclothiaz and its preparation have been described in EP-A1 454621. Methi- dathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Acetoprole and its preparation have been described in WO 98/28277. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its preparation have been described in US 6300348. Chloranthraniliprole has been described in WO 01/70671 , WO 03/015519 and WO 05/118552. Anthranilamide derivatives of formula M24.1 have been described in WO 01/70671 , WO 04/067528 and WO 05/1 18552. Cyantraniliprole has been described in WO 01/70671 , WO 04/067528 and WO 05/118552.The anthranilamides M 24.1 to M 24.6 have been described in WO 2008/72743 and WO 200872783. The phthalamide M 21.1 is known from WO 2007/101540. Cyflumetofen and its preparation have been described in WO
04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932. Sulfoximine sulfoxaflor has been described in WO 2006/060029 and WO 2007/149134. The alkynylether compound M22.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 2007060839. The carboxamide compound M 22.2 is known from WO 2007/83394. The oxazoline compounds M 22.3 to M 22.6 have been described in WO 2007/074789. The furanon compounds M 22.7 to M 22.16 have been described eg. in WO 2007/1 15644. The pyripyropene derivative M 22.17 has been described in WO 2008/66153 and WO 2008/108491. The pyridazin compound M 22.18 has been described in JP 2008/1 15155. The malononitrile compounds have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.
Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol, dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin, dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, pro- pineb, polycarbamate, thiram, ziram, zineb, heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fube- ridazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, pro- quinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thio- phanate-methyl, tiadinil, tricyclazole, triforine, copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate, nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl, phenylpyrroles such as fenpiclonil or fludioxonil, sulfur, other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifen- phos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamid, strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, me- tominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnemamides and analogs such as dimethomorph, flumetover or flumorph.
The animal pest, i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) of formulae I or Il or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions di- rectly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formulae I or II. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
"Locus" means a habitat, breeding ground, cultivated plants, plant propagation material (such as 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 ef- fective 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 formulae I and Il and their compositions can be used for protecting wooden materials such as 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 the formulae I or Il 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, plywood, 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.
The compounds of formulae I and Il can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formulae I and Il 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 formulae I or II. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and/or insecticide. For use in bait compositions, the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
In the treatment of seed, the application rates of the active ingredients are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
The present invention is now illustrated in further detail by the following examples.
A) Preparation Examples
The compounds of formulae I and Il were characterized by coupled High Performance Liquid Chromatography / mass spectroscopy (HPLC/MS), by NMR or by their melting points. HPLC: 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. MS: Quadrupol electrospray ionisation, 80 V (positive modus).
A.1 ) Preparation of compounds of formula 11
Example 1 : Preparation of acetic acid 2-{3-[1-(2,3-dimethylphenyl)-3-phenylbut-3-enyl]- thioureido}ethyl ester
A solution of 1-(2,3-dimethylphenyl)-3-phenylbut-3-enylamine (256 mg,
1.00 mmol, 1 eq, cf. example 38.3) and acetic acid 2-isothiocyanatoethylester (165 mg, 1.14 mmol, 1.1 eq, prepared according to Collect. Czech. Chem. Com- mun. 1986, 51 , 1 12) in toluene (30 ml) was stirred at 60 0C for 5 h. The obtained reaction mixture was concentrated in vacuo and the residue was purified by column chromatography to yield acetic acid 2-{3-[1-(2,3-dimethyl-phenyl)-3- phenylbut-3-enyl]thioureido}ethyl ester.
Example 2: Preparation of 1-[1-(2,3-dimethylphenyl)-3-phenylbut-3-enyl]-3-(2-hydroxy- ethyl)thiourea A mixture of acetic acid 2-{3-[1-(2,3-dimethylphenyl)-3-phenylbut-3-enyl]- thioureido}ethyl ester (142 mg, 0.36 mmol, 1 eq, cf. example 1 ), lithium hydroxide monohydrate (34 mg, 0.80 mmol, 2.3 eq) in water (0.5 ml) and tetrahydrofuran (4.3 ml) was stirred for 22 h. Water (5 ml) was then added and the obtained mixture was extracted with dichloromethane (3 x 5 ml_). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo to yield 1-[1-(2,3-Dimethylphenyl)-3-phenylbut-3-enyl]-3-(2-hydroxyethyl)thiourea.
Urea compounds (i. e. compounds of formula II, wherein X is O) can be prepared by anology to the method outlined in preparation example 1 by using isocyanato compounds instead of isothiocyanato compounds.
The les 3 to 17)
Figure imgf000108_0001
wherein n, Ar, R4, R5, R6 and R11 independently from one another have one of the meanings given in table 2 have been prepared in analogy to the preparation examples shown hereinbefore.
Figure imgf000108_0002
Figure imgf000109_0001
Figure imgf000110_0001
HPLC-MS data are reported as retention time (tr, [min]) and detected mass [m/z]; 1H-NMR(CDCI3) data are reported as chemical shift δ [ppm]; m.p. = melting point [0C].
A.2) Preparation of compounds of formula I
Example 18: Preparation of N-(4,5-dihydrothiazol-2-yl)-N-[1-(2,3-dimethylphenyl)- 3-phenylbut-3-enyl]amine
Diisopropylethylamine (74 mg, 0.57 mmol, 1.6 eq) and cyanomethyl-trimethyl- phosphonium iodide (175 mg, 0.72 mmol, 2 eq, cf. Tetrahedron 2001 , 57, 5451 ) were subsequently added to a solution of 1-[1-(2,3-dimethylphenyl)-3-phenylbut- 3-enyl]-3-(2-hydroxyethyl)thiourea (127 mg, 0.36 mmol, 1 eq, cf. example 2) in propionitrile (16 ml). After stirring at 90 0C for 22 h, the mixture was concentrated in vacuo and the residue was dissolved in ethyl acetate. The mixture was then washed with a saturated aqueous solution of ammonium chloride (3 x 15 ml) and with a saturated aqueous solution of potassium carbonate (15 ml). The organic phase was dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-(4,5-dihydrothiazol-2- yl)-N-[1 -(2,3-dimethylphenyl)-3-phenylbut-3-enyl]amine.
