WO2009153238A1 - Aminothiazoline compounds for combating insects, arachnids and nematodes - Google Patents

Aminothiazoline compounds for combating insects, arachnids and nematodes Download PDF

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WO2009153238A1
WO2009153238A1 PCT/EP2009/057351 EP2009057351W WO2009153238A1 WO 2009153238 A1 WO2009153238 A1 WO 2009153238A1 EP 2009057351 W EP2009057351 W EP 2009057351W WO 2009153238 A1 WO2009153238 A1 WO 2009153238A1
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alkyl
compounds
radicals
formula
alkoxy
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PCT/EP2009/057351
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French (fr)
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Markus Kordes
Ronan Le Vezouet
Ralph Paulini
Deborah L. Culbertson
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
    • C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
    • C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D263/28—Nitrogen atoms not forming part of a nitro radical
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to aminothiazoline compounds of the general formula (I):
  • A is a radical of the formulae A 1 or A 2 :
  • X is sulfur, oxygen, or NR k ;
  • R k has the meaning as defined for R 1 ;
  • R 1 is hydrogen, cyano, nitro, d-C ⁇ -alkyl, formyl, d-C ⁇ -alkylcarbonyl, d-C ⁇ - alkoxycarbonyl, d-C ⁇ -alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R # ,
  • R # is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, or d-Ce-alkylthio;
  • R a and R b are each independently hydrogen, d-C ⁇ -alkyl, C2-C6- alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R # ;
  • phenyl, phenyloxy, or benzyl each of which three radicals may be unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-C ⁇ -alkyl, d-C ⁇ - haloalkyl, d-C ⁇ -alkylthio, d-C ⁇ -haloalkylthio, d-C ⁇ -alkoxy or d-C ⁇ -haloalkoxy groups;
  • R 2 is halogen, OH, SH, NH 2 , SO 3 H, COOH, cyano, nitro, Ci-C 6 -alkyl, d-Ce-alkoxy, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, d-Cs-alkylthio, C2-C6-alkenyl, C2-C6- alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6-alkynyl, C2-C6- alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, d-C ⁇ -alkylsulfonyl, Ci-C ⁇ - alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, formyl, Ci-C
  • Y is a single bond, oxygen, sulfur, C-i-C ⁇ -alkandiyl or Ci-C ⁇ -alkandiyloxy
  • Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered het- eroaromatic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is unsubsti- tuted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R # ; and
  • Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals R # ;
  • radicals R 2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals R # ;
  • R 3 , R 4 are each independently hydrogen, Ci-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, Cs-C ⁇ -cycloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R # ,
  • phenyl or benzyl each unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, CrC 6 - haloalkylthio, Ci-C6-alkoxy or Ci-C ⁇ -haloalkoxy groups;
  • W is phenyl which is unsubstituted or substituted by 1 , 2, 3, or 4 independently selected substituents R 2 ; or
  • a 5- to 6-membered heteroaromatic ring which contains from 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur
  • the heteroaromatic ring may optionally be fused to a ring selected from phenyl and a 5- to 6-membered saturated, partially unsaturated or aromatic heterocyclic ring which contains from 1 to 3 heteroatoms selected from oxygen, ni- trogen and sulfur, and wherein the 5- to 6-membered heteroaromatic ring or the respective fused ring systems are unsubstituted or substituted by R 5 and/or any combination of 1 to 4 groups R 6 : wherein n is 0, 1 , 2, 3, or 4;
  • each of the last three mentioned radicals may be unsubstituted or substituted with 1 to 5 radicals, independently of one another selected from the group consisting of one to five halogen radicals, one to three Ci-C ⁇ -alkyl, one to three Ci-C ⁇ - haloalkyl, one to three d-C ⁇ -alkylthio, one to three Ci-C ⁇ - haloalkylthio, one to three Ci-C ⁇ -alkoxy and one to three Ci-C ⁇ - haloalkoxy radicals; and wherein R 5a , R 5b and R 5c are defined as below;
  • Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with one to five radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C6-alkyl, d-C ⁇ -haloalkyl, C-i-C ⁇ - alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and d-C ⁇ -alkylthio;
  • R 5a , R 5b , R 6a and R 6b are each independently selected from hydrogen, d-Ce-alkyl, d-Ce-haloalkyl, C 2 -C 6 - alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of one, two or three radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C ⁇ -alkyl, C2-C6- alkenyl, C2-C6-alkynyl, d-C ⁇ -alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, C-i-C ⁇ - haloalkoxy, d-C ⁇ -haloalkyl and C-i-C ⁇ - alkylthio; R 5c and R 6c are each independently selected
  • the present invention also relates also to a method of combating animal pests, se- lected from insects, arachnids and nematodes, which comprises contacting the animal pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by insects, arachnids or nematodes with a pesticidally effective amount of at least one aminothiazoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof.
  • the present invention also provides pesticidal compositions comprising at least one aminothiazoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof and a solid or liquid carrier.
  • the invention relates to pesticidal compositions, preferably in the form of directly sprayable solutions, emulsions, pastes oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprise at least one aminothia- zoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof and a solid or liquid carrier, admixed with one or more agronomically or veterinarily acceptable inert, solid or liquid carrier(s) and, if desired, at least one surfactant.
  • pesticidal compositions preferably in the form of directly sprayable solutions, emulsions, pastes oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprise at least one aminothia- zoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof and a solid or liquid carrier, admixed with one or more
  • WO 2006/74262 discloses pharmaceutically active aminothiazoline compounds which may carry an aryloxyalkyl ligand at the amino group. These compounds however do not also carry a benzyl ligand at the amino group as the compounds of the present invention.
  • the compounds of the general formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the present invention provides both the pure enantiomes or diastereomers or mixtures thereof.
  • the compounds of the general formula I may also exist in the form of different tautomers.
  • the invention comprises the single tautomers, if separable, as well as the tautomer mixtures.
  • Salts of the compounds of the formula I are especially agriculturally or veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
  • Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and bar- ium, 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.
  • substituded ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammo- nium and benzyltriethylammonium, 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 the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Suitable acid addition salts e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hy- drochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -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 particular fluorine, chlorine or bromine.
  • Ci-C ⁇ -alkyl refers to a saturated straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 4 carbon groups, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-
  • Ci-C4-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.
  • the carbon atoms may, in accordance with the respective definitions for the compound of formula I above, carry 1 , 2 or 3 radicals R # .
  • each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R # .
  • R # being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, especially by fluorine or chlorine.
  • radicals are also referred to as haloalkyl.
  • R # being cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C ⁇ -haloalkoxy, or C-i-C ⁇ -alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R # .
  • Ci-C ⁇ -haloalkyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, di- chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1- fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- chloro-2,2-difluoroethyl, 2,2-dichloro-2-flu
  • C-i-C ⁇ -alkoxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom.
  • Examples include Ci-C ⁇ -alkoxy such as methoxy, ethoxy, OCH2-C2H5, OCH(CHs) 2 , n-butoxy, OCH(CHs)-C 2 H 5 , OCH 2 -CH(CHs) 2 , OC(CHs) 3 , n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethyl-propoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-di
  • 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, i.e., for example, d-C ⁇ -haloalkoxy such as chloro- methoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 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
  • Ci-C ⁇ -alkylcarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group.
  • Ci-C ⁇ -alkylcarbonyl such CO-CH3, CO-C2H5, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1 ,1- dimethylethylcarbonyl, n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1 ,1-dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1- methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4- methylpentylcarbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2-dimethylbutyl,
  • Ci-C6-alkoxycarbonyl refers to a straight-chain or branched alkoxy group (as mentioned above) having 1 to 6 carbon atoms attached via the carbon atom of the carbonyl group.
  • Examples include (Ci-C6-alkoxy)carbonyl, for example CO- OCH 3 , CO-OC 2 H 5 , COO-CH 2 -C 2 H 5 , CO-OCH(CHs) 2 , n-butoxycarbonyl, CO-OCH(CH 3 )- C 2 H 5 , CO-OCH 2 CH(CHs) 2 , CO-OC(CH 3 )S, n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1- ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1-dimethylpropoxycarbonyl, 1 ,2- di
  • Ci-C ⁇ -alkylcarbonyloxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) bonded via the carbon atom of the carbonyloxy group at any bond in the alkyl group.
  • Ci-C ⁇ -alkylcarbonyloxy such O-CO-CH3, 0-CO-C 2 H 5 , n-propylcarbonyloxy, 1- methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2- methylpropylcarbonyloxy, 1 ,1-dimethylethylcarbonyloxy, n-pentylcarbonyloxy, 1- methylbutylcarbonyloxy, 2-methylbutylcarbonyloxy, 3-methylbutylcarbonyloxy, 1 ,1- dimethylpropylcarbonyloxy, 1 ,2-dimethylpropylcarbonyloxy and the like.
  • d-C ⁇ -alkylthio (C-i-C ⁇ -alkylsulfanyl: C-i-C ⁇ -alkyl-S-) refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example Ci-C4-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2- methylpropylthio, 1 ,1-dimethylethylthio, n-pentylthiocarbonyl, 1-methylbutylthio, 2- methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n- hexylthio, 1 ,1-dimethylpropylthio,
  • Ci-C ⁇ -alkylthiocarbonyl refers to a straight-chain or branched alkthio group (as mentioned above) having 1 to 6 carbon atoms attached via the carbon atom of the carbonyl group. Examples include CO-SCH3, CO-SC2H5,
  • CO-SCH 2 -C 2 H 5 CO-SCH(CHs) 2 , n-butylthiocarbonyl, CO-SCH(CHs)-C 2 H 5 , CO-SCH 2 - CH(CHs) 2 , CO-SC(CH 3 )S, n-pentylthiocarbonyl, 1-methylbutylthiocarbonyl, 2- methylbutylthiocarbonyl, 3-methylbutylthiocarbonyl, 2,2-dimethylpropylthiocarbonyl, 1- ethylpropylthiocarbonyl, n-hexylthiocarbonyl, 1 ,1-dimethylpropylthiocarbonyl, 1 ,2- dimethylpropylthiocarbonyl, 1-methylpentylthiocarbonyl, 2-methylpentylthiocarbonyl, 3- methylpentylthiocarbonyl, 4-methylpentylthiocarbonyl, 1 ,1-dimethylbutylthio
  • Examples include C-i-C ⁇ -alkylsulfinyl: SO-CH3, SO- C 2 H 5 , n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2- methylpropylsulfinyl, 1 ,1-dimethylethylsulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl, 2- methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1-dimethylpropylsulfinyl, 1 ,2- dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentylsulfiny
  • Ci-C6-alkylamino refers to a secondary amino group carrying one alkyl group as defined above e.g. methylamino, ethylamino, propylamino, 1- methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1- dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3- methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1 ,1- dimethylpropylamino, 1 ,2-dimethylpropylamino, 1-methylpentylamino, 2- methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1- dimethylbutylamino, 1 ,2-dimethylbutylamino, 1
  • di(Ci-C6-alkyl)amino refers to a tertiary amino group carrying two alkyl radicals as defined above e.g. dimethylamino, diethylamino, di-n-propylamino, diisopro- pylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N- methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N- methylamino, N-(isobutyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)-N- ethylamino, N-(isopropyl)-N-ethylamino, N-
  • Examples include d-C ⁇ -alkylsulfonyl such as SO2-CH3, SO2-C2H5, n- propylsulfonyl, SO2-CH(CH3)2, n-butylsulfonyl, 1-methylpropylsulfonyl, 2- methylpropylsulfonyl, SO2-C(CH3)3, n-pentylsulfonyl, 1-methylbutylsulfonyl, 2- methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n- hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpent
  • C2-C6-alkenyl 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-pen
  • each alkenyl radical the carbon atoms may, in accordance with the respective defini- tions for the compound of formula I above, carry 1 , 2 or 3 radicals R # .
