WO2011057942A1 - Insecticidal methods using pyridine compounds - Google Patents

Insecticidal methods using pyridine compounds Download PDF

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WO2011057942A1
WO2011057942A1 PCT/EP2010/066820 EP2010066820W WO2011057942A1 WO 2011057942 A1 WO2011057942 A1 WO 2011057942A1 EP 2010066820 W EP2010066820 W EP 2010066820W WO 2011057942 A1 WO2011057942 A1 WO 2011057942A1
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formula
compounds
alkyl
compound
alkoxy
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PCT/EP2010/066820
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French (fr)
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Steffen Gross
Dschun Song
Wolfgang Von Deyn
Florian Kaiser
Prashant Deshmukh
Joachim Dickhaut
Nina Gertrud Bandur
Arun Narine
Karsten KÖRBER
Eike Hupe
Christian Pilger
Deborah L. Culbertson
Cecille Ebuenga
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A01N47/06—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 no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/22—O-Aryl or S-Aryl esters thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems

Definitions

  • the present invention relates to new insecticidal methods of using Pyridine compounds and salts thereof.
  • the present invention relates also to new Pyridine derivatives and their uses in the agricultural field.
  • Animal pests destroy growing and harvested crops, as well as the seeds and attack wooden dwelling and commercial structures, causing damage in the agricultural field, large economic loss to the food supply and to the 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 animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
  • A, E, G, M are N or C-R c , wherein one of these groups being N,
  • R c is independently from one another hydrogen or selected from R b ,
  • ⁇ is selected from hydrogen, OH, C 1 -Cs-alkyl, C 1 -C 4 -haloalkyl, Z- C3-C6-cycloalkyl, C2-Cs-alkenyl, Z-Cs-Ce-cycloalkenyl, C2-C8- alkynyl, Z-C 1 -C6-alkoxy, Z-C 1 -C 4 -haloalkoxy, Z-Cs-Cs-alkenyl- oxy, Z-Cs-Cs-alkynyloxy, NR'R", C 1 -C 6 -alkylsulfonyl, Z-(tri-C 1 - C 4 -alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino, a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic hetero- cycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O,
  • R' and R" together with the nitrogen atom to which they are attached to may also form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;
  • R bb is C 1 -Ce-alkyl or d-C 6 -haloalkyl;
  • Z is a covalent bond or C 1 -C 4 -alkylene chain
  • R b together with the group R b optionally attached to the adjacent carbon atom may also form a 5- or 6-membered saturated or partially or fully unsaturated ring which, which in addition to carbon atoms, may also contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;
  • X, Y are selected from O, S or N-R 3 ;
  • R 1 is selected from 0-R A - S(0) n -R A or OS(0) n -R A ;
  • n 0, 1 or 2;
  • R 3 is selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C2-C6-alkenyl, C3- C6-alkynyl, Z-C3-Cio-cycloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -cyanoalkyl,
  • the carbon chains and/or the cyclic groups may be partially or fully substituted by groups R b ;
  • the present invention relates to following insecticidal methods applying such compounds of formula I.
  • It was an object of the present invention to provide methods of combating and controlling animal pests which methods comprise contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;
  • Another object of the present invention was to provide methods for protecting plant propargation material, especially seeds, from soil insects and seedlings' roots and shoots from soil and foliar insects, which methods comprise contacting the seeds before sowing and/or after pregermination with at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof; And another object of the present invention was to provide methods for treating, controlling, preventing or protecting animals against infestation or infection by parasites, which methods comprise administering or applying to the animals and/or to their enviroment a parasitically effective amount of at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or a veterinary acceptable salt thereof.
  • Object of the invention are also methods of using at least one compound of the formula I and/or an N-oxide, enantiomer, diastereomer and/or a veterinary acceptable salts thereof, for combating parasites in and on animals by treating the parasites with an parasitical active amount thereof.
  • the present invention relates also to new pyridine compounds of the general formulae II and III, their N-oxides, enantiomers, diastereomers or agricultural or veterinary useful salts thereof and to veterinary or agricultural compositions comprising them and at least one inert liquid and/or solid agronomically acceptable carrier, as well as to their uses as described above for compounds of formula I.