Example 19: Preparation of N-(4,5-dihydrothiazol-2-yl)-N-[3-(biphenyl-2-yl)-1-(2,3-dL methylphenyl)but-3-enyl]amine
A mixture of [3-(biphenyl-2-yl)-1 -(2,3-dimethylphenyl)but-3-enyl]amine (226 mg,
6.91 mmol, 1 eq), 2-(p-tolyloxy)thiazoline (130 mg, 6.71 mmol, 0.97 eq.) and methanesulfonic acid (33 mg, 0.35 mmol, 0.5 eq) in n-butanol (1.7 ml) was stirred at 1 10 0C for 8.5 h. The obtained reaction mixture was concentrated in vacuo. The residue was partitioned in tert-butyl methyl ether (10 ml) and a 5% aqueous solution of sodium hydroxide (5 ml). The organic layer was washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-(4,5-dihydrothiazol-2-yl)-N-[3-(biphenyl-2-yl)- 1-(2,3-dimethylphenyl)but-3-enyl]amine
Example 20: Preparation of N-(4,5-dihydrothiazol-2-yl)-N-[1-(2,3-dichlorophenyl)-3- methylbut-3-enyl]amine
20.1 Preparation of N-(2,3-dichlorobenzyl)-N-(4,5-dihydrothiazol-2-yl)amine
A solution of 2-chloroethyl isothiocyanate (3.45 g) in diethyl ether (20 ml) was added dropwise to a solution of 2,3-dichlorobenzylamine (5.00 g) in diethyl ether
(80 ml) at 0 0C and the mixture was allowed to warm up to room temperature over 3 h. An aqueous solution of sodium hydroxide (1 M, 100 ml) was then added and the mixure was further stirred for 1 h. After seperation of the phases, the organic phase was washed with water, dried over sodium sulfate and concentrated in vacuo. The residue was purified by column chromatography to yield
N-(2,3-dichlorobenzyl)-N-(4,5-dihydrothiazol-2-yl)amine.
20.2 Preparation of (2-(2,3-dichlorobenzylimino)thiazolidin-3-yl)carboxylic acid tert- butyl ester
Di-tert-butyl dicarbonate (Boc-anhydride, 9.77 g) was added to a solution of N-(2,3-dichlorobenzyl)-N-(4,5-dihydrothiazol-2-yl)amine (7.79 g, cf. example 20.1 ) in dichloromethane (100 ml) at 0 0C and the mixture was allowed to warm to room temperature overnight. The solution was washed with water, dried over so- dium sulfate and concentrated in vacuo. The residue was purified by column chromatography to yield 2-(2,3-dichlorobenzylimino)thiazolidin-3-ylcarboxylic acid tert-butyl ester.
20.3 Preparation of 2-[1 -(2,3-dichlorophenyl)-3-methyl-but-3-enylimino]thiazolidin- 3-ylcarboxylic acid tert-butyl ester
Preparation of solution A: sec-butyllithium (1.3 M solution in cyclohexane, 6.7 ml, 8.80 mmol, 2.2 eq) was added dropwise to a mixture of potassium tert-butoxide (990 mg, 8.80 mmol, 2.2 eq) in tetrahydrofuran (20 ml) at - 78 0C. The mixture was stirred for 15 min. A solution of 2-(2,3-dichlorobenzylimino)thiazolidin-3-yl- carboxylic acid tert-butyl ester (1.44 g, 4.00 mmol, 1 eq, cf. example 20.2) in tetrahydrofuran (10 ml) was then added dropwise and the mixture stirred for another 2 h.
Preparation of solution B: 3-bromo-2-methylpropene (648 mg, 4.80 mmol, 1.2 eq) in tetrahydrofuran (5 ml) was added to a mixture of sodium iodide (720 mg, 4.80 mmol, 2 eq) in tetrahydrofuran (10 ml) at 0 0C and the mixture was stirred for 1 h at room temperature.
Solution B was added dropwise to solution A at -78 0C and the mixture was stirred for 2.5 h. A saturated solution of aqueous ammonium chloride was then added and the mixture was extracted with ethyl acetate (x 3). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield 2-[1-(2,3-dichloro- phenyl)-3-methyl-but-3-enylimino]thiazolidin-3-ylcarboxylic acid tert-butyl ester.
20.4 Preparation of N-(4,5-dihydrothiazol-2-yl)-N-[1-(2,3-dichlorophenyl)-3-methylbut- 3-enyl]amine
2-[1-(2,3-Dichlorophenyl)-3-methyl-but-3-enylimino]thiazolidin-3-ylcarboxylic acid tert-butyl ester (380 mg, 0.91 mmol, cf. example 20.3) was stirred in aqueous hydrochloric acid (2 M, 25 ml) overnight, basified with an aqueous solution of sodium hydroxide (2 M) and extracted with ethyl acetate (x 3). The combined organic extracts were dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-(4,5-dihydro- thiazol-2-yl)-N-[1-(2,3-dichlorophenyl)-3-methylbut-3-enyl]amine.
Example 21 : Preparation of N-(4,5-dihydrothiazol-2-yl)-N-[(E)-1-(2,3-dichlorophenyl)- 4-phenylbut-3-enyl]amine
Triethylamine (5 ml), iodobenzene (356 mg, 1.75 mmol, 1.05 eq) and
N-(4,5-dihydrothiazol-2-yl)-N-[1 -(2,3-dichlorophenyl)but-3-enyl]amine (500 mg, 1.66 mmol, 1 eq, cf. example 23) were subsequently added to a mixture of palla- dium(ll) acetate (18.7 mg, 0.08 mmol, 0.05 eq) and triphenylphosphine (43.5 mg, 0.17 mmol, 0.1 eq) in acetonitrile (10 ml) under an argon atmosphere. After re- fluxing for 10 h, a 1 M aqueous solution of hydrochloric acid was added at 0 0C until the pH reached 6.5. The mixture was then extracted with tert-butyl methyl ether (2 x 25 ml). The organic extracts were combined, washed with water (15 ml) and a saturated aqueous solution of ammonium chloride (15 ml_), dried over sodium sulphate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-(4,5-dihydrothiazol-2-yl)-N-[(E)-1-(2,3-di- chlorophenyl)-4-phenylbut-3-enyl]amine
The compounds of formula (I)' shown in table 3 hereinafter (examples 22 to 37)
Figure imgf000113_0001
wherein n, Ar, R4, R5 and R6 independently from one another have one of the meanings given in table 2 have been prepared in analogy to the preparation examples shown hereinbefore.
Figure imgf000113_0002
Figure imgf000114_0001
HPLC-MS data are reported as retention time (tr, [min]) and detected mass [m/z]; 1H-NMR(CDCI3) data are reported as chemical shift δ [ppm]; 13C-NMR(CDCIs) data are reported as chemical shift δ [ppm]; m.p. = melting point [0C]. A.3) Preparation of starting compounds of formula III
Example 41 : Preparation of 1-(2,3-dimethylphenyl)but-3-enylamine
41.1 Preparation of N-[1-(2,3-dimethylphenyl)-3-iodobut-3-enyl]carbamic acid tert-butyl ester
Di-tert-butyl dicarbonate (725 mg, 3.32 mmol, 1 eq) was added to a solution of [1-(2,3-dimethylphenyl)-3-iodobut-3-enyl]amine (1.00 g, 3.32 mmol, 1 eq) in di- chloromethane (12 ml) and the mixture was stirred for 4 h. The obtained reaction mixture was concentrated in vacuo and the residue was purified by column chromatography to yield N-[1-(2,3-dimethylphenyl)-3-iodobut-3-enyl]carbamic acid tert-butyl ester.