  • each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R # .
  • R # being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, especially by fluorine or chlorine.
  • These radicals are also referred to as haloalkyl.
  • R # being cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C ⁇ -haloalkoxy, or d-C ⁇ -alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R # .
  • C2-C6-alkenyloxy refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy, etc.
  • C2-C6-alkenylthio refers to a straight-chain or branched satu- rated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylsulfanyl, allylsulfanyl (propen-3-ylthio), methallylsufanyl, buten-4-ylsulfanyl, etc..
  • C2-C6-alkenylamino refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylamino, allylamino (propen-3-ylamino), methallylamino, buten-4-ylamino, etc.
  • C2-C6-alkenylsulfonyl refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example vinylsulfonyl, allylsulfonyl (propen-3- ylsulfonyl), methallylsufonyl, buten-4-ylsulfonyl, etc.
  • SO2 sulfonyl
  • C2-C6-alkynyl as used herein and in the alkynyl moieties of C2-C6- alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, C2-C6-alkynylsulfonyl, C2-C6- alkynylcarbonyl, C2-C6-alkynyloxycarbonyl, and Ci-C ⁇ -alkynylcarbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 10 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
  • each alkynyl radical the carbon atoms may, in accordance with the respective definitions for the compound of formula I above, carry 1 , 2 or 3 radicals R # .
  • each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R # .
  • R # being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, espe- cially by fluorine or chlorine.
  • halogen espe- cially by fluorine or chlorine.
  • R # being cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C ⁇ -haloalkoxy, or d-C ⁇ -alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R # .
  • C2-C6-alkynyloxy refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propin-3-yloxy), butin-3-yloxy, butin-4-yloxy, etc.
  • C2-C6-alkynylthio refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is at- tached via a sulfur atom, for example propargylsulfanyl (propin-3-ylthio), butin-3- ylsufanyl, butin-4-ylsulfanyl, etc.
  • C2-C6-alkynylamino refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example propargylamino (propin-3-ylamino), butin-3- amino, butin-4-ylamino, etc.
  • C2-C6-alkynylsulfonyl refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example propargylsulfonyl (propin-3- yltsulfonyl), butin-3-ylsufonyl, butin-4-ylsulfonyl, etc.
  • SO2 sulfonyl
  • Cs-Cs-cycloalkyl refers to a mono- or bi- or polycyclic hydro- carbon radical having 3 to 12 carbon atoms, in particular 3 to 6 carbon atoms.
  • monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl.
  • bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl.
  • Each cycloalkyl radical may carry 1 to 3 of the aforementioned radicals R # .
  • 1 to 3 of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R # .
  • Preferred radicals R # on cycloalkyl are selected from halogen, especially fluorine or chlorine, and d-C ⁇ -alkyl.
  • the term "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 comprise a fused 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 of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the fused ring comprises C5-C7-cycloalkyl, C5-C7-cycloalkenyl, or 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 carrying a fused phenyl ring are quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl.
  • 5 to 7-membered heterocyclyl comprises monocyclic heteroaromatic rings as defined above and nonaromatic saturated or partially unsaturated heterocyclic rings having 5, 6 or 7 ring members.
  • non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydro- furanyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl,
  • R 1 is hydrogen, Ci-C ⁇ -alkylcarbonyl, or Ci- C ⁇ -alkoxycarbonyl.
  • R 3 is hydrogen or Ci-C4-alkyl, especially hydrogen or methyl and most preferred hydrogen.
  • R 4 is hydrogen or Ci-C4-alkyl, especially hydrogen or methyl and most preferred hydrogen.
  • W is phenyl which is unsubstituted or sub- stituted by 1 , 2, 3, or 4, preferably with 1 , 2, or 3 independently selected substituents R 2 .
  • W is phenyl which is unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R 2 , preferably phenyl which is unsubstituted or substituted with 1 or 2 substituents R 2 .
  • W is phenyl which is substituted with 2 independently selected substituents R 2 , preferably with halogen, Ci-C4-alkyl, C1-C4- alkoxy, or Ci-C4-haloalkyl, most preferably with chlorine, bromine, methyl, trifluoro- methyl, or methoxy.
  • W is phenyl which is disubstituted in the 3,5-positions with 2 independently selected substituents R 2 , preferably with 2 methyl groups.
  • a in formula I is a radical A 2 with X being S, and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R 2A and R 2B each independently are as defined above for compounds of formula I for R 2 .
  • a in formula I is a radical A 1 with X being O and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R 2A and R 2B each independently are as defined above for compounds of formula I for R 2 .
  • a in formula I is a radical A 1 with X being S and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R 2A and R 2B each independently are as defined above for compounds of formula I for R 2 .
  • the compounds of the present invention can be e.g. prepared from the corresponding amines III or a salt thereof by the synthetic routes outlined in schemes 1 and 2.
  • the amine III is converted into the corresponding isothiocyanate IV by conventional means, e.g. by reacting III with thiophosgene (see e.g. Houben-Weyl, E4, "Methoden der Organischen Chemie", chapter INc, pp. 837-842.
  • the isothiocyanate IV is then reacted with an aminoethanol of the general formula V, thereby obtaining the thiourea compound of the formula II.
  • the reaction of the aminoethanol V wherein R 7 is hydrogen with isothiocyanate IV can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Bio- chem. 1992, 56 (7), 1062-1065.
  • an amine III or a salt thereof can be converted to the corresponding ami- nothiocarbonylaminoethane compound II, by reacting the amine III with an isothiocyanate Vl according to scheme 2.
  • lsothiocyanates Vl wherein R 7 is d-C ⁇ -alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl, or benzoyl can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117.
  • the thus obtained thioureas of formula Il can be cyclized by conventional means thereby obtaining the desired thiazoline compound of the formula I, wherein A is A 2 with X being S.
  • Cyclization of compound Il can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters1999, 40, 3125-3128) in particular if R 7 is hydrogen.
  • the R 7 group can be cleaved prior to cyclisation, e.g. by saponification if R 7 is C-i-C ⁇ - alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl or benzoyl.
  • the compounds of the formula I according to the invention wherein X is O or S can be prepared by the method shown in scheme 4.
  • the variable Hal is halogen, especially chlorine.
  • an amine IV or a salt thereof can be converted to an azoline I by reaction with 2- chloroethylisothiocyanate or 2-chloroethylisocyanate e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22 and subsequent cyclization in the presence or absence of base.
  • 2- chloroethylisothiocyanate or 2-chloroethylisocyanate e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22 and subsequent cyclization in the presence or absence of base.
  • 2- chloroethylisothiocyanatoethane CAS-reg.-no.: 6099-88-3
  • 2- chloroethylisocyanate CAS-reg.-no.: 1943-83-5
  • LG is a leaving group such as e.g. Cl, Br, I, OSO2R, OCO2R, wherein the R is C1-C4- alkyl.
  • a compound I-H is treated with a suitable electrophile.
  • Amines IX and X are known in the art or can be prepared by methods familiar to an organic chemist, for instance as described in Tetrahedron Letters 2004, 45, 1503-1505, Heterocycles 1989, 28 (2), 1015-31 or in Synthesis 2003, 10, 1626-38 and as demonstrated below in the preparation procedure and as outlined in scheme 7.
  • the conversion of amines X to amines III is done according to standard procedures for cleavage of amine protective groups, e.g. as described in P. J. Kocienski, Protective groups, 1 st ed., Thieme, 1994, and in analogy to the experimental procedures described in the experimental section below.
  • the compounds of formula I 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 formula I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefi- nation, reduction, metal catalyzed coupling reactions, oxidation and the like.
  • substituents and indices are as defined above for compounds I, and wherein R 7 is hydrogen, Ci-C ⁇ -alkylcarbonyl, Ci-C ⁇ -alkoxycarbonyl, or benzoyl, are also a subject of the present invention.
  • Compounds Il can also be used for their pesticidal activity. Pesticidal use and methods to combat animal pests and to protect crops, plants and animals from animal pests with compounds Il is also a subject of the present invention. Therefore the methods and uses as described below for compounds I are also applicable for compounds II.
  • 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.
  • inventive compounds I may be present in different crystalline modifications which may differ in their biological activity. These are also subject of the present invention.
  • the compounds of formulae I and Il may be used for controlling animal pests.
  • 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 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 formula lor 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 infesta- tion and comprises treating the plant propagation material (such as seed) with a pesti- cidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural 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 lor 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 a salt thereof or a mixture of several active compounds of formula lor 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 tautomers or mixtures of tautomers.
  • the compound of formula I and the pestidicidal compositions comprising it are effective agents for controlling arthropod pests and nematodes.
  • Animal pests controlled by the compound of formula I 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 Coldoptera
  • 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 Iongicornis, 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
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;
  • Hymenopterans e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, 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;
  • 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 nematodes Dolichodorus
  • 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 compounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
  • the compounds of formula I 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 formula I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • the formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq.
  • 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 examples include 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 sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
  • 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 po- lyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybute-nes, 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 112, 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, pig- ment 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, dusta- ble 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 formula- tion 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 compound ⁇ ), 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 addition 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.
  • Granules (GR, FG, GG, MG) 0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound ⁇ ) is obtained.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
  • the compound of formula I is also suitable for the treatment of plant propagation materials (such as seed).
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersi- ble 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 preger-minated 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 formula lfor 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 formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • 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 cock- roaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • Formulations of compounds of formula I as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethyl- fomaamide, 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
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the compounds of formula I and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vapor- izers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g.
  • 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, nonwov- ens, 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 pyrethroid not used for insect control such as ⁇ (+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucaly
  • 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 formula I or spraying them onto the nets.
  • seed treatment refers to all methods that bring seeds and the compounds of formula I into contact with each other
  • seed dressing to methods of seed treatment which provide the seeds with an amount of the compounds of formula I, i.e. which generate a seed comprising the compounds of formula I.
  • the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed.
  • the seed can be treated immediately before, or during, the planting 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 seed.
  • the term "unsown seed” is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
  • a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device 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 appropriate, this is followed by a drying step.
  • a suitable device for example a mixing device for solid or solid/liquid mixing partners
  • the compounds of formula I 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 formula I 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 lor 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 a parasiticidally effective amount of a compound of formula lor the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • compounds of formula I are suitable for corn-bating endo- and ectoparasites in and on animals.
  • Compounds of formula I 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.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • Compounds of formula I 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 formula I 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 formula I are especially useful for combating ectoparasites.
  • the compounds of formula I 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
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
  • 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.
  • Trichostrongylus spp. Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
  • Thorny headed worms 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 formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the compounds of formula I also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
  • Administration can be carried out both prophylactically and therapeutically.
  • Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • 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 formulae I and II, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the compounds of formula I may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds of formula I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds of formula I may be formulated into an implant for subcutaneous administration.
  • the compounds of formula I may be transdermally 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 formula I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on for- mulations 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 formula I 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 accord- ing to what is described above for injection solutions, sterile procedures not being necessary.
  • Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • 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 methyl pyrrol i
  • 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. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monoste
  • 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.
  • Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
  • 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 formula I.
  • the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 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 formula I against endopara- sites 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 formula I are applied dermally / topically.
  • the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the 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 formula I 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;
  • Lipid biosynthesis inhibitors spirodiclofen, spiromesifen, spirotetramat
  • Anthranilamides chloranthraniliprole,cyantraniliprole,
  • M.26. Microbial disruptors Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus,
  • Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Ben- clothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357.
  • the phthalamide M 21.1 is known from WO 2007/101540. Cyflumetofen and its preparation have been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932. Sulfoximine sulfoxaflor has been described in WO 2006/060029 and WO 2007/149134. The alkynylether compound M22.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 2007060839. The carboxamide compound M 22.2 is known from WO 2007/83394. The oxazoline compounds M 22.3 to M 22.6 have been described in WO 2007/074789.