  • the present invention relates also to compounds of formula I, which are of formula II:
  • Y is S or O
  • X is S or O
  • R 1 is selected from hydrogen, C 1 -C 6 -alkylcarbonyl or C 1 -C 6 -alkoxycarbonyl, and
  • R c2 , R c3 , R c3' , R c4 , c4' and R c5' are selected independently from one another from the group consisting of hydrogen, OH, CN, NO2, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy.
  • the present invention relates also to compounds of formula I ,which are of formula III:
  • X is O or S
  • R 1 is selected from hydrogen, C 1 -C 6 -alkylcarbonyl or C 1 -C 6 -alkoxycarbonyl;
  • R 2 is phenyl or pyridyl, which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C1-C4- alkoxy and C 1 -C 4 -haloalkoxy;
  • R c2 , R c3 , R c4 are selected independently from one another from the group consisting of hydrogen, OH, CN, NO2, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy;
  • R 3 is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyridyl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl and isoxazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy and C 1 -C 4 -haloalkoxy, wherein
  • Z is a covalent bond or C 1 -C 4 -alkylene chain, wherein the carbon chain may optionally carry one or more substituents selected from C 1 -C 8 -alkyl or C1-C4- haloalkyl;
  • pyridopyrazines have been described in WO 2008/009908 and WO 2008/071918 for their herbicidal uses.
  • Other pyridine compounds have been described in WO2009/090401 and WO2009/090402 also for herbicidal activity.
  • Further herbicidal pyridine compounds are described in unpublished applications PCT/EP2009/063387 and PCT/EP2009/063386.
  • the compounds of the formula I, II and III, their N-oxides, enantiomers, diastereo- mers and their agriculturally or veterinary acceptable salts thereof are highly active against animal pest, i.e. harmful arthropodes and nematodes. They may be used against difficult to control insects and acaridae.
  • the present invention relates to and includes the following embodiments: agricultural and veterinary compositions comprising an amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
  • a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
  • a method for protecting crops from attack or infestation by animal pests which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
  • a method for the protection of plant propargation material, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propargation material, especially the seeds, before sowing and/or after pregermination with at least one compound of the formula I, II or III, or the N-oxide, enantiomers, diastereomers or salts thereof; seeds comprising a compound of the formula I ,11 or III, or an N-oxide, enanti- omer, diasteromer or salt thereof;
  • a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of an compound of formula I, II or III, or the N-oxide, enantiomers, diastereomers and/or veterinary acceptable salt thereof;
  • compositions for treating, controlling, preventing or protecting animals against infestation or infection by parasites wherein the composition comprisess a parasiticidally effective amount of an compound of formula I, II or III, or the enantiomers, diastereomers and/or veterinary acceptable salt thereof.
  • the compounds of the present invention can contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures.
  • Subject matter of this invention are not only compositions containing these mixtures but also those containing the pure enantiomers or diastereomers.
  • the compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of the formula I, II or III or as well mixtures of their different crystalline states.
  • Salts of the compounds of formulae I, II and III are preferably agriculturally and veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formulae I, II or III has a basic functionality or by reacting an acidic compound of formulae I, II or III 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.
  • Suit-able 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 C 1 -C 4 -alkyl, C 1 -C 4 -hydroxyalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkoxy- C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammo-nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 -C 4 -alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy-drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of the present invention 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 the present invention con- taining a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hydrochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in par- ticu-lar fluorine, chlorine or bromine.
  • Examples for C 1 -C3-alkyl are methyl, ethyl, propyl and 1 -methylethyl (isopropyl).
  • Examples for C1-C6 alkyl further encompass, butyl, 1 -methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethyl- ethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3 methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2 dimethylpropyl, 1 -methylpentyl, 2-methyl- pentyl, 3 methylpentyl, 4-methylpentyl, 1 ,1 dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-di- methylbut
  • C 1 -C 6 -haloalkyl as used herein and in the haloalkyl moieties of C1-C6- haloalkoxy, C 1 -C 6 -haloalkylthio, C 1 -C 6 -haloalkylcarbonyl and C 1 -C 6 -haloalkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C 1 -C3-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoro- methyl, chloro-fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1
  • Examples for C 1 -C3-alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy) and
  • C 1 -C 6 -alkoxy further encompass n-butoxy, OCH(CH 3 )C 2 H 5 (sec-butoxy), OCH 2 CH(CH 3 ) 2 (isobutoxy), OC(CH 3 ) 3 (tert-butoxy), n- pentoxy, 1 methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2- dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, n-hexoxy, 1 methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethyl- butoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbut- oxy, 1 -ethylbutoxy, 2-ethylbutoxy
  • C 1 -C 6 -haloalkoxy refers to a C 1 -C 6 -alkoxy group as men-tioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • C 1 -C3-haloalkoxy groups i.e.