41.2 Preparation of N-[1-(2,3-Dimethyl-phenyl)-3-phenyl-but-3-enyl]carbamic acid tert- butyl ester
Phenylboronic acid (332 mg, 2.72 mmol, 1.06 eq) was added to a mixture of N-[1-(2,3-dimethylphenyl)-3-iodobut-3-enyl]carbamic acid tert-butyl ester (1.00 g, 2.49 mmol, 1 eq, cf. example 38.1 ), tetrakis(triphenylphosphine)palladium(0)
(72.7 mg, 0.06 mmol, 2.5 mol%) and a solution of sodium carbonate (434 mg Na2CU3 in 2.9 ml H2O, 4.09 mmol, 1.6 eq) in toluene (32 ml) under an argon atmosphere. The mixture was stirred for 4 h at 70 0C after which further amounts of tetrakis(triphenylphosphine)palladium(0) (1 1.4 mg, 0.01 mmol, 0.4 mol%) and phenylboronic acid (34.6 mg, 0.09 mmol) were added. After stirring for further 2 h at 70 0C, an aqueous solution of hydrogen peroxide (30% strenght, 0.4 ml) was added at room temperature and the mixture was stirred for a further 15 min. After addition of a saturated aqueous solution of sodium chloride (15 ml), the reaction mixture was extracted with tert-butyl methyl ether (3 x 15 ml). The organic ex- tracts were combined, washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-[1-(2,3-dimethylphenyl)- 3-phenyl-but-3-enyl]carbamic acid tert-butyl ester.
41.3 Preparation of 1-(2,3-dimethylphenyl)-3-phenylbut-3-enylamine
A mixture of N-[1-(2,3-dimethylphenyl)-3-phenyl-but-3-enyl]carbamic acid tert- butyl ester (500 mg, 1.42 mmol, cf. example 38.2) and HCI (2 M solution in diethyl ether, 30 ml, 60 mmol) in tert-butyl methyl ether (25 ml) was stirred for 24 h. Water (50 ml) was then added and the mixture stirred for 5 min. After seperation of the phases, the aqueous phase was basified with a 10% aqueous solution of sodium hydroxide and extracted with ethyl acetate (3x). The combined organic extracts were washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo to yield 1-(2,3- dimethylphenyl)-3-phenylbut-3-enylamine.
Example 42: Preparation of 1-(2,3-dichlorophenyl)but-3-enylamine
A solution of lithium bis(trimethylsilyl)amide (1 M in tetrahydrofuran, 63 ml, 63.0 mmol, 1.1 eq) was added dropwise to a solution of 2,3-dichlorobenzaldehyde (10.0 g, 57.1 mmol, 1 eq) in tetrahydrofuran (50 ml) at 0 0C. After stirring for 1 h at 00C, a solution of allylmagnesium bromide in diethyl ether (1 M, 92 ml, 92.0 mmol, 1.6 eq) was added dropwise and the mixture was allowed to warm up to room temperature overnight. After quenching with a 25% aqueous solution of ammonia, the resulting mixture was extracted with diethyl ether (x 3), the combined organic extracts were washed with water, dried over sodium sulphate, fil- tered and concentrated in vacuo. The residue was then purified by column chromatography to yield 1-(2,3-dichlorophenyl)but-3-enylamine in an amount of 8.3 g.
Example 43: Preparation of 1-(2,3-dimethylphenyl)-3-iodobut-3-enylamine
43.1 Preparation of 1 -(2, 3-dimethylphenyl)-but-3-ynylamine
Preparation of solution A: 1 ,2-dibromoethane (12.9 g, 69.0 mmol, 0.12 eq) was added to zinc (123 g, 1.89 mol, 3.3 eq) in tetrahydrofuran (80 ml.) and the mixture was refluxed for 1 h. A solution of chlorotrimethylsilane (7.50 g, 69.0 mmol, 0.12 eq) in tetrahydrofuran (165 ml.) was then added at room temperature followed by the dropwise addition of propargylbromide (204 g, 1.71 mol, 3 eq) in tetrahydrofuran (165 ml.) at -10 0C. The resulting mixture was then stirred at -10 0C for 1.5 h.
Preperation of solution B: in a separate flask, lithium bis(trimethylsilyl)amide (1 M in tetrahydrofuran, 629 ml_, 629 mmol, 1.1 eq) was added dropwise to a solution of 2,3-dimethylbenzaldehyde (76.5 g, 571 mmol, 1 eq) in tetrahydrofuran (80 ml.) at 0 0C. The solution was then stirred at this temperature for 15 min and then 1 h at room temperature. Solution B was then added dropwise to solution A at -10 0C and the mixture was allowed to warm up to room temperature overnight. A saturated aqueous solution of K2CO3 (350 ml.) was then added at 0 0C, followed by water (1.3 L) and methyl-tert-butyl ether (500 ml_). The phases were separated, and the aqueous portion was further extracted with methyl-tert-butyl ether (5 x 500 ml_). The combined organic extracts were concentrated in vacuo. The resi- due was dissolved in methyl-tert-butyl ether (200 ml.) and the solution was washed subsequently with water (2 x 200 ml.) and saturated aqueous sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo to yield 1-(2,3-dimethylphenyl)-but-3-ynylamine in an amount of 103 g.
43.2 Preparation of 1-(2,3-dimethylphenyl)-3-iodobut-3-enylamine
Chlorotrimethylsilane (176 g, 1.62 mol, 5 eq) and water (14.5 ml, 808 mmol, 2.5 eq) were subsequently added over 5 minutes each to a mixture of sodium iodide (242 g, 1.62 mmol, 5 eq) in acetonitrile (1.4 I). After stirring for 20 minutes, 1-(2,3- dichlorophenyl)-but-3-ynylamine (56 g, 324 mmol, 1 eq) was added over 15 min- utes and the mixture stirred at 70 0C for 2 h. Ethyl acetate (1.6 I), a saturated aqueous solution of sodium hydrogen carbonate (1.2 I) and sodium chloride (200 g) were then added. After seperation of the phases the aqueous layer was further extracted with ethyl acetate (400 ml). The combined organic extracts were washed with aqueous sodium thiosulfate (450 g in 750 ml), dried over sodium sulfate, filtered and concentrated in vacuo. The residue was taken up in tert-butyl methyl ether (350 ml), concentrated hydrochloric acid (60 ml) was then added slowly and the resulting mixture was stirred for 1 h. The precipitate was partitioned between tert-butyl methyl ether (150 ml) and concentrated hydrochloric acid (20 ml), the mixture was stirred for 30 min, and the solid was then filtered and washed with tert-butyl methyl ether (200 ml portionwise). The crystals were dissolved in a mixture of ethyl acetate (200 ml) and a 15% aqueous solution of sodium hydroxide (140 ml.) and the mixture stirred for 30 min. The organic layer was seperated, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield 1-(2,3-dimethylphenyl)- 3-iodo-but-3-enylamine.