  • the furanon compounds M 22.7 to M 22.16 have been described eg. in WO 2007/115644.
  • 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 2008/115155.
  • 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 formula I or composition ⁇ ) containing them by any application method known in the art.
  • "contacting” includes both direct contact (applying the compounds/compositions directly 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 environ-ment in which a pest or parasite is grow- ing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of formula I 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 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 formula I can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % 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.
  • plant propagation material is to be understood to denote 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 emergence 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.
  • cultivadas plants is to be understood as including 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) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g.
  • cultiva plants is to be understood also including 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.
  • HPPD hy- droxy-phenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonyl ureas see e. g.
  • EP-A-0242236, EP-A-242246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • mutagenesis for example Clearfield ® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox.
  • cultiva plants is to be understood also including 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 Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cry ⁇ c; vegetative insecticidal proteins (VIP), e. g.
  • VIP vegetative insecticidal proteins
  • VIP1 , VIP2, VIP3 or VIP3A insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases
  • 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 com- bination of protein domains, (see, for example WO 02/015701 ).
  • Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, 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.
  • cultivars are to be understood also including 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 example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (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 example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lyso-zym e. g. potato
  • cultiva plants is to be understood also including 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 content or protein content), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • cultiva plants is to be understood also including 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 is to be understood also including 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).
  • HPLC/MS High Performance Liquid Chromatography / mass spectroscopy
  • NMR nuclear magnetic resonance
  • MS Quadrupol electrospray ionisation 80 V (positive modus).
  • Example 1 3-amino-3-(2,3-dimethyl-phenyl)-propionic acid: A mixture of 2,3-dimethylbenzaldehyde (27 g, 0.2 mol) and NH 4 OAc (31 g, 0.4 mol) in EtOH (300 ml) was stirred at 45 0 C and malonic acid (42.1 g, 0.4 mol) in EtOH was added. The resulting mixture was refluxed overnight, filtered and the desired product was obtained as a white solid (15 g, 39% yield).
  • Lithiumaluminiumhydride LiAIH 4 , 5.89 g was added to a solution of 3-amino-3-(2,3- dimethylphenyl)-propionic acid (from example 1) (15 g) in THF (200 ml) at 0 0 C. Then the mixture was warmed up to 60-80 0 C and stirred overnight. Aqueous workup yielded the crude product after evaporation (13 g).
  • Example 7 1-(2-hydroxy-ethyl)-3-(3-phenoxy-1-phenyl-propyl)-thiourea (compound lla.1 of Table 1 )
  • Example 8 (4,5-dihydro-thiazol-2-yl)-(3-phenoxy-1-phenyl-propyl)-amine (compound la.1 of Table 2) To a solution of 1-(2-hydroxy-ethyl)-3-(3-phenoxy-1-phenyl-propyl)-thiourea (0.66 g) and 0.36 g diisopropylethylamine in 10 ml of propionitrile was added at 20-25 ° C 0.61 g cyanomethyl-trimethylphosphonium iodide (prepared according to Tetrahedron 2001 , 57, 5451-54). The reaction mixture was heated up to 90 0 C for 5 h and stirred overnight.
  • Cotton Aphid (Aphis gossypii) The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic ® 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.
  • 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 coty-ledons 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.
  • R-3603 non-toxic Tygon® tubing
  • 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 cov- ered 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 oC and 20- 40% relative humid-ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.

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Abstract

The present invention relates to aminothiazoline compounds of the general formula (I): wherein A is a radical of the formulae A1 or A2: wherein * denotes the binding site and wherein the indices and variables are as defined in the description, methods of combating animal pests selected from insects, arachnids and nematodes and for protecting crops from attack or infestation by insects, arachnids or nematodes employing such compounds of formula (I), and agricultural compositions comprising compounds of formula (I). It also relates to open thiourea derivatives of the previous compounds as pesticides.

Description

Aminothiazoline compounds for combating insects, arachnids and nematodes
The present invention relates to aminothiazoline compounds of the general formula (I):
Figure imgf000002_0001
wherein A is a radical of the formulae A1 or A2:
Figure imgf000002_0002
A1 A2
wherein * denotes the binding site and wherein m is 0, 1 , 2, 3, or 4; j is 1 , 2, or 3;
X is sulfur, oxygen, or NRk;
Rk has the meaning as defined for R1;
R1 is hydrogen, cyano, nitro, d-Cε-alkyl, formyl, d-Cβ-alkylcarbonyl, d-Cβ- alkoxycarbonyl, d-Cβ-alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R#,
R# is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, or d-Ce-alkylthio;
C(O)NRaRb, or (SO2)NRaRb,
wherein Ra and Rb are each independently hydrogen, d-Cβ-alkyl, C2-C6- alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R#;
phenyl, phenyloxy, or benzyl, each of which three radicals may be unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Cβ-alkyl, d-Cβ- haloalkyl, d-Cβ-alkylthio, d-Cβ-haloalkylthio, d-Cβ-alkoxy or d-Cβ-haloalkoxy groups;
R2 is halogen, OH, SH, NH2, SO3H, COOH, cyano, nitro, Ci-C6-alkyl, d-Ce-alkoxy, Ci-Cε-alkylamino, di(Ci-C6-alkyl)amino, d-Cs-alkylthio, C2-C6-alkenyl, C2-C6- alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6-alkynyl, C2-C6- alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, d-Cβ-alkylsulfonyl, Ci-Cβ- alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, formyl, Ci-Cβ- alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ- alkoxycarbonyl, C2-C6-alkenyloxycarbonyl, C2-C6-alkynyloxycarbonyl, carbony- loxy, Ci-Cβ-alkylcarbonyloxy, Ci-Cβ-alkenylcarbonyloxy, Ci-Cβ-alkynyl- carbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R#,
C(O)NRaRb, (SO2)NRaRb, wherein Ra and Rb are as defined for R1 above;
a radical Y-Ar or a radical Y-Cy, wherein
Y is a single bond, oxygen, sulfur, C-i-Cβ-alkandiyl or Ci-Cβ-alkandiyloxy, Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered het- eroaromatic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is unsubsti- tuted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R#; and
Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals R#;
and wherein two radicals R2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals R#;
R3, R4 are each independently hydrogen, Ci-Cβ-alkyl, C-i-Cβ-haloalkyl, Cs-Cβ-cycloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R#,
phenyl or benzyl, each unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, CrC6- haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups;
W is phenyl which is unsubstituted or substituted by 1 , 2, 3, or 4 independently selected substituents R2; or
a 5- to 6-membered heteroaromatic ring which contains from 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, wherein the heteroaromatic ring may optionally be fused to a ring selected from phenyl and a 5- to 6-membered saturated, partially unsaturated or aromatic heterocyclic ring which contains from 1 to 3 heteroatoms selected from oxygen, ni- trogen and sulfur, and wherein the 5- to 6-membered heteroaromatic ring or the respective fused ring systems are unsubstituted or substituted by R5 and/or any combination of 1 to 4 groups R6:
Figure imgf000004_0001
wherein n is 0, 1 , 2, 3, or 4;
R5 is hydrogen, cyano, nitro, formyl, C(=O)R5c, C(=S)R5c, d-Ce-alkyl, C2- Cβ-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, Ci-Cβ-alkoxy, (Ci-Cβ- alkoxy)methylen, Ci-Cβ-alkylsulfinyl, Ci-Cβ-alkylsulfenyl or Ci-Cβ- alkylsulfonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ- alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ- haloalkoxy and Ci-C6-alkylthio; or
C(O)NR5aR5b, C(O)NR5aR5b, C(O)NR5aR5b, (SO2)NR5aR5b, (SO2)NR5aR5b or (SO2)NR5aR5b; or phenyl, phenyloxy or benzyl, each of the last three mentioned radicals may be unsubstituted or substituted with 1 to 5 radicals, independently of one another selected from the group consisting of one to five halogen radicals, one to three Ci-Cβ-alkyl, one to three Ci-Cβ- haloalkyl, one to three d-Cβ-alkylthio, one to three Ci-Cβ- haloalkylthio, one to three Ci-Cβ-alkoxy and one to three Ci-Cβ- haloalkoxy radicals; and wherein R5a, R5b and R5c are defined as below;
R6 is selected from halogen, OH, SH, NH2, SO3H, COOH, cyano, azido, nitro, formyl, CONH2, CSNH2, CH=N-OH, CH=N-O-(Ci-C6)-alkyl, C(=O)R6c, C(=S)R6c, d-Cβ-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8- cycloalkyl, Ci-Cβ-alkylamino, C2-C6-alkenylamino, C2-C6-alkynylamino, di(Ci-C6-alkyl)amino, di(C2-C6-alkenyl)amino, di(C2-C6-alkynyl)amino, d-Ce-alkylthio, C2-C6-alkenylthio, C2-C6-alkynylthio, CrC6- alkylsulfonyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, (Ci-Cβ- alkyl)carbonyl, (C2-C6-alkenyl)-carbonyl, (C2-C6-alkynyl)-carbonyl, Ci-
Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, (C1-C6- a I koxy)ca rbonyl , (C2-C6-a I kenyloxy) ca rbonyl , (C2-C6-a I kynyloxy)- carbonyl, (Ci-C6-alkyl)carbonyloxy, (C2-C6-alkenyl-)carbonyl-oxy, (C2- C6-alkynyl-)carbonyloxy, (Ci-C6-alkyl)carbonyl-amino, (C2-Cβ- alkenyl)carbonyl-amino, (C2-C6-alkynyl)carbonyl-amino, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of one, two or three radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, d-Cβ-haloalkoxy, d-Cβ-haloalkyl and d-Cβ-alkylthio; or C(O)NR6aR6b or (SO2)NR6aR6b; wherein R6a, R6b and R6c are defined as below, a radical Y-Ar or a radical Y-Cy, wherein Y is a single bond, oxygen, sulfur, NH, d-Cβ-alkandiyl or d-Cβ- alkandiyloxy; Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered heteroaromatic ring, which contains 1 , 2, 3 or 4 heteroatoms selected from 1 or 2 oxygen, 1 or 2 sulfur and 1 to 3 nitrogen at- oms as ring members, wherein Ar is unsubstituted or substituted with any combination of one to five radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-haloalkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio;
Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with one to five radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C6-alkyl, d-Cβ-haloalkyl, C-i-Cβ- alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and d-Cβ-alkylthio;
and wherein
R5a, R5b, R6a and R6b are each independently selected from hydrogen, d-Ce-alkyl, d-Ce-haloalkyl, C2-C6- alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of one, two or three radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C2-C6- alkenyl, C2-C6-alkynyl, d-Cβ-alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, C-i-Cβ- haloalkoxy, d-Cβ-haloalkyl and C-i-Cβ- alkylthio; R5c and R6c are each independently selected from hydrogen, d-Cε al- kyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, CrC6- alkylthio,Ci-C6-alkoxy, (Ci-C6-alkyl)amino, di(Ci-C6- alkyl)amino, hydrazino, (Ci-C6-alkyl)hydrazino, di(Ci-C6- alkyl)hydrazino, phenyl and heteroaryl, which can be a mono- or bicyclic 5 to 10 membered heteroaromatic ring, which contains 1 ,2,3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen;
and the enantiomers, diastereomers, and agriculturally and veterinarily acceptable salts thereof.
The present invention also relates also to a method of combating animal pests, se- lected from insects, arachnids and nematodes, which comprises contacting the animal pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by insects, arachnids or nematodes with a pesticidally effective amount of at least one aminothiazoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof.
The present invention also provides pesticidal compositions comprising at least one aminothiazoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof and a solid or liquid carrier.