  • C 1 -C3-alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bro- mine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2- iodoethoxy,
  • C 1 -C 6 -haloalkoxy further encompass 4-fluorobutoxy, 4- chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoro-1 -pentoxy, 5-chloro-1 -pent- oxy, 5 bromo-1 -pentoxy, 5-iodo-1 -pentoxy, 5,5,5-trichloro-1 -pentoxy, undecafluoropen- toxy, 6-fluoro-1 -hexoxy, 6-chloro-1 -hexoxy, 6-bromo-1 -hexoxy, 6-iodo-1 -hexoxy, 6,6,6 trichloro-1 -hexoxy and dodecafluorohexoxy.
  • Particularly preferred are chloromethoxy, fluorometh-oxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2 chloroethoxy and 2,2,2-trifluoroethoxy.
  • Examples for C 1 -C 6 -alkylcar- bonyl further encompass n-pentylcarbonyl, 1 -methylbutylcarbonyl, 2-methylbutylcar- bonyl, 3-methylbutylcarbonyl, 1 ,1 -dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl,
  • C 1 -C 4 -alkoxycarbonyl examples include -C(0)OCH 3 , -C(0)OC 2 H 5 , -C(0)0-CH 2 -C 2 H 5 , -C(0)OCH(CH 3 ) 2 , n-butoxycarbonyl, -C(0)OCH(CH 3 )- C 2 H 5 , -C(0)-OCH 2 CH(CH 3 ) 2 and C(0)OC(CH 3 ) 3 .
  • C 1 -C 6 -alkoxycarbonyl further encompass n-pentoxycarbonyl, 1 -methylbutoxycarbonyl, 2-methylbutoxycar- bonyl, 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,
  • C 1 -C 6 -alkylthio (C 1 -C 6 -alkylsulfanyl: C 1 -C 6 -alkyl-S-)
  • C 1 -C 3 -alkylthio examples include methylthio, ethylthio, propylthio and 1 methyl- ethylthio.
  • C 1 -C 6 -alkylthio further encompass butylthio, 1 -methylpropylthio, 2-methylpropylthio and 1 ,1 -dimethylethylthio.
  • R'R In case when in the term "NR'R”" one of R' or R" is C 1 -C 6 -alkyl or d-Ce-alkylcarbo- nyl, this is represented by the term “C 1 -C6-alkylamino” or the term “C 1 -C6-alkylamino- carbonyl", or when both of R' and R" are C 1 -C6-alkyl or C 1 -C6-alkylcarbonyl this represented by the term "di(C 1 -C6-alkyl)amino)" or the term "di(C 1 -C6-alkylamino)-carbonyl".
  • C 1 -C6-alkylamino refers to a secondary amino group carrying one alkyl group as defined above, e.g.
  • di(C 1 -C6-alkyl)amino) refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g.
  • C2-C6-alkenyl as used herein and in the alkenyl moieties of C2-C6-al- kenyloxy, C2-C6-alkenylamino and C2-C6-alkenylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -bu- tenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2 methyl-1 -propenyl, 1 -methyl-2-pro- penyl, 2-methyl-2-propenyl; 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 - butenyl, 2-methyl-1 -butenyl, 3-methyl-1 -buten
  • C2-C6-alkenyloxy refers to a straight-chain or branched al-kenyl group having 2 to 6 carbon atoms which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy and the like.