Example 44: Preparation of 4,4-dibromo-1-(2,3-dichlorophenyl)but-3-en-1-ylamine
44.1 Preparation of N-(1-(2,3-dichlorophenyl)-3-oxopropyl)carbamic acid benzyl ester
A mixture of N-(1-(2,3-dichlorophenyl)-3-hydroxypropyl)carbamic acid benzyl ester (400 mg, 1.13 mmol, 1 eq), tetrabutylammonium bromide (36 mg, 0.1 1 mmol, 0.1 eq), 2,2,6,6-tetramethyl-1-piperidinyloxy (18 mg, 0.11 mmol, 0.1 eq) and N-chlorosuccinimide (230 mg, 1.69 mmol, 1.5 eq) in a mixture of chloroform (35 ml), an aqueous solution of sodium hydrogen carbonate (0.5 M, 18 ml.) and an aqueous solution of potassium carbonate (0.05 N, 18 ml) was stirred for 4 h. The phases were then separated and the organic layer concentrated in vacuo. The residue was purified by column chromatography to deliver N-(1-(2,3-dichloro- phenyl)-3-oxopropyl)carbamic acid benzyl ester.
44.2 Preparation of N-(4,4-dibromo-1-(2,3-dichlorophenyl)-but-3-enyl)carbamic acid benzyl ester Triphenylphosphine (4.71 g, 18.0 mmol, 3.4 eq) was added to a solution of carbon tetrabromide (3.13 g, 9.45 mmol, 1.8 eq) in dichloromethane (85 ml) at 0 0C and after stirring for 15 min triethylamine (537 mg, 5.31 mmol, 1 eq) was added. A solution of the aldehyde (1.87 g, 5.31 mmol, 1 eq) in dichloromethane (15 ml) was then added at -78 0C and the mixture stirred at this temperature for 2 h followed by 3 h at room temperature. The mixture was then washed with a saturated aqueous solution of ammonium chloride, a saturated aqueous solution of sodium carbonate, a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield N-(4,4-dibromo-1-(2,3-dichlorophenyl)-but-3- enyl)carbamic acid benzyl ester.
44.3 Preparation of 4,4-dibromo-1 -(2,3-dichlorophenyl)-but-3-enylamine
A mixture of N-(4,4-dibromo-1-(2,3-dichlorophenyl)-but-3-enyl)carbamic acid benzyl ester (1.92 g, 3.78 mmol) and concentrated hydrochloric acid (18 ml) in ethanol (50 ml) was stirred overnight at 80 0C. The solution was then basified with a 50% aqueous solution of sodium hydroxide, extracted with ethyl acetate (x 3) and the combined organic extracts were washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by column chromatography to yield 4,4-dibromo- 1-(2,3-dichlorophenyl)-but-3-enylamine.
B) Biological examples
Action against pests:
The action of the compounds of the general formulae I and Il against pests was evalu- ated by the following experiments:
I. Cotton Aphid (Aphis gossypii)
The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Ki- netic® surfactant.
Cotton plants in the cotyledon stage (variety 'Delta Pine') are infested with approximately 100 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The cotyledons of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days. In this test, the compounds of examples 3, 13, 18, 20, 21 , 23, 25, 27, 30, 31 , 32, 35, 36, 37, 38 and 39 at 300 ppm showed over 70 % mortality in comparison with untreated controls.
II. Green Peach Aphid (Myzus persicae)
The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® surfactant.
Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') are infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The leaves of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
In this test, the compounds of examples 3, 4, 8, 11 , 12, 13, 18, 20, 21 , 23, 25, 27, 28, 30, 31 , 32, 35, 36, 38 and 39 at 300 ppm showed over 70 % mortality in comparison with untreated controls.
III. Cowpea aphid (Aphis craccivora)
The active compounds were formulated in 50:50 acetone : water and 100 ppm Kinetic® surfactant.
Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population has been recorded. Population reduction was recorded after 24, 72, and 120 hours.
In this test, the compounds of examples 18, 20, 21 , 25, 28, 29, 30, 31 , 32, 33, 35, 36, 37, 38 and 39 at 300 ppm showed over 70% mortality in comparison with untreated controls.
IV. Silverleaf whitefly
The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® surfactant.
Selected cotton plants were grown to the cotyledon state (one plant per pot). The cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry. Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced. The insects were colleted using an aspirator and a 0.6 cm, non-toxic Tygon® tubing (R- 3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. The cups were covered with a re-usable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 0C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
In this test, the compounds of examples 13, 18, 19, 36 and 38 at 300 ppm showed over 70% mortality in comparison with untreated controls.

Claims

Claims:
Azolin-2-ylamino compounds of general formula (I),
Figure imgf000121_0001
wherein
n is 0, 1 , 2 or 3;
Ar is phenyl, which is unsubstituted or carries 1 , 2, 3, 4 or 5 substituents RAr, wherein
RAr is selected from halogen, CN, N3, NO2, d-Ce-alkyl, C2-C6-alkenyl and C2-C6-alkynyl, wherein each carbon atom in the aforementioned radicals may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, NH2, OH, SH, COOH, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, C-i-Cβ-haloalkoxy and C-i-Cβ-alkylthio, and
RAr may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, -C(=NRf)ORb, -C(=NRf)NRcRd, -C(=NRf)SRe, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra, -O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe, -SRe, -S(=O)Re, -S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb, -NRf-C(=O)NRcRd, -N=CRaRa', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein Ra, Ra', Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below, and
RAr may further be selected from cyclic radicals -Y-Cy or -Y-Ar1, wherein Ar1 has one of the meanings given below,
Y is a single bond, C-i-Cβ-alkandiyl, C-i-Cβ-alkandiyloxy, -C(=O)-, -C(=S)-, -C(=NRf)-, -C(=NRf)O-, -C(=NRf)S-, -C(=NRf)NRc, -C(=O)O-, -C(=O)NRC-, -C(=O)S-, -C(=S)O-, -C(=S)NRC-, -C(=S)S-, -O-, -O-C(=O)-, -O-C(=O)O-, -O-C(=O)-NRC-, -O-C(=O)S-, -S-, -S(=O)-, -S(=O)2-, -S(=O)2O-, -S(=O)2NRC-, -NRC-, -NRf-C(=O)-, -NRf-C(=O)O-, -NRf-C(=O)NRc-, -N=CRa-, -NRf-NRc-, -NRf-C(=O)S-, -NRf-C(=S)NRc-, wherein Ra, Rb, Rc and Rf independently of one another have one of the meanings given below,
Cy is C3-Ci2-cycloalkyl or a saturated or partially unsaturated 5, 6 or 7-membered heterocycle containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, wherein C3-Ci2-cycloalkyl and the heterocycle are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, halogen, CN, NO2, OH, SH, NH2, COOH, Ci-C6-alkyl, Ci-Cβ-haloalkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy and d-Cβ-alkylthio,
and/or two radicals RAr bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5-, 6- or 7-membered carbocycle or a fused 5-, 6- or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy and C-i-Cβ-alkylthio;