Furthermore, the invention relates to pesticidal compositions, preferably in the form of directly sprayable solutions, emulsions, pastes oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprise at least one aminothia- zoline compound of formula I and/or at least one enantiomer, diastereomer, or salt thereof and a solid or liquid carrier, admixed with one or more agronomically or veterinarily acceptable inert, solid or liquid carrier(s) and, if desired, at least one surfactant.
WO 2006/74262 discloses pharmaceutically active aminothiazoline compounds which may carry an aryloxyalkyl ligand at the amino group. These compounds however do not also carry a benzyl ligand at the amino group as the compounds of the present invention.
Animal pests and in particular insects, arachnids and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating insects, arachnids and nematodes.
It is therefore an object of the present invention to provide compounds having a good pesticidal activity and show a broad activity spectrum against a large number of different animal pests, especially against difficult to control insects, arachnids and nematodes.
This object has been achieved by providing the new compounds of formula I. These compounds have a high pesticidal activity and are active against a broad spectrum of animal pests selected from insects, arachnids and nematodes.
The compounds of the general formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The present invention provides both the pure enantiomes or diastereomers or mixtures thereof. The compounds of the general formula I may also exist in the form of different tautomers. The invention comprises the single tautomers, if separable, as well as the tautomer mixtures.
Salts of the compounds of the formula I are especially agriculturally or veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality or by reacting an acidic compound of formula I with a suitable base.
Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and bar- ium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 +) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci- C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituded ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammo- nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2- hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammo- nium and benzyltriethylammonium, 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 the compounds of the formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hy- drochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
Examples of other meanings are :
The term "Ci-Cβ-alkyl" as used herein and in the alkyl moieties of d-Cβ-alkoxy, C-i-Cβ- alkylamino, di(Ci-C6-alkyl)amino, C-i-Cβ-alkylthio, Ci-Cβ-alkylsulfonyl, C-i-Cβ- alkylsulfoxyl, d-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, Ci-Cβ-alkylthiocarbonyl and Ci-Cβ-alkylcarbonyloxy refer to a saturated straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 4 carbon groups, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1 ,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3- methylpentyl, 4-methylpentyl, 1 ,1 -dim ethyl butyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. Ci-C4-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl. In each alkyl radical the carbon atoms may, in accordance with the respective definitions for the compound of formula I above, carry 1 , 2 or 3 radicals R#. In other words, each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R#. In case of R# being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, especially by fluorine or chlorine. These radicals are also referred to as haloalkyl. In case of R# being cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, or C-i-Cβ-alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R#.
The term "Ci-Cβ-haloalkyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C4-haloalkyl, such as chloromethyl, bromomethyl, di- chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro- fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1- fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like.
The term, C-i-Cβ-alkoxy" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom. Examples include Ci-Cβ-alkoxy such as methoxy, ethoxy, OCH2-C2H5, OCH(CHs)2, n-butoxy, OCH(CHs)-C2H5, OCH2-CH(CHs)2, OC(CHs)3, n-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1-dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethyl-propoxy, 1-ethylpropoxy, n-hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy, 1 -ethyl-2- methylpropoxy and the like.
The term "Ci-Cβ-haloalkoxy" as used herein 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, i.e., for example, d-Cβ-haloalkoxy such as chloro- methoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 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, pentafluoroethoxy, 2-fluoropropoxy, 3- fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3- trifluoropropoxy, 3,3,3-trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropro- poxy, 1-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloroethoxy, 1- (bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nona- fluorobutoxy, 5-fluoro-1-pentoxy, 5-chloro-1-pentoxy, 5-bromo-i-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 or dodecafluoro- hexoxy, in particular chloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trifluoroethoxy.
The term "Ci-Cβ-alkylcarbonyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group. Examples include Ci-Cβ-alkylcarbonyl such CO-CH3, CO-C2H5, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl, 1 ,1- dimethylethylcarbonyl, n-pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 1 ,1-dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1- methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4- methylpentylcarbonyl, 1 ,1-dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3- dimethylbutylcarbonyl, 2,2-dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3- dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2- trimethylpropylcarbonyl, 1 ,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1-ethyl-2-methylpropylcarbonyl and the like.
The term "Ci-C6-alkoxycarbonyl" as used herein refers to a straight-chain or branched alkoxy group (as mentioned above) having 1 to 6 carbon atoms attached via the carbon atom of the carbonyl group. Examples include (Ci-C6-alkoxy)carbonyl, for example CO- OCH3, CO-OC2H5, COO-CH2-C2H5, CO-OCH(CHs)2, n-butoxycarbonyl, CO-OCH(CH3)- C2H5, CO-OCH2CH(CHs)2, CO-OC(CH3)S, n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1- ethylpropoxycarbonyl, n-hexoxycarbonyl, 1 ,1-dimethylpropoxycarbonyl, 1 ,2- dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2-methylpentoxycarbonyl, 3- methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1 ,1-dimethylbutoxycarbonyl, 1 ,2- dimethylbutoxycarbonyl, 1 ,3-dimethylbutoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3- dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1-ethylbutoxycarbonyl, 2- ethylbutoxycarbonyl, 1 ,1 ,2-trimethylpropoxycarbonyl, 1 ,2,2-trimethylpropoxycarbonyl, 1 -ethyl-1 -methylpropoxycarbonyl or 1 -ethyl-2-methylpropoxycarbonyl
The term "Ci-Cβ-alkylcarbonyloxy" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) bonded via the carbon atom of the carbonyloxy group at any bond in the alkyl group. Examples include Ci-Cβ-alkylcarbonyloxy such O-CO-CH3, 0-CO-C2H5, n-propylcarbonyloxy, 1- methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2- methylpropylcarbonyloxy, 1 ,1-dimethylethylcarbonyloxy, n-pentylcarbonyloxy, 1- methylbutylcarbonyloxy, 2-methylbutylcarbonyloxy, 3-methylbutylcarbonyloxy, 1 ,1- dimethylpropylcarbonyloxy, 1 ,2-dimethylpropylcarbonyloxy and the like.
The term "d-Cε-alkylthio (C-i-Cβ-alkylsulfanyl: C-i-Cβ-alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example Ci-C4-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2- methylpropylthio, 1 ,1-dimethylethylthio, n-pentylthiocarbonyl, 1-methylbutylthio, 2- methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n- hexylthio, 1 ,1-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1-methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1-dimethylbutylthio, 1 ,2- dimethylbutylthio, 1 ,3-dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2- trimethylpropylthio, 1 -ethyl-1 -methylpropylthio or 1-ethyl-2-methylpropylthio.
The term "Ci-Cβ-alkylthiocarbonyl" as used herein refers to a straight-chain or branched alkthio group (as mentioned above) having 1 to 6 carbon atoms attached via the carbon atom of the carbonyl group. Examples include CO-SCH3, CO-SC2H5,
CO-SCH2-C2H5, CO-SCH(CHs)2, n-butylthiocarbonyl, CO-SCH(CHs)-C2H5, CO-SCH2- CH(CHs)2, CO-SC(CH3)S, n-pentylthiocarbonyl, 1-methylbutylthiocarbonyl, 2- methylbutylthiocarbonyl, 3-methylbutylthiocarbonyl, 2,2-dimethylpropylthiocarbonyl, 1- ethylpropylthiocarbonyl, n-hexylthiocarbonyl, 1 ,1-dimethylpropylthiocarbonyl, 1 ,2- dimethylpropylthiocarbonyl, 1-methylpentylthiocarbonyl, 2-methylpentylthiocarbonyl, 3- methylpentylthiocarbonyl, 4-methylpentylthiocarbonyl, 1 ,1-dimethylbutylthiocarbonyl, 1 ,2-dimethylbutylthiocarbonyl, 1 ,3-dimethylbutythiocarbonyl, 2,2- dimethylbutylthiocarbonyl, 2,3-dimethylbutylthiocarbonyl, 3,3-dimethylbutylthiocarbonyl, 1-ethylbutlthioycarbonyl, 2-ethylbutylthiocarbonyl, 1 ,1 ,2-trimethylpropylthiocarbonyl, 1 ,2,2-trimethylpropylthiocarbonyl, 1 -ethyl-1 -methylpropylthiocarbonyl or 1 -ethyl-2- methylpropylthiocarbonyl
The term "Ci-C6-alkylsulfinyl" (Ci-C6-alkylsulfoxyl: Ci-C6-alkyl-S(=O)-), as used herein refers to a straight-chain or branched saturated hydrocarbon group (as mentioned above) having 1 to 6 carbon atoms bonded through the sulfur atom of the sulfinyl group at any bond in the alkyl group. Examples include C-i-Cβ-alkylsulfinyl: SO-CH3, SO- C2H5, n-propylsulfinyl, 1-methylethylsulfinyl, n-butylsulfinyl, 1-methylpropylsulfinyl, 2- methylpropylsulfinyl, 1 ,1-dimethylethylsulfinyl, n-pentylsulfinyl, 1-methylbutylsulfinyl, 2- methylbutylsulfinyl, 3-methylbutylsulfinyl, 1 ,1-dimethylpropylsulfinyl, 1 ,2- dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, n-hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4- methylpentylsulfinyl, 1 ,1-dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 ,3- dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3- dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1 ,1 ,2- trimethylpropylsulfinyl, 1 ,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl or 1- ethyl-2-methylpropylsulfinyl.
The term "Ci-C6-alkylamino" refers to a secondary amino group carrying one alkyl group as defined above e.g. methylamino, ethylamino, propylamino, 1- methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1 ,1- dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3- methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropylamino, hexylamino, 1 ,1- dimethylpropylamino, 1 ,2-dimethylpropylamino, 1-methylpentylamino, 2- methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1- dimethylbutylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2- dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1- ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2-trimethylpropylamino, 1 ,2,2- trimethylpropylamino, 1 -ethyl-1 -methylpropylamino, 1 -ethyl-2-methylpropylamino.
The term "di(Ci-C6-alkyl)amino" refers to a tertiary amino group carrying two alkyl radicals as defined above e.g. dimethylamino, diethylamino, di-n-propylamino, diisopro- pylamino, N-ethyl-N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N- methylamino, N-(n-butyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N- methylamino, N-(isobutyl)-N-methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)-N- ethylamino, N-(isopropyl)-N-ethylamino, N-(n-butyl)-N-ethylamino, N-(n-pentyl)-N- ethylamino, N-(2-butyl)-N-ethylamino, N-(isobutyl)-N-ethylamino, N-(n-pentyl)-N- ethylamino, etc.
The term "Ci-Cβ-alkylsulfonyl" (Ci-C6-alkyl-S(=O)2-) as used herein refers to a straight- chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) which is bonded via the sulfur atom of the sulfonyl group at any bond in the alkyl group. Examples include d-Cβ-alkylsulfonyl such as SO2-CH3, SO2-C2H5, n- propylsulfonyl, SO2-CH(CH3)2, n-butylsulfonyl, 1-methylpropylsulfonyl, 2- methylpropylsulfonyl, SO2-C(CH3)3, n-pentylsulfonyl, 1-methylbutylsulfonyl, 2- methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl, 1 ,2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, n- hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4- methylpentylsulfonyl, 1 ,1-dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3- dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3- dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2- trimethylpropylsulfonyl, 1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl or 1-ethyl-2-methylpropylsulfonyl and the like. The term "C2-C6-alkenyl" as used herein and in the alkenyl moieties of C2-C6- alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6-alkenylsulfonyl, C2-C6- alkenylcarbonyl, C2-C6-alkenyloxycarbonyl, and C2-C6-alkenylcarbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl- ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1- methyl-2-propenyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2- methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl- 3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1- pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2- pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3- pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4- pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2- dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1-butenyl, 1 ,3-dimethyl-2- butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3- dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2- butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2- ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2- propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;
In each alkenyl radical the carbon atoms may, in accordance with the respective defini- tions for the compound of formula I above, carry 1 , 2 or 3 radicals R#. In other words, each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R#. In case of R# being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, especially by fluorine or chlorine. These radicals are also referred to as haloalkyl. In case of R# being cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cε-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, or d-Cε-alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R#.