  • C2-C6-alkynyl as used herein and in the alkynyl moieties of
  • C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio and C2-C6-alkynylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1 -yn-1 -yl, prop-2-yn-1 -yl, n-but-1 -yn-1 -yl, n-but-1 -yn-3-yl, n-but-1 -yn-4-yl, n-but-2-yn-1 -yl, n-pent- 1 -yn-1 -yl, n-pent-1 -yn-3-yl, n-pent-1 -yn-4-yl, n-pent-1 -yn-5-yl, n-pent-2-yn-1 -yl,
  • C2-C6-alkynyloxy refers to a straight-chain or branched al-kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, butyn-4-yloxy and the like.
  • monocyclic radicals comprise cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • Phenyl fused to benzene is naphthyl.
  • Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl,
  • saturated or (partially) unsaturated heterocycle comprises nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms as ring members.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • non-aromatic rings examples include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3- dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4- dioxanyl, thiopyranyl, dihydrothiopyrany
  • aromatic heterocycle or "heteroaryl” (“mono or bicyclic 5- to 10- membered”) as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyclic or heterocyclic 5, 6 or 7 mem- bered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the heteraryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the carbocyclic or heterocyclic fused ring is selected from C5-C7-cycloalkyl, 5 to 7 membered heterocyclyl and phenyl.
  • Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxa- zolyl.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl,
  • benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
  • linear or branched C 1 -C 6 -alkanediyl as used herein and in the term
  • C 1 -C 6 -alkanediyloxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms
  • linear C 1 -C 6 -alkanediyl comprise methyldiyl, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl.
  • Examples for branched C 1 -C 6 -alkanediyl comprise ethyl-1 ,1 -diyl, propyl-1 ,1 -diyl, butyl- 1 ,1 -diyl, 1 -methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1 -ethylethane-1 ,2 diyl, 1 -methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.
  • substituents and variables of the Pyridine compounds of formula I used in each case on their own or in combination.
  • the compounds of formula (I) used are characterized in that R 1 is selected from hydrogen, C 1 -C 6 -alkyl- carbonyl or C 1 -C 6 -alkoxycarbonyl.
  • the compounds of formula (I) used are characterized in that Y is O.
  • the compounds of formula (I) used are characterized in that Y is S.
  • the compounds of formula (I) used are characterized in that Y is N-R 3 , and wherein R 3 is a 5- or 6- membered monocyclic heterocycle attached via Z and selected from the group consisting of pyrimidyl, pyridyl, thienyl, furyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, quinolinyl, isoquinolinyl, indolyl, benzofuryl, benzthienyl, ben- zoxazolyl, benzthiazolyl and benzimidazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle or Z may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C 1 -C 4
  • the compounds of formula (I) used are characterized in that X is O.
  • the compounds of formula (I) used are characterized in that X is S.
  • the compounds of formula (I) used are characterized in that A is N and E, G and M are C-R c , wherein R c is independently from one another hydrogen or selected from R b as defined above.
  • the compounds of formula (I) used are characterized in that A is N, X is O, Y is O or S and E, G and M are C-R c , and wherein R c is independently from one another hydrogen or selected from R b as defined as above.
  • the compounds used are characterized in that the pyridine compound is of formula I.
  • R c2 , R c3 and R c4 are selected independently from one another from R c as defined above, and m is 0, 1 , 2, 3 or 4.
  • Y, R 1 , R c2 , R c3 and R c4 are defined as in table II below, and R c3' , R 04' and R c5' are defined as in tables lla to tables Mm thereinafter.
  • R 1 , R c2' , R c3' and R c4' are defined as in table III below, and R 3 is defined as in tables Ilia to lllp thereinafter.
  • R 1 , R c2' , R c3' and R c4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
  • R 1 , R c2' , R c3' and R c4' for a compound cor- responds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
  • R 3 is and the combination of R 1 , R c2' , R c3' and R c4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
  • R 1 , R c2' , R c3' and R c4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
  • This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chem- istry 1994, 37(3), 273-282) or other known coupling agents.
  • a base such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025)
  • a catalyst such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chem- istry 1994, 37(3), 273-282) or other known coupling agents.
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclo- hexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p- xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chloro
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxid
  • tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Suitable leaving groups L 1 are, in general, groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.
  • This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chemistry 1994, 37(3), 273-282) or other known coupling agents.
  • a base such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025)
  • a catalyst such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chemistry 1994, 37(3), 273-282) or other known coupling agents.