is a radical of the formulae A1 or A2,
Figure imgf000122_0001
wherein
* indicates the point of attachment to the remaining part of the compound;
X is S, O or N(R10);
R7a, R7b, R7c and R7d are selected independently from one another from hydrogen, halogen, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, Ci-Cβ-alkylamino and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals may be unsubsti- tuted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -SRe, -NRcRd, C(=O)-Ra, C(=O)ORb and Ar2, wherein Ar2, Ra, Rb, Rc, Rd and Re have one of the meanings given below and wherein
C3-C6-cycloalkyl additionally may carry any combination of 1 , 2 or 3 substituents of one another selected from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cβ-haloalkyl,
R8, R9 and R10 are selected each independently from one another from hydrogen, CN, NO2, C-i-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl and Ar3, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one an- other selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=O)Ra,
-C(=O)ORb, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, -Ar4, -O- Ar4, -S-Ar4 or -CH2-Ar4, wherein Ar3, Ar4, Ra, Rb, Rc, Rd, Re and Rf have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry any combination of 1 , 2 or 3 or substituents, independently of one another selected from Ci-Cβ-alkyl, C-i-Cβ-haloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, and
R8, R9 and R10 may further be selected from -B-C(=O)Ra, -B-C(=S)Ra,
-B-C(=NRf)Ra, -B-C(=NRf)ORb, -B-C(=NRf)NRcRd, -B-C(=NRf)SRe, -B-C(=O)ORb, -B-C(=O)NRcRd, -B-C(=O)SRe, -B-C(=S)ORb, -B-C(=S)NRcRd, -B-C(=S)SRe, -B-ORb, -B-O-C(=O)Ra, -B-O-C(=O)ORb, -B-O-C(=O)-NRcRd, -B-O-C(=O)SRe, -B-SRe, -B-NRcRd, -B-NRf-C(=O)Ra, -B-NRf-C(=O)ORb, -B-NRf-C(=O)NRcRd,
-B-N=CRaRa', -B-NRf-NRcRd, -B-NRf-C(=O)SRe, -B-NRf-C(=S)NRcRd, -B-S(=O)Re, -B-S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -P(=O)RsRh and P(=S)R9Rh, wherein
B is a single bond or linear or branched Ci-C4-alkanediyl, and
Ra, Ra', Rb, Rc, Rd, Re, Rf, Rs and Rh independently of one another have one of the meanings given below;
is selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl,
C2-C6-alkynyl, Cs-Cβ-cycloalkyl, phenyl and benzyl, wherein each carbon atom of the aforementioned radicals is unsubstituted or carries any combi- nation of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -0Rb, NRcRd, -SRe, -C(=O)Ra and -C(=O)ORb, wherein Ra, Rb, Rc, Rd and Re have one of the meanings given below, and wherein C3-C6-cycloalkyl, phenyl and benzyl additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl,
C2-C6-alkenyl, C2-C6-alkynyl and C-i-Cβ-haloalkyl;
R2 and R3 are selected each independently of one another from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cβ-cycloalkyl, phenyl and benzyl, wherein each carbon atom of the aforementioned radicals is unsub- stituted or carries any combination of 1 , 2 or 3 radicals selected independently of one another from the group consisting of halogen, CN, NO2, -ORb, NRcRd, -SRe, -C(=O)Ra and -C(=O)ORb, wherein Ra, Rb, Rc, Rd and Re have one of the meanings given below, and wherein Cs-Cβ-cycloalkyl, phenyl and benzyl additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Ce-haloalkyl;
R4 is selected from hydrogen, halogen, CN, N3, NO2, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycle containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members, and Ar5, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycle are unsubstituted or carry any combi- nation of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=O)Ra, -C(=O)ORb, Ar6, -CH2-Ar6, -O-Ar6, and -S-Ar6, wherein Rb, Rc, Rd Re, Ar5 and Ar6 have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycle additionally may carry 1 , 2, 3, 4 or 5 substituents selected independ- ently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and
Ci-Cβ-haloalkyl, and
R4 may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, -C(=NRf)ORb, -C(=NRf)NRcRd, -C(=NRf)SRe, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra,
-O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe, -SRe, -S(=O)Re, -S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb, -NRf-C(=O)NRcRd, -N=CRaRa', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein Ra, Ra', Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below; or R4 and R5 together with the carbon atoms to which they are bound form a partially unsaturated 5, 6 or 7-membered carbocycle or a partially unsaturated 5, 6 or 7-membered heterocycle, wherein the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, and wherein each carbocycle or heterocycle may be unsubstituted or may carry 1 or 2 substituents, independently of one another selected from halogen, CN, NO2, -0Rb -SRe, -NRcRd, -C(=O)Ra, -C(=O)ORb, d-Ce-alkyl, C-2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ar7, -CH2-Ar7, -O-Ar7, -S-Ar7, wherein Ra, Rb, Rc, Rd, Re and Ar7 have one of the meanings given below;
R5 and R6 are selected each independently of one another from hydrogen, halogen, CN, N3, NO2, C-i-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, and Ar8, wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -ORb, -NRcRd, -SRe, -C(=O)Ra, -C(=O)ORb, Ar9, -CH2-Ar9, -O-Ar9 and
-S-Ar9, wherein Ra, Rb, Rc, Rd, Re, Ar8 and Ar9 have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C-i-Cβ-haloalkyl, and
R5 or R6 may further be selected from -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, -C(=NRf)ORb, -C(=O)ORb, -C(=O)NRcRd, -C(=O)SRe, -C(=S)ORb, -C(=S)NRcRd, -C(=S)SRe, -ORb, -O-C(=O)Ra, -O-C(=O)ORb, -O-C(=O)-NRcRd, -O-C(=O)SRe, -SRe, -S(=O)Re, -S(=O)2Re, -S(=O)2ORb, -S(=O)2NRcRd, -NRcRd, -NRf-C(=O)Ra, -NRf-C(=O)ORb, -NRf-C(=O)NRcRd,
-N=CRaRa', -NRf-NRcRd, -NRf-C(=O)SRe and -NRf-C(=S)NRcRd, wherein Ra, Ra', Rb, Rc, Rd, Re and Rf independently of one another have one of the meanings given below, or
R5 and R6 together with the carbon atom to which they are bound form a 5,
6 or 7-membered carbocycle or 5, 6 or 7-membered heterocycle, wherein the heterocycle contains 1 , 2, 3 or 4 heteroatoms selected independently from one another from S, O and N as ring members, and wherein each carbocycle or heterocycle may be unsubstituted or may carry 1 or 2 sub- stituents, independently of one another selected from halogen, CN, NO2,
-ORb, -SRe, -NRcRd, -C(=O)Ra, -C(=O)ORb, Ci-C6-alkyl, C-2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, Ar10, -CH2-Ar10, -O-Ar10, -S-Ar10, wherein Ra, Rb, Rc, Rd, Re and Ar10 have one of the meanings given below;