The term, "C2-C6-alkenyloxy" as used herein refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy, etc.
The term "C2-C6-alkenylthio" as used herein refers to a straight-chain or branched satu- rated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylsulfanyl, allylsulfanyl (propen-3-ylthio), methallylsufanyl, buten-4-ylsulfanyl, etc.. The term "C2-C6-alkenylamino" as used herein refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example vinylamino, allylamino (propen-3-ylamino), methallylamino, buten-4-ylamino, etc.
The term "C2-C6-alkenylsulfonyl" as used herein refers to a straight-chain or branched saturated alkenyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example vinylsulfonyl, allylsulfonyl (propen-3- ylsulfonyl), methallylsufonyl, buten-4-ylsulfonyl, etc.
The term "C2-C6-alkynyl" as used herein and in the alkynyl moieties of C2-C6- alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, C2-C6-alkynylsulfonyl, C2-C6- alkynylcarbonyl, C2-C6-alkynyloxycarbonyl, and Ci-Cβ-alkynylcarbonyloxy refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2-yn- 1-yl, n-but-1-yn-1-yl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-1-yl, n-pent-1-yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1-yl, n-hex-1- yn-3-yl, n-hex-1-yn-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn- 4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1- yn-1-yl, 3-methylpent-1 -yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4- methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl and the like.
In each alkynyl radical the carbon atoms may, in accordance with the respective definitions for the compound of formula I above, carry 1 , 2 or 3 radicals R#. In other words, each of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R#. In case of R# being halogen usually 1 , 2, 3 or all of the hydrogen atoms in said alkyl radical are replaced by halogen, espe- cially by fluorine or chlorine. These radicals are also referred to as haloalkyl. In case of R# being cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cε-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, or d-Cε-alkylthio usually 1 or 2 of the hydrogen atoms in said alkyl radikal may be replaced by the radical R#.
The term, "C2-C6-alkynyloxy" as used herein refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propin-3-yloxy), butin-3-yloxy, butin-4-yloxy, etc.
The term "C2-C6-alkynylthio" as used herein refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is at- tached via a sulfur atom, for example propargylsulfanyl (propin-3-ylthio), butin-3- ylsufanyl, butin-4-ylsulfanyl, etc.
The term "C2-C6-alkynylamino" as used herein refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfur atom, for example propargylamino (propin-3-ylamino), butin-3- amino, butin-4-ylamino, etc.
The term "C2-C6-alkynylsulfonyl" as used herein refers to a straight-chain or branched saturated alkynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via a sulfonyl (SO2) group, for example propargylsulfonyl (propin-3- yltsulfonyl), butin-3-ylsufonyl, butin-4-ylsulfonyl, etc.
The term "Cs-Cs-cycloalkyl" as used herein refers to a mono- or bi- or polycyclic hydro- carbon radical having 3 to 12 carbon atoms, in particular 3 to 6 carbon atoms. Examples of monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl.
Each cycloalkyl radical may carry 1 to 3 of the aforementioned radicals R#. In other words, 1 to 3 of the hydrogen atoms in these radicals may independently from the others be replaced by one of the aforementioned radicals R#. Preferred radicals R# on cycloalkyl are selected from halogen, especially fluorine or chlorine, and d-Cε-alkyl.
The term "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 comprise a fused 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 of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The fused ring comprises C5-C7-cycloalkyl, C5-C7-cycloalkenyl, or 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 carrying a fused phenyl ring are quinolinyl, isoquinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl. Ex- amples for 5- to 6-membered heteroaromatic rings carrying a fused cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
The term "5 to 7-membered heterocyclyl" comprises monocyclic heteroaromatic rings as defined above and nonaromatic saturated or partially unsaturated heterocyclic rings having 5, 6 or 7 ring members. Examples for non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydro- furanyl, 1 ,3-dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, diox- anyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like.
As regards the pesticidal activity of the compounds of general formula I, preference is given to those compounds of the formula I, wherein the variables have independently of each other or, more preferably, in combination the following meanings.
Preference is given to compounds wherein m is 0, 1 or 2, especially 1 or 2, preferably 2.
Preference is given to compounds wherein j is 1.
Preference is given to compounds wherein X is sulfur or oxygen, preferably sulfur. Preference is given to compounds wherein X is sulfur.
Preference is given to compounds wherein R1 is hydrogen, Ci-Cβ-alkylcarbonyl, or Ci- Cβ-alkoxycarbonyl.
Preference is given to compounds wherein R1 is hydrogen or acetyl.
Special preference is given to compounds wherein R1 is hydrogen.
Preference is given to compounds wherein R2 when attached to the phenyl group of compounds I which is not W is halogen, especially fluorine, chlorine, or bromine, C1-C4- alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, or 2 groups R2 which are bound to adjacent carbon atoms of the phenyl ring together form a group -O-CH2CH2-, -O-CH2CH2CH2-, -O-CH2- O-, -O-CH2CH2-O-, -(CH2)S-, -(CH2J4- ,Or -CH=CH-CH=CH-.
Preference is given to compounds wherein R2 when attached to the phenyl group of compounds I which is not W is chlorine, Ci-C4-alkyl, especially methyl, or 2 groups R2 which are bound to adjacent carbon atoms of the phenyl ring together form a group -O- CH2CH2-, -0-CH2CH2CH2-, -0-CH2-O-, -0-CH2CH2-O-, -(CH2J3-, -(CH2J4- ,or -CH=CH-CH=CH-.
Preference is given to compounds wherein m is 2 and R2 when attached to the phenyl group of compounds I which is not W is in the 2- and 3-position of the phenyl ring.
Preference is given to compounds wherein R3 is hydrogen or Ci-C4-alkyl, especially hydrogen or methyl and most preferred hydrogen.
Preference is given to compounds wherein R4 is hydrogen or Ci-C4-alkyl, especially hydrogen or methyl and most preferred hydrogen.
Preference is given to compounds wherein W is phenyl which is unsubstituted or sub- stituted by 1 , 2, 3, or 4, preferably with 1 , 2, or 3 independently selected substituents R2.
Preference is given to compounds wherein W is phenyl which is unsubstituted or substituted with 1 , 2 or 3 independently selected substituents R2, preferably phenyl which is unsubstituted or substituted with 1 or 2 substituents R2.
Preference is given to compounds wherein W is phenyl which is substituted with 2 independently selected substituents R2, preferably with halogen, Ci-C4-alkyl, C1-C4- alkoxy, or Ci-C4-haloalkyl, most preferably with chlorine, bromine, methyl, trifluoro- methyl, or methoxy.
Special preference is given to compounds wherein W is phenyl which is disubstituted in the 3,5-positions with 2 independently selected substituents R2, preferably with 2 methyl groups.
Amongst compounds I, preference is given to those wherein A is a radical of formula A2, in particular compounds of the formula I with A being A2 wherein R1 is hydrogen. These compounds are tautomers of the compounds of formula I with A being A1 wherein R1 is hydrogen. These tautomers are present as their equilibrium mixture.
Amongst compounds of the formula I, preference is given to the following compounds of the formula I-A, wherein A is a radical A2 with X being O:
(I-A)
Figure imgf000017_0001
wherein m and w are each independently 0, 1 , 2, 3, or 4, and R2A and R2B each independently are as defined above for compounds of formula I for R2. Examples of these compounds are those wherein (R2A)W and (R2B)m have the meanings given in each line of table A (Compounds I-A.1 to I-A.108). In table A, the number in front of the radical indicates its position on the phenyl ring.
Table A
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Amongst compounds of the formula I, preference is given to the following compounds of the formula I-B, wherein A in formula I is a radical A2 with X being S, and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R2A and R2B each independently are as defined above for compounds of formula I for R2.
Figure imgf000021_0001
Examples of these compounds are those wherein (R2A)W and (R2B)m have the meanings given in each line of table A (Compounds I-B.1 to I-B.108).
Amongst compounds of the formula I, preference is also given to the following compounds of the formula I-C, wherein A in formula I is a radical A1 with X being O and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R2A and R2B each independently are as defined above for compounds of formula I for R2.
Figure imgf000021_0002
Examples of these compounds are those wherein (R2A)W and (R2B)m have the meanings given in each line of table A (Compounds I-C.1 to I-C.108).
Amongst compounds of the formula I, preference is also given to the following compounds of the formula I-D, wherein A in formula I is a radical A1 with X being S and wherein m and w are each independently 0, 1 , 2, 3, or 4, and R2A and R2B each independently are as defined above for compounds of formula I for R2.
Figure imgf000021_0003
Examples of these compounds are those wherein (R2A)W and (R2B)m have the meanings given in each line of table A (Compounds I-D.1 to I-D.108).
The compounds of the present invention can be e.g. prepared from the corresponding amines III or a salt thereof by the synthetic routes outlined in schemes 1 and 2.
Scheme 1 : thiophosgene
Figure imgf000022_0001
compounds (II)
Figure imgf000022_0002
According to the method outlined in scheme 1 , the amine III is converted into the corresponding isothiocyanate IV by conventional means, e.g. by reacting III with thiophosgene (see e.g. Houben-Weyl, E4, "Methoden der Organischen Chemie", chapter INc, pp. 837-842. The isothiocyanate IV is then reacted with an aminoethanol of the general formula V, thereby obtaining the thiourea compound of the formula II. The reaction of the aminoethanol V wherein R7 is hydrogen with isothiocyanate IV can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Bio- chem. 1992, 56 (7), 1062-1065.
Scheme 2:
compounds (II)
Figure imgf000022_0003
Alternatively, an amine III or a salt thereof can be converted to the corresponding ami- nothiocarbonylaminoethane compound II, by reacting the amine III with an isothiocyanate Vl according to scheme 2. lsothiocyanates Vl wherein R7 is d-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, or benzoyl can be prepared according to the procedures described in Coll. Czech. Chem. Commun. 1986, 51 , 1 12-117.
According to scheme 3, the thus obtained thioureas of formula Il can be cyclized by conventional means thereby obtaining the desired thiazoline compound of the formula I, wherein A is A2 with X being S. Cyclization of compound Il can be achieved e.g. under acid catalysis or under dehydrating conditions e.g. by Mitsunobu's reaction (see Tetrahedron Letters1999, 40, 3125-3128) in particular if R7 is hydrogen. Alternatively, the R7 group can be cleaved prior to cyclisation, e.g. by saponification if R7 is C-i-Cβ- alkylcarbonyl, Ci-Cβ-alkoxycarbonyl or benzoyl.
Scheme 3
Figure imgf000023_0001
Compounds of the formula I, wherein A is a radical A2 with X being O and R1 being H can be obtained by a route similar to this method (see also Pestic. Biochem. Physiol.1988, 30, 190-197). Unlike the method of scheme 1 , the amine III is converted into the corresponding isocyanate , e.g. by reaction with phosgen, diphosgen or another phosgene equivalent. The isocyante is then reacted with aminoethanol V and the thus obtained urea is cyclized.
Alternatively, the compounds of the formula I according to the invention wherein X is O or S can be prepared by the method shown in scheme 4. In scheme 4, the variable Hal is halogen, especially chlorine.
