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WO2009115491A1 - Composés azolin-2-ylamino pour lutter contre des animaux nuisibles - Google Patents

Composés azolin-2-ylamino pour lutter contre des animaux nuisibles 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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Ronan Le Vezouet
Markus Kordes
Christopher Koradin
Ernst Baumann
Deborah L. Culbertson
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • 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

La présente invention porte sur des composés azolin-2-ylamino représentés par les formules (I) et (II), dans lesquelles n représente 0 à 3; Ar représente phényle; A représente un radical représenté par les formules A1 ou A2, dans lesquelles * indique le point d'attachement; X représente S, O ou N(R10); R7a-d représentent H, halogène, alkyle en C1-C6, alcoxy en C1-C6, alkylamino en C1-C6 ou cycloalkyle en C3-C6; R8-10 représentent H, CN, NO2, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C8, Ar3, -B-C(=O)Ra, -B-C(=S)Ra, -B-C(=NRf)Ra, etc., où B représente une simple liaison ou un alcanediyle en C1-C4; R1 représente H, halogène, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C6, phényle ou benzyle; R2,3 représentent H, halogène, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C6, phényle ou benzyle; R4 représente H, halogène, CN, N3, NO2, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C8, un hétérocycle, Ar5, -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, etc.; ou R4 et R5 forment ensemble un carbocycle ou un hétérocycle; R5,6 représentent H, halogène, CN, N3, NO2, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C8, hétérocycle, Ar8, -C(=O)Ra, -C(=S)Ra, -C(=NRf)Ra, etc.; ou R5 et R6 forment ensemble un carbocycle ou un hétérocycle; Ra-h représentent H, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C8, des hétérocycles ou Ar10; Ar1 à 11 représentent phényle, naphtyle ou hétéroaryle; et A' représente un radical représenté par la formule A3, dans laquelle W représente halogène ou OR11; R11 représente H ou -C(=O)-Ri; Ri représente H, alkyle en C1-C6, alcényle en C2-C6, alcynyle en C2-C6, cycloalkyle en C3-C8, hétérocycle ou Ar12; et Ar12 représente phényle, naphtyle ou hétéroaryle. L'invention porte également sur une composition pour l'agriculture contenant de tels composés, sur l'utilisation de tels composés pour lutter contre des animaux nuisibles, sur une graine comprenant de tels composés, sur un procédé de lutte contre des animaux nuisibles et sur un procédé de traitement ou de protection d'animaux contre une infection par des parasites.
PCT/EP2009/053079 2008-03-17 2009-03-16 Composés azolin-2-ylamino pour lutter contre des animaux nuisibles Ceased WO2009115491A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (fr) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft Composes 1-(azolin-2-yl) amino-1,2-diphenylethane destines a la lutte contre les insectes, les arachnides et les nematodes
WO2007060121A1 (fr) * 2005-11-25 2007-05-31 Basf Se Composes indanyle et tetrahydronaphthyl-amino-azoline utiles pour lutter contre les parasites des animaux
WO2008119511A1 (fr) * 2007-04-03 2008-10-09 Bayer Cropscience Ag Insecticides dérivés de benzylamines substituées
WO2008138499A1 (fr) * 2007-05-14 2008-11-20 Bayer Cropscience Ag Dérivés substitués du thio-urée, servant d'insecticides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (fr) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft Composes 1-(azolin-2-yl) amino-1,2-diphenylethane destines a la lutte contre les insectes, les arachnides et les nematodes
WO2007060121A1 (fr) * 2005-11-25 2007-05-31 Basf Se Composes indanyle et tetrahydronaphthyl-amino-azoline utiles pour lutter contre les parasites des animaux
WO2008119511A1 (fr) * 2007-04-03 2008-10-09 Bayer Cropscience Ag Insecticides dérivés de benzylamines substituées
WO2008138499A1 (fr) * 2007-05-14 2008-11-20 Bayer Cropscience Ag Dérivés substitués du thio-urée, servant d'insecticides

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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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