Ra, Ra', Rb, Rc, Rd, Re, Rf, Rs and Rh are each independently of one another se- lected from hydrogen, d-Cε-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs- cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocy- cles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S, N as ring members, and Ar10, wherein Ci-Cβ-alkyl, C2- Cβ-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocycles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, OH, Ci-Cβ-alkoxy, C-i-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Cβ-haloalkylthio, d-Cβ-alkylcarbonyl, Ci-Cβ-haloalkylcarbonyl, Ci-Cβ-alkoxycarbonyl, d-Cβ-haloalkoxycarbonyl, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Cs-Cβ-cycloalkyl,
Cs-Ce-halocycloalkyl, Ar11, -CH2-Ar11, -O-Ar11 and -S-Ar11, wherein Ar10 and Ar11 have one of the meanings given below, and wherein Cs-Cs-cycloalkyl and the heterocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Ce-haloalkyl; and
Ar1, Ar2, Ar3, Ar4, Ar5, Ar6, Ar7, Ar8, Ar9, Ar10 and Ar11 are each independently of one another selected from phenyl, naphthyl and mono- or bicyclic 5- to 10- membered heteroaryl, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein phenyl, naphtyl and hetaryl are unsubstituted or carry any combination of 1 to 5 substituents, independently of one another selected from halogen, CN, NO2, OH, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Cβ-haloalkylthio, d-Cβ-alkylcarbonyl, Ci-Cβ-haloalkylcarbonyl, d-Cβ-alkoxycarbonyl, d-Cβ-haloalkoxycarbonyl,
Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Cs-Cβ-cycloalkyl, Cs-Cβ-halocycloalkyl, unsubstituted phenyl and phenyl carrying 1 , 2, 3, 4 or 5 substituents selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and Ci-C6-haloalkoxy;
or the enantiomers, diastereomers or salts thereof.
2. An azolin-2-ylamino compound according to claim 1 , wherein Ar is phenyl, which carries 1 , 2 or 3 radicals RAr, wherein
RAr is selected from halogen, CN, Ci-Cβ-alkyl, Cs-Cs-cycloalkyl, formyl, d-Ce-alkylcarbonyl, -C(=O)OH, d-Ce-alkoxycarbonyl, -C(=O)NH2, d-Ce-alkylaminocarbonyl, di(Ci-C6-alkyl)aminocarbonyl, -OH, Ci-Cβ-alkoxy, -SH, Ci-Cβ-alkylthio, -IMH2, Ci-Cβ-alkylamino and di(Ci-C6-alkyl)amino, wherein each of the aforementioned radicals may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, OH, Ci-Cβ-alkoxy, C-i-Cβ-haloalkoxy, d-Cβ-alkylthio, and/or
two radicals RAr bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, Ci-C6-alkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio.
3. An azolin-2-ylamino compound according to claim 2, wherein RAr is selected from halogen, CN, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy.
4. An azolin-2-ylamino compound according to any of the preceding claims, wherein Ar is phenyl, which carries 2 radicals RAr in the 2- and 3-postion, relative to the bonding position.
5. An azolin-2-ylamino compound according to any of the preceding claims, wherein R1 is selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, d-Cβ-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and d-Cβ-alkylthio, and wherein Cs-Cβ-cycloalkyl addi- tionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl.
6. An azolin-2-ylamino compound according to claim 5, wherein R1 is selected from hydrogen and Ci-Cβ-alkyl.
7. An azolin-2-ylamino compound according to claim 6, wherein R1 is hydrogen.
8. An azolin-2-ylamino compound according to any of the preceding claims, wherein R2 and R3 are independently of one another selected from hydrogen, halogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, d-Ce-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and C-i-Cε-alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl.
9. An azolin-2-ylamino compound according to claim 8, wherein R2 and R3 are independently of one another selected from hydrogen, halogen and d-Cε-alkyl.
10. An azolin-2-ylamino compound according to claim 9, wherein R2 and R3 are hydrogen.
1 1. An azolin-2-ylamino compound according to any of the preceding claims, wherein n is 1 or 2.
12. An azolin-2-ylamino compound according to claim 1 1 , wherein n is 1.
13. An azolin-2-ylamino compound according to any of the preceding claims, wherein the group -[C(R2)(R3)]n- is methylene.
14. An azolin-2-ylamino compound according to any of the preceding claims, wherein R4 is selected from hydrogen, halogen, Ci-Cβ-alkyl, C-i-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Cs-Cs-cycloalkyl and Ar5, wherein Ci-Cβ-alkyl, Ci-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -OH, d-Cβ-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH, d-Cβ-alkylthio, Ar6, -CH2-Ar6, -O-Ar6 and -S-Ar6, wherein Ar5 and Ar6 have one of the meanings given in claim 1 , and wherein Cs-Cs-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Ce-haloalkyl.
15. An azolin-2-ylamino compound according to claim 14, wherein R4 is selected from hydrogen, halogen, Ci-Cβ-alkyl and Ar5, wherein Ci-Cβ-alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar6, wherein Ar5 and Ar6 have one of the meanings given in claim 1.
16. An azolin-2-ylamino compound according to claim 15, wherein R4 is selected from Ci-Cβ-alkyl and Ar5, wherein Ci-Cβ-alkyl may carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar6, wherein Ar5 and Ar6 have one of the meanings given in claim 1.
17. An azolin-2-ylamino compound according to any of claims 14 to 16, wherein Ar5 and Ar6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy.
18. An azolin-2-ylamino compound according to any of the preceding claims, wherein R5 and R6 are selected independently of one another from hydrogen, halogen, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkynyl, C2-C6-alkynyloxy, Cs-Cs-cycloalkyl and Ar8, wherein d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy and Cs-Cs-cycloalkyl are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, CN, NO2, -OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2, d-Ce-alkylamino, di(d-C6-alkyl)amino, -SH, Ci-C6-alkylthio, Ar9, -CH2-Ar9, -O-Ar9 and -S-Ar9, wherein Ar8 and Ar9 have one of the meanings given in claim 1 , and wherein Cs-Cs-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Ce-haloalkyl.
19. An azolin-2-ylamino compound according to claim 18, wherein R5 and R6 are selected independently of one another from hydrogen, halogen, Ci-Cβ-alkyl and
Ar8, wherein Ci-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkoxy, Ci-Cβ-haloalkoxy and Ar9, wherein Ar8 and Ar9 have one of the meanings given in claim 1.
20. An azolin-2-ylamino compound according to any of claims 18 and 19, wherein Ar8 and Ar9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-C6-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy.