Scheme 4:
Figure imgf000023_0002
E. g., an amine IV or a salt thereof can be converted to an azoline I by reaction with 2- chloroethylisothiocyanate or 2-chloroethylisocyanate e.g. as described in Bioorg. Med. Chem. Lett. 1994, 4, 2317-22 and subsequent cyclization in the presence or absence of base. "l-ChloiO-2-isothiocyanatoethane (CAS-reg.-no.: 6099-88-3) and 2- chloroethylisocyanate (CAS-reg.-no.: 1943-83-5) are commercially available.
Compounds of the formula I according to the invention wherein X is NR1 may be prepared by the method shown in scheme 5.
Scheme 5:
Figure imgf000024_0001
(base) LG is a leaving group such as e.g. Cl, Br, I, OSO2R, OCO2R, wherein the R is C1-C4- alkyl.
Compounds of the formula I may be obtained by reacting an appropriate substituted amine III or a salt thereof with a 2-substituted imidazoline VII in an appropriate solvent. This reaction can be carried out, for example analogous to the methods described in US 5,130,441 or EP 0389765.
Compounds of formula I, wherein A in formula I is a radical A1 with R1 being different from hydrogen or a radical A2 with R1 different from hydrogen, can be obtained from compounds of the formula I as outlined in scheme 6.
Figure imgf000024_0002
For instance, a compound I-H is treated with a suitable electrophile. Suitable electro- philes are e.g. an alkylating or acylating agent R56-LG (LG = leaving group; e.g. Cl, Br, I, OSO2R, OCO2R, wherein the R is Ci-C4-alkyl), e. g. as described in WO 2005063724. Preparation of starting materials
Amines IX and X are known in the art or can be prepared by methods familiar to an organic chemist, for instance as described in Tetrahedron Letters 2004, 45, 1503-1505, Heterocycles 1989, 28 (2), 1015-31 or in Synthesis 2003, 10, 1626-38 and as demonstrated below in the preparation procedure and as outlined in scheme 7. The conversion of amines X to amines III is done according to standard procedures for cleavage of amine protective groups, e.g. as described in P. J. Kocienski, Protective groups, 1st ed., Thieme, 1994, and in analogy to the experimental procedures described in the experimental section below.
Scheme 7:
reduction
e.g. LiAIH4
N-protection
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000025_0003
As a rule, the compounds of formula I 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 formula I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefi- nation, reduction, metal catalyzed coupling reactions, oxidation and the like. Compounds of formula Il
Figure imgf000026_0001
wherein the substituents and indices are as defined above for compounds I, and wherein R7 is hydrogen, Ci-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl, or benzoyl, are also a subject of the present invention.
The preferences of the substituents and of the indices for compounds Il are the same as described above for compounds of formula I.
Compounds Il can also be used for their pesticidal activity. Pesticidal use and methods to combat animal pests and to protect crops, plants and animals from animal pests with compounds Il is also a subject of the present invention. Therefore the methods and uses as described below for compounds I are also applicable for compounds II.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colourless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or digestion.
The inventive compounds I may be present in different crystalline modifications which may differ in their biological activity. These are also subject of the present invention.
Due to their excellent activity, the compounds of formulae I and Il may be used for controlling animal pests.
Accordingly, the present invention also provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the 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 formula lor a salt thereof or a composition as defined above.
Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infesta- tion and comprises treating the plant propagation material (such as seed) with a pesti- cidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
In the sense of the present invention, "animal pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
The invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of formula lor at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may contain a single active compound of formula I or a salt thereof or a mixture of several active compounds of formula lor 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 tautomers or mixtures of tautomers.
The compound of formula I and the pestidicidal compositions comprising it are effective agents for controlling arthropod pests and nematodes. Animal pests controlled by the compound of formula I include for example:
insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris bras- sicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci;
hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, NiIa- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli,
Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furcifera Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
Siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp ; The compositions and compounds of formula I are useful for the control of nematodes, especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla,Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species;
cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Het- erodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; AwI nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Paratylen- chus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhyn- chus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
In a preferred embodiment of the invention the compounds of formula I are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina. The compounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
The compounds of formula I or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pes- ticidally effective amount of compounds of formula I. The term "crop" refers both to growing and harvested crops.
The compounds of formula I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active com- pound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
Suitable emulsifiers are non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emul- sions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
A suitable preservative is e.g. dichlorophen.
Seed treatment formulations may additionally comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also po- lyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybute-nes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, 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, pig- ment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®).
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
The compounds of formula I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusta- ble products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight. The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
The following are examples of formulations:
1. Products for dilution with water for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
A) Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formula- tion with 10 % (w/w) of active compound(s) is obtained.
B) Dispersible concentrates (DC)
20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
E) Suspensions (SC, OD, FS) In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active compound^), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
I) Dustable powders (DP, DS)
5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)
J) Granules (GR, FG, GG, MG) 0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound^) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV solutions (UL)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.
The compound of formula I is also suitable for the treatment of plant propagation materials (such as seed). Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersi- ble 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 preger-minated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Other preferred FS formulations of compounds of formula lfor seed treatment comprise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
The compounds of formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, compounds of formula I are preferably used in a bait composition. The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cock- roaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g. kerosenes) having boiling ranges of approximately 50 to 2500C, dimethyl- fomaamide, N methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
The compounds of formula I and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vapor- izers and also in moth papers, moth pads or other heat-independent vaporizer systems. Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula I and 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, nonwov- ens, 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 pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and diethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the active compounds of formula I or spraying them onto the nets.
Methods which can be employed for treating the seed are, in principle, all suitable seed treatment and especially seed dressing techniques known in the art, such as seed coating (e.g. seed pelleting), seed dusting and seed imbibition (e.g. seed soaking). Here, "seed treatment" refers to all methods that bring seeds and the compounds of formula I into contact with each other, and "seed dressing" to methods of seed treatment which provide the seeds with an amount of the compounds of formula I, i.e. which generate a seed comprising the compounds of formula I. In principle, the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed. The seed can be treated immediately before, or during, the planting of the seed, for example using the "planter's box" method. However, the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
Expediently, the treatment is applied to unsown seed. As used herein, the term "unsown seed" is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Specifically, a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device 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 appropriate, this is followed by a drying step.
The compounds of formula I 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 formula I 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 lor 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 a parasiticidally effective amount of a compound of formula lor the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, nonemetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly, it has been found that compounds of formula I are suitable for corn-bating endo- and ectoparasites in and on animals. Compounds of formula I 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 infec- tions in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds of formula I 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 formula I 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 formula I are especially useful for combating ectoparasites.
The compounds of formula I are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intes- tinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Lep- toconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar- gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sar- cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,
actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp,
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp, Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
The compounds of formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of compounds of formula I and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula I and compositions containing them for combating flies is a further preferred embodiment of the present invention. Furthermore, the use of the compounds of formula I and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula I and of the compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of formula I also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the compounds of formulae I and Il may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addi-tion, the compounds of formulae I may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formulae I and II, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of formula I may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula I may be formulated into an implant for subcutaneous administration. In addition the compounds of formula I may be transdermally administered to animals. For parenteral administra- tion, 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 formula I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on for- mulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of formulae I or II. In addition, the compounds of formula I may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are: Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
Solid preparations such as powders, premixes or concentrates, granules, pellets, tab- lets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and accord- ing to what is described above for injection solutions, sterile procedures not being necessary. Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N methyl pyrrol i- done, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols. Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyl- dodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose. In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compounds of formula I.
Generally, it is favorable to apply the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most preferably from 5 to 40 percent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight.
Furthermore, the preparations comprise the compounds of formula I against endopara- sites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formula I are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally, it is favorable to apply solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formulae I or II. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
Compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
These agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds of formula I or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
The following list M of pesticides together with which the compounds according to the invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation:
M.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-ethyl, azinphos- methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos- methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicro- tophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phor- ate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirim- fos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamido- thion;
M.2. Carbamates: aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxy- carboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, pro- poxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
M.3. Pyrethroids: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta- cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha- cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flu- cythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, teflu- thrin, tetramethrin, tralomethrin, transfluthrin;
M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, car- tap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thio- cyclam, thiosultap-sodium and AKD1022.
M.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole
M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
M.9. METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
M.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
M.13. Synergists: piperonyl butoxide, tribufos;
M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;
M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;
M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid; M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;
M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, te- flubenzuron, triflumuron;
M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
M.20. Octapaminergic agonsits: amitraz;
M.21. Ryanodine receptor modulators: flubendiamide; (R)-, (S)- 3- Chlor-N1-{2-methyl- 4-[1 ,2,2,2 -tetrafluor-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2- methylsulfonylethyl)phthalamid (M21.1 )
M.22. Various: aluminium phosphide, amidoflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor , 4-But-2-ynyloxy-6-(3,5-dimethyl- piperidin-1-yl)-2-fluoro-pyrimidine (M22.1), 3-Benzoylamino-N-[2,6-dimethyl-4-(1 ,2,2,2- tetrafluoro-1-trifluoromethyl-ethyl)-phenyl]-2-fluoro-benzamide (M22.2), 4-[5-(3,5- Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2- ylmethyl-benzamide (M22.3),4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoro-ethyl)-benzamide (M22.4),4-[5-(3,5-Dichloro- phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-thiazol-2-ylmethyl- benzamide (M22.5), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3- yl]-2-methyl-N-(tetrahydro-furan-2-ylmethyl)-benzamide (M22.6), 4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.7), 4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on(M22.8), 4-{[(2-Chloro1 ,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.9), 4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M22.10), 4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on(M22.11 ), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on(M22.12), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on(M22.13), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on(M22.14), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on(M22.15), 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on(M22.16), Cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2- cyclopropylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy- 4,6a, 12b-trimethyl-11 -oxo-9-(3-pyridinyl)-2H , 11 H-naphtho[2, 1 -b]pyrano[3,4-e]pyran- 3,6-diyl] ester(M22.17),
8-(2-Cyclopropylmethoxy-4-methyl-phenoxy)-3-(6-methyl-pyridazin-3-yl)-3-aza- bicyclo[3.2.1 ]octane(M22.18), M.23. N-R'-2,2-dihalo-1-R"cyclo-propanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p- tolyl)hydrazone or N-R'-2,2-di(R'")propionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)- hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R"' is methyl or ethyl;
M.24. Anthranilamides: chloranthraniliprole,cyantraniliprole,
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 - cyclopropyl-ethylcarbamoyO-θ-methyl-phenylJ-amide (M24.1 ), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1- cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M24.2),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6-
(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M24.3),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6- (1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M24.4),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1 - cyclopropyl-ethylcarbamoyO-phenyO-amide (M24.5),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2-(1 - cyclopropyl-ethylcarbamoyO-θ-methyl-phenyO-amide (M24.6),
M.25. Malononitrile compounds: CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF3,
(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoro-propyl)malononitrile),
CF2HCF2CF2CF2CH2C(CN)2CH2CH2CF2CF3 (2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-
(3,3,4,4,4-pentafluorobutyl)-malonodinitrile);
M.26. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus,
Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
The commercially available compounds of the group M may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.
Lepimectin is known from Agro Project, PJB Publications Ltd, November 2004. Ben- clothiaz and its preparation have been described in EP-A1 454621. Methidathion and Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Metaflumizone and its preparation have been described in EP-A1 462 456. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. Pyrafluprole and its preparation have been described in JP 2002193709 and in WO 01/00614. Pyriprole and its preparation have been described in WO 98/45274 and in US 6335357. Amidoflumet and its preparation have been described in US 6221890 and in JP 21010907. Flufenerim and its preparation have been described in WO 03/007717 and in WO 03/007718. AKD 1022 and its preparation have been described in US 6300348. Chloranthraniliprole has been described in WO 01/70671 , WO 03/015519 and WO 05/118552. Cyantraniliprole has been described in WO 01/70671 , WO 04/067528 and WO 05/118552.The anthranila- mides M 24.1 to M 24.6 have been described in WO 2008/72743 and WO 200872783. The phthalamide M 21.1 is known from WO 2007/101540. Cyflumetofen and its preparation have been described in WO 04/080180. The aminoquinazolinone compound pyrifluquinazon has been described in EP A 109 7932. Sulfoximine sulfoxaflor has been described in WO 2006/060029 and WO 2007/149134. The alkynylether compound M22.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 2007060839. The carboxamide compound M 22.2 is known from WO 2007/83394. The oxazoline compounds M 22.3 to M 22.6 have been described in WO 2007/074789. The furanon compounds M 22.7 to M 22.16 have been described eg. in WO 2007/115644. 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 2008/115155. The malononitrile compounds have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.
Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol, dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin, dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram, zineb, heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thiophanate-methyl, tiadinil, tricyclazole, triforine, copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate, nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl, phenylpyrroles such as fenpiclonil or fludioxonil, sulfur, other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifen- phos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamid, strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, me- tominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnemamides and analogs such as dimethomorph, flumetover or flumorph.
The animal pest, i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) of formula I or composition^) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formulae I or II. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
"Locus" means a habitat, breeding ground, cultivated plants, plant propagation material (such as seed), soil, area, material or environ-ment in which a pest or parasite is grow- ing or may grow.
In general "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The compounds of formula I 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 are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywood, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
The compounds of formula I can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and/or insecticide.
For use in bait compositions, the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare. In the treatment of seed, the application rates of the active ingredients are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
The term "plant propagation material" is to be understood to denote 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 emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 JuI- Aug;17(4):720-8., Protein Eng Des SeI. 2004 Jan;17(1 ):57-66, Nat Protoc. 2007;2(5):1225-35., Curr Opin Chem Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1):1 13-21 )
The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
The term "cultivated plants" is to be understood also including 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 Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi ) or Cryθc; vegetative insecticidal proteins (VIP), e. g.
VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel block- ers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new com- bination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
The term "cultivated plants" is to be understood also including 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 content or protein content), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato).
The present invention is now illustrated in further detail by the following examples.
The compounds of the invention as well as intermediates were characterized by coupled High Performance Liquid Chromatography / mass spectroscopy (HPLC/MS), by NMR or by their melting points. HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % TFA in a ratio of from 5:95 to 95:5 in 5 minutes at 40 0C. MS Quadrupol electrospray ionisation, 80 V (positive modus).
Preparation examples:
Example 1 : 3-amino-3-(2,3-dimethyl-phenyl)-propionic acid: A mixture of 2,3-dimethylbenzaldehyde (27 g, 0.2 mol) and NH4OAc (31 g, 0.4 mol) in EtOH (300 ml) was stirred at 450C and malonic acid (42.1 g, 0.4 mol) in EtOH was added. The resulting mixture was refluxed overnight, filtered and the desired product was obtained as a white solid (15 g, 39% yield). 1H-NMR (400 MHz, DMSO): δ [ppm]: 2.25 (s, 6 H), 2.85-2.95 (m, 1 H), 3.00-3.15 (m, 1 H), 4.73-4.85 (m, 1 H), 7.14-7.16 (m, 2 H), 7.41-7.46 (m, 1 H), 8.54 (s, 1 H).
Example 2: 3-amino-3-(2,3-dimethylphenyl)-propan-1-ol:
Lithiumaluminiumhydride (LiAIH4, 5.89 g) was added to a solution of 3-amino-3-(2,3- dimethylphenyl)-propionic acid (from example 1) (15 g) in THF (200 ml) at 0 0C. Then the mixture was warmed up to 60-80 0C and stirred overnight. Aqueous workup yielded the crude product after evaporation (13 g). 1H NMR (400 MHz, DMSO): δ [ppm]: 1.55- 1.63 (m, 2 H), 2.15-2.19(m, 3 H), 2.20-2.22 (m, 3H), 3.43-3.52 (m, 2 H), 4.17-4.24 (m, 1 H), 6.93-6.97 (m, 1 H), 7.00-7.05(m, 1 H), 7.27-7.30 (m, 1 H).
Example 3: [1-(2,3-dimethylphenyl)-3-hydroxypropyl]-carbamic acid tert-butyl ester:
To a solution of 3-amino-3-(2,3-dimethylphenyl)-propan-1-ol (from example 2) (25 g, 0.14 mol) in dichloromethane (200 ml) at 0 0C was added a solution of di-tert-butyl di- carbonate (45.7 g, 0.21 mol) in dichloromethane (100 ml) portion-wise and the resulting solution was stirred overnight at 20-25°C. The solvent was removed in vacuo. The residue was dissolved in ethyl acetate and washed with water. The organic phase was dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography to give [1-(2,3-dimethyl-henyl)-3-hydroxypropyl]-carbamic acid tert- butyl ester (25 g, 64%). 1H NMR (400 MHz, DMSO): δ [ppm]: 1.15(s, 1 H), 1.33(s, 8 H), 1.66-1.72(m, 2 H), 2.18-2.22(m, 6 H), 3.35-3.48 (m, 1 H), 4.19-4.52(m, 1 H), 4.90- 4.95 (m, 1 H), 6.95-7.05 (m, 2 H), 7.12-7.16(m, 1 H), 7.28-7.32(m, 1 H).
Example 4: [1-(2,3-dimethyl-phenyl)-3-phenoxypropyl]-carbamic acid tert-butyl ester:
To a solution of 1-(2,3-dimethyl-phenyl)-3-hydroxy-propyl]-carbamic acid tert-butyl ester (1.0 g, 3.6 mmol), phenol (340 mg, 3.6 mmol) and P(C6H5)S (1.13 g, 4.3 mmol) in dry tetrahydrofuran (20 ml.) was added DEAD (diethyl azodicarboxylate, 750 mg, 4.3 mmol) drop wise over a period of 5 min under a nitrogen atmosphere at 0 0C. After complete addition, the resulting mixture was stirred overnight at 20-25°C. The solvent was removed in vacuo. The residue was dissolved in ethyl acetate and washed with water. The organic phase was dried over Na2SU4, filtered and concentrated. The residue was purified by column chromatography to give the target compound (800 mg, 62.5%). 1H NMR (400 MHz, DMSO): δ [ppm]: 1.1 1 (s, 1 H), 1.29(s, 8 H), 1.82-1.96(m, 2 H), 2.15-2.19(m, 6 H), 3.75-3.82 (m, 1 H), 3.92-4.01 (m, 1 H), 4.95-5.05 (m, 1 H), 6.85- 6.91 (m, 3 H), 6.95-7.05(m, 2 H), 7.15-7.27(m, 3 H), 7.42-7.50(m, 1 H).
Example 5: 3-(3,5-dimethylphenoxy)-1 -(2,3-dimethyl-phenyl)-propylamine:
To a solution of [3-(3,5-dimethyl-phenoxy)-1-(2,3-dimethyl-phenyl)-propyl]-carbamic acid tert-butyl ester (4g, 11 mmol) in dichloromethane (50ml) was added trifluoroacetic acid (TFA, 3.8 g, 33 mmol) drop wise. Stirring was continued at 20-25°C for 18 hours. The mixture was washed with sat. aqueous NaHCθ3-solution. The organic phase was dried over Na2SO4, filtered and concentrated. The residue was purified by column chromatography (1.3 g, 40%). 1H NMR (400 MHz, DMSO): δ [ppm]: 1.75-1.91 (m, 2H), 2.14-2.21 (m, 12H), 3.85-3.92 (m, 1 H), 4.01-4.08 (m, 1 H), 4.25-4.31 (m, 1 H), 6.47-6.54 (m, 3H), 6.95-7.06 (m, 2H), 7.31-7.35 (m, 1 H).
Example 6: 3-phenoxy-1 -phenyl-propyl isothiocyanate
A mixture of 0.89 g thiophosgene in chloroform (10 ml) and potassium carbonate solu- tion (2,7 g in 10 ml of water) was treated at 20-25°C with a solution of 3-phenoxy-1 - phenyl-propylamine (1 ,5 g) in chloroform (10 ml) and stirring continued overnight. Water was added and the product extracted with dichlormethane, dried over sodiuim sulfate and the solvent evaporated in vacuo to yield 1 ,51 g of a crude product that was used for the next step without any further purification.
Example 7: 1-(2-hydroxy-ethyl)-3-(3-phenoxy-1-phenyl-propyl)-thiourea (compound lla.1 of Table 1 )
Crude 3-phenoxy-1 -phenyl-propyl isothiocyanate obtained as described in example 6 was dissolved in toluene (10 ml), and ethanolamine (0.37 g) was added and the mixture heated to reflux for 3 hours. After evaporation of the solvent, the residue was purified by column chromatography to yield the product (1.03 g, m.p. 97-98 0C)
Example 8: (4,5-dihydro-thiazol-2-yl)-(3-phenoxy-1-phenyl-propyl)-amine (compound la.1 of Table 2) To a solution of 1-(2-hydroxy-ethyl)-3-(3-phenoxy-1-phenyl-propyl)-thiourea (0.66 g) and 0.36 g diisopropylethylamine in 10 ml of propionitrile was added at 20-25°C 0.61 g cyanomethyl-trimethylphosphonium iodide (prepared according to Tetrahedron 2001 , 57, 5451-54). The reaction mixture was heated up to 90 0C for 5 h and stirred overnight. Extraction with ethyl acetate, washing with potassium carbonate solution and water followed by drying and evaporation of the solvent yielded a crude product which was purified by column chromatography to give 0.23 g of the title compound (m. p. 96- 97 0C)..
The intermediate compounds of the general formula Na (examples I Ia.2 to I Ia.11 ) can be prepared accordingly. The spectroscopical data of these compounds are listed in table 1.
Table 1 :
Figure imgf000061_0001
Figure imgf000061_0002
Figure imgf000062_0002
The compounds of the general formula Ia (examples Ia.2 to Ia.6) can be prepared accordingly. The spectroscopical data of these compounds are listed in table 2.
Table 2:
Figure imgf000062_0001
Figure imgf000062_0003
Biological Activity
Action against pests: The action of the compounds of the general formula I against pests was evaluated by the following experiments:
Cotton Aphid (Aphis gossypii) The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® 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 Ia.1 , la.2, Ia.3, Ia.4, Ia.6, at 300 ppm showed over 50 % mortality in comparison with untreated controls.
II. Green Peach Aphid (Myzus persicae)
The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® surfactant. Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') are infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The leaves of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
In this test, the compounds of examples Ia.1 , la.2, Ia.3, Ia.4, Ia.6, at 300 ppm showed over 70 % mortality in comparison with untreated controls.
III. Cowpea aphid (Aphis craccivora)
The active compounds were formulated in 50:50 acetone : water and 100 ppm Kinetic® surfactant. Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population has been recorded. Population reduction was recorded after 24, 72, and 120 hours.
In this test, the compounds of examples Ia.1 , la.2, Ia.4, Ia.5, Ia.6 at 300 ppm showed over 90% mortality in comparison with untreated controls.
IV. Silverleaf whitefly
The active compounds were formulated in 50 : 50 acetone : water and 100 ppm Kinetic® surfactant. Selected cotton plants were grown to the cotyledon state (one plant per pot). The coty-ledons 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 cov- ered 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 oC and 20- 40% relative humid-ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
In this test, the compounds of examples la.2, Ia.6 at 300 ppm showed over 50% mortality in comparison with untreated controls.