21. An azolin-2-ylamino compound according to claim 19, wherein R5 and R6 are selected from hydrogen and halogen.
22. An azolin-2-ylamino compound according to claim 21 , wherein R5 and R6 are hydrogen.
23. An azolin-2-ylamino compound according to any of the preceding claims, wherein X is sulfur.
24. An azolin-2-ylamino compound according to any of the preceding claims, wherein X is oxygen.
25. An azolin-2-ylamino compound according to any of the preceding claims, wherein X is N(R10).
26. An azolin-2-ylamino compound according to any of claims 23 to 25, wherein R7a, R7b, R7c, R7d are independently of one another selected from hydrogen, halogen, C-i-Ce-alkyl and d-Ce-haloalkyl.
27. An azolin-2-ylamino compound according to claim 26, wherein R7a, R7b, R7c and Rd are hydrogen.
28. An azolin-2-ylamino compound according to any of claims 23 to 27, wherein R8, R9, R10 are selected independently of one another from hydrogen, CN, NO2, d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl,
wherein Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cs-cycloalkyl are unsub- stituted or carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, -OH, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, -SH, d-Cβ-alkylthio, d-Ce-haloalkylthio, -C(=O)H, d-Ce-alkylcarbonyl, d-Ce-haloalkylcarbonyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S, N as ring members, -Ar4 or -CH2-Ar4, wherein Ar4 has one of the meanings given in claim 1 , and wherein Cs-Cs-cycloalkyl additionally may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from Ci-C6-alkyl,
Ci-Cβ-haloalkyl, C2-C6-alkenyl and C2-C6-alkynyl, and
R8, R9, R10 may further be selected from -B-C(=O)Ra, -B-C(=O)ORb, -B-C(=O)SRe, -B-C(=S)ORb, -B-C(=S)NRcRd, -B-C(=S)SRe, -B-ORb, -B-SRe, -S(=O)Re, -B-NRcRd, -S(=O)2Re and -S(=O)2ORb, wherein
B is a single bond or -CH2-, and
wherein Ra, Rb, Rc, Rd and Re independently of one another have one of the meanings given in any of the preceding claims.
29. An azolin-2-ylamino compound according to claim 28, wherein R8, R9 and R10 are independently of one another selected from hydrogen, CN, d-Cε-alkyl, -C(=O)Ra, -C(=O)ORb, -ORb and -B-NRcRd wherein Ra, Rb, Rc and Rd are selected independently of one another from hydrogen, Ci-Cβ-alkyl and phenyl, wherein d-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 sub- stituents, independently of one another selected from halogen, CN, NO2, OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy.
30. An azolin-2-ylamino compound according to claim 29, wherein R8, R9 and R10 are hydrogen.
31. An azolin-2-ylamino compound according to claim 1 , wherein
n is 1 or 2;
Ar is phenyl, which carries 1 , 2 or 3 radicals RAr, wherein
RAr is selected from halogen, CN, Ci-Cβ-alkyl, Cs-Cs-cycloalkyl, formyl, d-Ce-alkylcarbonyl, -C(=O)OH, d-Ce-alkoxycarbonyl, -C(=O)NH2, Ci-Cβ-alkylaminocarbonyl, di(Ci-C6-alkyl)aminocarbonyl, -OH, d-Ce-alkoxy, -SH, d-Ce-alkylthio, -NH2, Ci-Ce-alkylamino and di(Ci-C6-alkyl)amino, wherein each carbon atom of the aforemen- tioned radicals may carry any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, CN, NO2, OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, and/or
two radicals RAr bound to adjacent carbon atoms of the phenyl ring together with said carbon atoms form a fused benzene, a fused saturated or partially unsaturated 5 or 6-membered carbocycle or a fused 5- or 6-membered heterocycle, which contains 1 , 2, 3 or 4 heteroa- toms selected from O, S and N as ring members, wherein each fused benzene, carbocycle or heterocycle is unsubstituted or carries 1 , 2, 3 or 4 substituents, independently of one another selected from halogen, CN, NO2, OH, SH, NH2, COOH, Ci-C6-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and d-Cβ-alkylthio;
A is a radical of the formulae A1 or A2 as defined in claim 1 , wherein
X is S, O or N(R10); R7a, R7b, R7c and R7d are independently of one another selected from hydrogen, halogen, Ci-Cβ-alkyl and d-Cβ-haloalkyl,
R8, R9 and R10 are independently of one another selected from hydrogen,
CN, d-Cβ-alkyl, -C(=O)Ra, -C(=O)ORb, -ORb and -B-NRcRd wherein Ra, Rb, Rc and Rd are selected independently of one another from hydrogen, Ci-Cβ-alkyl and phenyl, wherein Ci-Cβ-alkyl is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 substituents, inde- pendently of one another selected from halogen, CN, NO2, OH, d-Cβ-alkoxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio and wherein phenyl is unsubstituted 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and Ci-C6-haloalkoxy;
R1 is selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and C3-C6-cycloalkyl, wherein each carbon atom of the aforementioned radicals is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, d-Cβ-alkoxy, Ci-C6-haloalkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, NH2,
Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and d-Cβ-alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Ci-C6-haloalkyl;
R2 and R3 are selected independently of one another from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and Cs-Cβ-cycloalkyl, wherein each carbon atom of the aforementioned radicals is unsubstituted or carries any combination of 1 , 2 or 3 substituents selected independently of one another from halogen, CN, NO2, -OH, Ci-C6-alkoxy, Ci-Ce-haloalkoxy, C2-C6-alkenyloxy,
C2-C6-alkynyloxy, NH2, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, -SH and Ci-Cβ-alkylthio, and wherein Cs-Cβ-cycloalkyl additionally may carry 1 , 2 or 3 substituents selected independently of one another from Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cβ-haloalkyl;
R4 is selected from hydrogen, halogen, Ci-Cβ-alkyl and Ar5, wherein C-i-Cβ- alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar6, wherein
Ar5 and Ar6 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, Ci-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy; and
R5, R6 are selected each independently of one another from hydrogen, halogen, d-Cβ-alkyl and Ar8, wherein d-Cβ-alkyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkoxy, d-Cβ-haloalkoxy and Ar9, wherein
Ar8 and Ar9 are independently of one another selected from phenyl, wherein phenyl is unsubstituted or carries any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, d-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy and d-Cβ-haloalkoxy;
or the enantiomers, diastereomers or salts thereof.
32. An agricultural composition containing at least one azolin-2-ylamino compound of formula I as defined in any of claims 1 to 31 and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
33. A method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of an azolin-2-ylamino compound of formula I or a salt thereof as defined in any of claims 1 to 31 or with a pesticidally effective amount of an agricultural composition as defined in claim 32.
34. The method as claimed in claim 33, for protecting seed and/or the plants which grow therefrom, which method comprises treating the seed with a pesticidally effective amount of an azolin-2-ylamino compound of formula I or an agriculturally acceptable salt thereof as defined in any of claims 1 to 31 or with a pesticidally effective amount of an agricultural composition as defined in claim 32.
35. Seed, comprising at least one azolin-2-ylamino compound of formula I as defined in any of claims 1 to 31 and/or an agriculturally acceptable salt thereof.
36. A method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally ef- fective amount of an azolin-2-ylamino compound of formula I or a veterinally acceptable salt thereof as defined in any of claims 1 to 31.
37. Use of azolin-2-ylamino compounds of formula I or a salt thereof as defined in any of claims 1 to 31 for controlling animal pests.
38. Compounds of general formula (II),
Figure imgf000134_0001
wherein n, Ar, R1, R2, R3, R4, R5 and R6 independently from one another have one of the meanings given for the compounds of formula I in any of claims 1 to 31 , and
A' is a radical of formula A3,
Figure imgf000134_0002
wherein W is halogen or OR 11
R7a, R7b, R7c, R7d, R8, R9 and X independently from one another have one of the meanings given for the compounds of formula I in any of claims 1 to 31 ,
* indicates the point of attachment to the remaining part of the compound; and
R11 is selected from hydrogen and -C(=O)-R', wherein R1 is selected from hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-Cβ-cycloalkyl, saturated or partially unsaturated 5, 6 or 7-membered heterocycles containing 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members, and Ar12, wherein Ci-Cβ- alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Cs-Cs-cycloalkyl and the heterocy- cles are unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 sub- stituents, independently of one another selected from halogen, CN, NO2, OH, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-Cβ-haloalkylthio, d-Cβ-alkylcarbonyl, d-Cβ-haloalkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, Ar13,
-CH2-Ar13, -O-Ar13 and -S-Ar13, wherein C3-C8-cycloalkyl and the het- erocycles additionally may carry 1 , 2, 3, 4 or 5 substituents selected independently of one another from C-i-Cε-alkyl, C2-C6-alkenyl, C2-C6-alkynyl and d-Cε-haloalkyl; and wherein
Ar12 and Ar13 are independently of one another selected from phenyl, naphthyl and mono- or bicyclic 5- to 10-membered heteroaryl, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, wherein phenyl, naphtyl and hetaryl are un- substituted or carry any combination of 1 to 5 substituents, in- dependently of one another selected from halogen, CN, NO2,
OH, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-halo- alkylthio, C-i-Cβ-alkylcarbonyl, C-i-Cβ-haloalkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-haloalkoxycarbonyl, C-i-Cε-alkyl- amino, di(Ci-C6-alkyl)amino, Cs-Cβ-cycloalkyl, Cs-Cβ-halo- cycloalkyl, unsubstituted phenyl and phenyl carrying 1 , 2, 3, 4 or 5 substituent selected from halogen, d-Cε-alkyl, Ci-Cβ-haloalkyl, C-i-Cβ-alkoxy and Ci-C6-haloalkoxy;
or the enantiomers, diastereomers or salts thereof.
39. A compound of formula Il according to claim 38, wherein R11 is selected from hydrogen and -C(=O)-R', wherein
R1 is selected from hydrogen, C-i-Cε-alkyl, and Ar12, wherein C-i-Cε-alkyl is unsubstituted or carries any combination of 1 , 2 or 3 substituents, independently of one another selected from halogen, Ci-Cβ-alkoxy, Ci-Cβ-haloalkoxy and Ar13, wherein
Ar12 and Ar13 are independently of one another selected from phenyl or pyridyl, wherein phenyl or pyridyl are each unsubstituted or carry any combination of 1 , 2, 3, 4 or 5 substituents, independently of one another selected from halogen, C-i-Cε-alkyl, C-i-Cε-haloalkyl and d-Cβ-haloalkoxy.
40. A compound of formula Il according to claim 39, wherein R11 is selected from hydrogen and d-Cβ-alkylcarbonyl.
41. An agricultural composition containing at least one compound of formula Il as defined in any of claims 38 to 40 and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
42. A method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, seed, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest at- tack or infestation with a pesticidally effective amount of a compound of formula Il or a salt thereof as defined in any of claims 38 to 40 or with a pesticidally effective amount of an agricultural composition as defined in claim 41.
43. The method as claimed in claim 42, for protecting seed and/or the plants which grow therefrom, which method comprises treating the seed with a pesticidally effective amount of a compound of formula Il or an agriculturally acceptable salt thereof as defined in any of claims 38 to 40 or with a pesticidally effective amount of an agricultural composition as defined in claim 41.
44. Seed, comprising at least one compound of formula Il as defined in any of claims 38 to 40 and/or an agriculturally acceptable salt thereof.
45. A method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally ef- fective amount of a compound of formula Il or a veterinally acceptable salt thereof as defined in any of claims 38 to 40.
46. Use of a compound of formula Il or a salt thereof as defined in any of claims 38 to 40 for controlling animal pests.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (en) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft 1-(azolin-2-yl) amino-1,2-diphenylethane compounds for combatting insects, arachnids and nematodes
WO2007060121A1 (en) * 2005-11-25 2007-05-31 Basf Se Indanyl-and tetrahydronaphthyl-amino-azoline compounds for combating animal pests
WO2008119511A1 (en) * 2007-04-03 2008-10-09 Bayer Cropscience Ag Insecticidal derivatives of substituted benzylamines
WO2008138499A1 (en) * 2007-05-14 2008-11-20 Bayer Cropscience Ag Insecticidal substituted thiourea derivatives

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (en) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft 1-(azolin-2-yl) amino-1,2-diphenylethane compounds for combatting insects, arachnids and nematodes
WO2007060121A1 (en) * 2005-11-25 2007-05-31 Basf Se Indanyl-and tetrahydronaphthyl-amino-azoline compounds for combating animal pests
WO2008119511A1 (en) * 2007-04-03 2008-10-09 Bayer Cropscience Ag Insecticidal derivatives of substituted benzylamines
WO2008138499A1 (en) * 2007-05-14 2008-11-20 Bayer Cropscience Ag Insecticidal substituted thiourea derivatives

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
A. HIRASHIMA ET. AL.: "Synthesis and Octopaminergic Agonist Activity of 2-(Substituted benzylamino)-2-thiazolines.", BIOSCIENCE, BIOTECHNOLOGY AND BIOCHEMISTRY, vol. 56, no. 7, 1992, pages 1062 - 1065, XP002527074 *
K. R. JENNINGS ET. AL.: "A Biorationally Synthesized Octopamineric Insecticide: 2-(4-Chloro-o-toluidino)-2-oxazoline.", PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY, vol. 30, no. 2, 1988, pages 190 - 197, XP002527076 *
L. TROISI ET. AL.: "Palladium catalysed cyclocarbonylation of unsaturated amines. Chemo- and stereoselective synthesis of N-heteroaryl-gamma- and delta- lactams.", ARKIVOC, no. 6, 2006, pages 161 - 173, XP002527075 *

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