Claims

Claims:
Aminothiazoline compounds of the general formula (I):
Figure imgf000065_0001
wherein A is a radical of the formulae A1 or A2:
Figure imgf000065_0002
A1 A2 wherein * denotes the binding site and wherein m is 0, 1 , 2, 3, or 4; j is 1 , 2, or 3; X is sulfur, oxygen, or NRk;
Rk has the meaning as defined for R1;
R1 is hydrogen, cyano, nitro, Ci-Cβ-alkyl, formyl, d-Cβ-alkylcarbonyl, Ci-Cβ- alkoxycarbonyl, d-Cβ-alkylthiocarbonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R#,
R# is halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ- alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ- haloalkoxy, or d-Cβ-alkylthio;
C(O)NRaRb, or (SO2)NRaRb,
wherein Ra and Rb are each independently hydrogen, Ci-Cβ-alkyl, C2-C6- alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R#;
phenyl, phenyloxy, or benzyl, each of which three radicals may be unsub- stituted or substituted with any combination of 1 to 5 halogen, 1 to 3 Ci-Cβ- alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy or
Ci-Cβ-haloalkoxy groups;
R2 is halogen, OH, SH, NH2, SO3H, COOH, cyano, nitro, Ci-C6-alkyl, Ci-C6- alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, d-Cs-alkylthio, C2-C6- alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6- alkynyl, C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, Ci-Cβ- alkylsulfonyl, Ci-Cβ-alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6- alkynylsulfonyl, formyl, Ci-Cβ-alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6- alkynylcarbonyl, Ci-Cβ-alkoxycarbonyl, C2-C6-alkenyloxycarbonyl, C2-C6- alkynyloxycarbonyl, carbonyloxy, Ci-Cβ-alkylcarbonyloxy, Ci-Cβ- alkenylcarbonyloxy, Ci-Cβ-alkynylcarbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals R#,
C(O)NRaRb, (SO2)NRaRb, wherein Ra and Rb are as defined for R1 above;
a radical Y-Ar or a radical Y-Cy, wherein
Y is a single bond, oxygen, sulfur, C-i-Cβ-alkandiyl or Ci-Cβ-alkandiyloxy,
Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered het- eroaromatic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is unsubsti- tuted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R#; and Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals R#;
and wherein two radicals R2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals R#;
R3, R4 are each independently hydrogen, Ci-Cβ-alkyl, C-i-Cβ-haloalkyl, C3-C6- cycloalkyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals R#,
phenyl or benzyl, each unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci- Cβ-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups;
W is phenyl which is unsubstituted or substituted by 1 , 2, 3, or 4 independently selected substituents R2; or
a 5- to 6-membered heteroaromatic ring which contains from 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, wherein the heteroaromatic ring may optionally be fused to a ring selected from phenyl and a 5- to 6-membered saturated, partially unsaturated or aromatic heterocyclic ring which contains from 1 to 3 heteroatoms selected from oxygen, nitrogen and sulfur, and wherein the 5- to 6-membered heteroaromatic ring or the respective fused ring systems are unsubstituted or substituted by R5 and/or any combination of 1 to 4 groups R6:
Figure imgf000067_0001
wherein n is 0, 1 , 2, 3, or 4;
R5 is hydrogen, cyano, nitro, formyl, C(=O)R5c, C(=S)R5c, CrC6- alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, CrC6- alkoxy, (Ci-C6-alkoxy)methylen, Ci-C6-alkylsulfinyl, CrC6- alkylsulfenyl or Ci-C6-alkylsulfonyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals, independently of one a- nother selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-C6-alkyl, CrC6- alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and Ci-C6-alkylthio; or C(O)NR5aR5b, C(O)NR5aR5b, C(O)NR5aR5b, (SO2)NR5aR5b,
(SO2)NR5aR5b or (SO2)NR5aR5b; or phenyl, phenyloxy or benzyl, each of the last three mentioned radicals may be unsubstituted or substituted with 1 to 5 radicals, independently of one another selected from the group consisting of one to five halogen radicals, one to three CrC6- alkyl, one to three Ci-C6-haloalkyl, one to three Ci-C6-alkylthio, one to three Ci-C6-haloalkylthio, one to three Ci-C6-alkoxy and one to three Ci-C6-haloalkoxy radicals; and wherein R5a, R5b and R5c are defined as below;
R6 is selected from halogen, OH, SH, NH2, SO3H, COOH, cyano, azido, nitro, formyl, CONH2, CSNH2, CH=N-OH, CH=N-O-(Cr C6)-alkyl, C(=O)R6c, C(=S)R6c, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, Cs-Cs-cycloalkyl, CrC6-alkylamino, C2-C6-alkenylamino, C2-C6-alkynylamino, di(CrC6-alkyl)amino, di(C2-C6- alkenyl)amino, di(C2-C6-alkynyl)amino, CrC6-alkylthio, C2-C6- alkenylthio, C2-C6-alkynylthio, CrC6-alkylsulfonyl, C2-C6- alkenylsulfonyl, C2-C6-alkynylsulfonyl, (CrC6-alkyl)carbonyl, (C2- C6-alkenyl)-carbonyl, (C2-C6-alkynyl)-carbonyl, CrC6-alkoxy, C2- C6-alkenyloxy, C2-C6-alkynyloxy, (CrC6-alkoxy)carbonyl, (C2-C6- alkenyloxy)carbonyl, (C2-C6-alkynyloxy)-carbonyl, (Ci-Cβ- alkyl)carbonyloxy, (C2-C6-alkenyl-)carbonyl-oxy, (C2-Cβ- alkynyl-)carbonyloxy,
Figure imgf000068_0001
(C2-Cβ- alkenyl)carbonyl-amino, (C2-C6-alkynyl)carbonyl-amino, wherein
5 the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of one, two or three radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci- Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, d-Ce-alkoxy, C2-C6-
10 alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, d-Cβ-haloalkyl and Ci-Cβ-alkylthio; or
C(O)NR6aR6b or (SO2)NR6aR6b; wherein R6a, R6b and R6c are defined as below, a radical Y-Ar or a radical Y-Cy, wherein 15 Y is a single bond, oxygen, sulfur, NH, C-i-Cβ-alkandiyl or
C-i-Cβ-alkandiyloxy; Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10- membered heteroaromatic ring, which contains 1 , 2, 3 or 4 heteroatoms selected from 1 or 2 oxygen, 1 or 2 sulfur
20 and 1 to 3 nitrogen atoms as ring members, wherein Ar is unsubstituted or substituted with any combination of one to five radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C-i-Cβ-
25 haloalkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, C-i-Cβ-haloalkoxy and C-i-Cβ-alkylthio; Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with one to five radicals, independently of one another selected from the group consisting of halogen, cyano, nitro,
30 hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, Ci-C6- haloalkyl, Ci-C6-alkoxy, C2-C6-alkenyloxy, C2-C6- alkynyloxy, Ci-drhaloalkoxy and Ci-dralkylthio;
and wherein
35 R5a, R5b, R6a and R6b are each independently selected from hydrogen, Ci-C6-alkyl, Ci-drhaloalkyl, C2-C6-alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may
40 carry any combination of one, two or three radicals, independently of one another selected from the group consisting of halogen, cyano, nitro, hydroxy, mer- capto, amino, carboxyl, d-Cε-alkyl, C2- Cβ-alkenyl, C2-C6-alkynyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci- Cβ-haloalkoxy, Ci-C6-haloalkyl and Ci-
Ce-alkylthio;
R5c and R6c are each independently selected from hydrogen, Ci- C6 alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8- cycloalkyl, Ci-C6-alkylthio,Ci-C6-alkoxy, (Ci-C6- alkyl)amino, di(Ci-C6-alkyl)amino, hydrazino, (Ci- C6-alkyl)hydrazino, di(Ci-C6-alkyl)hydrazino, phenyl and heteroaryl, which can be a mono- or bicyclic 5 to 10 membered heteroaromatic ring, which con- tains 1 ,2,3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen;
and the enantiomers, diastereomers, and agriculturally and veterinarily acceptable salts thereof.
2. The compounds as claimed in claim 1 , wherein m is 2.
3. The compounds as claimed in claims 1 or 2, wherein X is sulfur.
4. The compounds as claimed in any of claims 1 , 2, or 3, wherein A in formula I is a radical A2, wherein R1 is hydrogen.
5. The compounds as claimed in any of claims 1 to 4, wherein W is phenyl which is unsubstituted or substituted as defined in claim 1.
6. Compounds of formula Il
Figure imgf000069_0001
wherein j, m W, R1, R2, R3 and R4 are defined as in claim 1 , and R7 is hydrogen, C-i-Cβ-alkylcarbonyl, Ci-Cβ-alkoxycarbonyl or benzoyl.
7. The compounds as claimed in claim 6, wherein m is 2.
8. The compounds as claimed in claims 6 or 7, wherein
W is phenyl, which is unsubstituted or substituted as defined in claim 1.
9. A method of combating animal pests selected from insects, arachnids and nema- todes which comprises contacting said animal pests, their habit, breeding ground, food supply, plant, plant propagation material, crop, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from attack or infestation by insects, arachnids or nematodes with a pesticidally effective amount of at least one aminothiazoline compound of the general formula I as defined in any of claims 1 to 8 and/or at least one enantiomer, diastereomers, or salt therof.
10. A method for protecting crops, plants and/or plant propagation material from at- tack or infestation by insects, arachnids or nematodes which comprises contacting the plants, crops and/or the plant propagation material with a pesticidally effective amount of at least one aminothiazoline compound of the general formula I as defined in any of claims 1 to 8 and/or at least one enantiomer, diastereomer, or salt thereof.
1 1. The method according claim 10, wherein the plant propargation material are seeds.
12. An agricultural composition comprising at least one compound of the formula I, as defined in any of claims 1 to 8, an enantiomer, diastereoisomer and/or an agriculturally acceptable salt thereof, and at least one inert liquid and/or solid agriculturally acceptable carrier.
13. A veterinary composition comprising at least one compound of the formula I, as defined in any of claims 1 to 8, an enantiomer, diastereoisomer and/or a veteri- narily acceptable salt thereof, and at least one inert liquid and/or solid veterinarily acceptable carrier.
14. The use of a compound as defined in any of claims 1 to 8, an enantiomer, di- astereoisomer and/or an agriculturally or veterinarily acceptable salt thereof, for combating animal pests selected from insects, arachnids and nematodes.
15. The use of a compound as defined in any of claims 1 to 8, an enantiomer, diastereoisomer and/or a veterinarily acceptable salt thereof, for treating or protect- ing an animal from infestation or infection by animal pests.
16. The use of a compound as defined in any of claims 1 to 8, an enantiomer, di- astereoisomer and/or a veterinarily acceptable salt thereof, for the preparation of a veterinary medicament.
17. Plant propagation material, comprising at least one compound of the formula I as defined in any of claims 1 to 8, an enantiomer, diastereoisomer and/or an agriculturally acceptable salt thereof.
18. The plant propargation material according to claim 17, wherein the plant propar- gation material are seeds.
19. A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesti- cidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 8, an enantiomer, diastereoisomer and/or a veterinarily acceptable salt thereof.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (en) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft 1-(azolin-2-yl) amino-1,2-diphenylethane compounds for combatting insects, arachnids and nematodes
WO2006125745A2 (en) * 2005-05-23 2006-11-30 Basf Aktiengesellschaft 1-(1,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests
WO2007020377A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Chemical compounds
WO2007071585A1 (en) * 2005-12-22 2007-06-28 Basf Se Pestcidal compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005063724A1 (en) * 2003-12-23 2005-07-14 Basf Aktiengesellschaft 1-(azolin-2-yl) amino-1,2-diphenylethane compounds for combatting insects, arachnids and nematodes
WO2006125745A2 (en) * 2005-05-23 2006-11-30 Basf Aktiengesellschaft 1-(1,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests
WO2007020377A2 (en) * 2005-08-15 2007-02-22 Syngenta Participations Ag Chemical compounds
WO2007071585A1 (en) * 2005-12-22 2007-06-28 Basf Se Pestcidal compositions

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