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably methylene chloride and toluene. It is also possible to use mixtures of
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alka- line earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alk
  • alkali metal and alkaline earth metal carbonates such as lithium carbonate, potas- sium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • Suitable agents H-L 1 are alcohols, optionally subst. phenols, ⁇ , ⁇ -dialkylhydroxyl- amine, in particular pentafluorophenol or ⁇ , ⁇ -dimethylhydroxylamine.
  • the compounds of the formula VII are cyclized to give the compounds of the formula I.
  • This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf. Silverman, Richard B. J. Am. Chem. Soc. 1981 , 103(13), 3910].
  • Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile and dimethylformamide. It is also possible to use mixtures of
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometal- lic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkal
  • alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
  • the starting materials are generally reacted with one another in equimolar amounts.
  • the compounds of the formula I can also be obtained via a reverse reaction sequence, i.e. the reaction of the compounds of the formula IV with compounds
  • H-L 1 gives the activated derivatives of the formula VIII.
  • this reaction is carried out under the conditions mentioned for the reaction of the formula VI with H-L 1 .
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products.
  • Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from vola- tile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.
  • the Pyridine compounds of formula I, II and III can be reacted with conventional salt builders as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, benzene sulfonic acid, p-toluol-sulfonic acid, dode- cylbenzene sulfonic acid, methyl bromide, dimethyl sulfate or diethyl sulfate in temperature range of 0 to 150°C, preferably 20 to 120 °C.
  • the formation of the salt is usually conducted in a dissolving or diluting agent.
  • Suitable are e.g. aliphatic hydrocarbons as n-pentane, n-hexane or petrol ether, aromatic hydrocarbons, as benzole, toluole or xylole, benzine or ethers as diethyl ether, methyl- tert. -butyl ether, tetrahydrofurane or dioxane, further ketones, as acetone, methyl-ethyl- ketone or methyl-isopropyl-ketone, as well as halogenated hydrocarbons as chloroben- zole, methylene chloride, ethylenen chloride, chloroform or tetrachlor ethylene. Also mixtures of those solvents can be used.
  • the educts are employed usually in a stoichiometric ratio.
  • the excess of one or the other component can be useful.
  • 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 compounds of the present invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • Animal pests controlled by the compounds of the present invention include for example:
  • Insects from the order of the lepidopterans for example Agrotis ypsi- lon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia con-clerosislla, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia 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, Grapholith
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes ob- scurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp
  • mosquitoes e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis,
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frank- liniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
  • cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis;
  • Paravespula vulgaris Paravespula pennsylvanica
  • Paravespula germanica Paravespula germanica
  • crickets grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroc- canus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hiero- glyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminif- era, and Locustana pardalina;
  • arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambry- omma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Orni- thodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanys
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panony- chus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,
  • Earwigs e.g. forficula auricularia
  • Nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne ja- vanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- Kunststoffsis and other Globodera species; Heterodera avenae, Heterodera glycines, Hete- rodera 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 nemato- des, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes,
  • Hirshmanniella species Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longi- dorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Bur- rowing 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, Paratri- chodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchor
  • the compounds of the present invention are also useful for controlling arachnids (Arachnoidea), such as acarians (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.
  • arachnoidea such as acar
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • insects preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species:
  • Thysanoptera Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scir- tothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens,
  • Hemiptera in particular aphids: 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, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dys
  • Compounds of the present invention are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.
  • the compounds of the present invention can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions.
  • the use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the present invention.
  • auxiliaries suitable for the formulation of agrochemicals such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
  • Solvents/carriers which are suitable, are e.g.:
  • solvents such as water, aromatic solvents (for example Solvesso products, xy- lene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexa- none, gamma-butyrolactone), pyrrolidones (N-metyhl-pyrrolidone (NMP),N- octylpyrrolidone NOP), acetates (glycol diacetate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modified oils such as alkylated plant oils.
  • solvent mixtures may also be used,
  • ground natural minerals and ground synthetic minerals such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and 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.
  • 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.
  • Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
  • dispersants examples include lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants 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, polyoxy- ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, al- kylphenyl polyglycol ethers,
  • 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.
  • Suitable preservatives are for example dichlorophen und benzyl alcohol hemiformal
  • Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this context, for example, of commercial thickeners based on polysaccharides, such as Xanthan Gum ® (Kelzan ® from Kelco), Rhodopol ® 23 (Rhone Poulenc) or Veegum ® (from R.T. Vanderbilt), or organic phyllosilicates, such as Atta- clay ® (from Engelhardt).
  • Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon ® SRE, Wacker or Rhodorsil ® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof.
  • Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trademarks Proxel ® from Avecia (or Arch) or Acticide ® RS from Thor Chemie and Kathon ® MK from Rohm & Haas.
  • Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound com- position. If appropriate, the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds.
  • buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • weak inorganic or organic acids such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin
  • Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers.
  • solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nut- shell 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
  • the formulations comprise from 0.01 to 95% by weight, preferably from
  • the active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold lead- ing 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 compound of formula I or formula II can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.
  • formulations are examples of formulations:
  • Products for dilution with water may be applied to the seed diluted or undiluted.
  • a dispersant for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compounds is obtained.
  • Emulsions EW, EO, ES
  • 25 parts by weight of the active compound is 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 is obtained.
  • an emulsifier machine e.g. Ultraturrax
  • 50 parts by weight of the active compound is 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 is obtained.
  • 75 parts by weight of the active compound 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, whereby a formulation with 75% (w/w) of active compound is obtained.
  • 0.5 part by weight of the active compound is ground finely and associated with 95.5 parts by weight of 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.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wet- table powders (sprayable powders, oil dispersions) by adding water.
  • the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emul- sifier.
  • concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
  • the active ingredients may also be used successfully in the ultra-low-volume proc- ess (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
  • UUV ultra-low-volume proc- ess
  • Formulations of compounds of the present invention as aerosols e.g in spray cans
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • compounds of the present invention may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxi- cants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • Organo(thio)phosphate compounds acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fam- phur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, mono- crotophos, naled, omethoate, oxyde
  • Carbamate compounds aldicarb, alanycarb, bendiocarb, benfuracarb, buto- carboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobu- carb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; M.3.
  • Pyrethroid compounds acrinathrin, allethrin, d-cis-trans allethrin, d-trans al- lethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cyclo- prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cyper- methrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpro- pathrin, fenvalerate, flucythr
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
  • Nicotinic receptor agonists/antagonists compounds acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, niten- pyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiaclo- prid, thiocyclam, 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, le- pimectin;
  • METI I compounds fenazaquin, fenpyroximate, pyrimidifen, pyridaben, te- bufenpyrad, tolfenpyrad, flufenerim, rotenone;
  • METI II and III compounds acequinocyl, fluacyprim, hydramethylnon;
  • M.1 Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbutatin oxide, propargite, tetradifon;
  • Moulting disruptors cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
  • Mite growth inhibitors clofentezine, hexythiazox, etoxazole;
  • Lipid biosynthesis inhibitors spirodiclofen, spiromesifen, spirotetramat
  • Anthranilamide compounds chloranthraniliprole, cyantraniliprole, 5-Bromo-2- (3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 -cyclopropyl-ethyl- carbamoyl)-6-methyl-phenyl]-amide (M23.1 ), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H- pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]- amide (M23.2), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bro- mo-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl
  • Microbial disruptors Bacillus thuringiensis subsp. Israelensi, Bacillus sphaeri- cus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
  • the isoxazoline compounds M 22.1 to M 22.8 have been described in e.g. WO2005/085216, WO 2007/079162, WO 2007/026965, WO 2009/126668 and WO2009/051956.
  • the aminofuranone compounds M 26.1 to M 26.10 have been described eg. in WO 2007/1 15644.
  • the pyripy- ropene derivative M 27.2 has been described in WO 2008/66153 and WO
  • fungicidal active substances which, in combination with the compounds of the present invention, can be used in pesticidal mixtures is intended to illustrate the possible combinations, but does not limit them:
  • Inhibitors of complex III at Qo site e.g. strobilurins
  • strobilurins azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picox- ystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyri- carb/chlorodincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl- allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;
  • oxazolidinediones and imidazolinones famoxadone, fenamidone;
  • Inhibitors of complex II e.g. carboxamides: carboxanilides: benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flu- opyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5- carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyra- zole-4-carboxamide and N-(
  • Inhibitors of complex III at Qi site cyazofamid, amisulbrom;
  • nitrophenyl derivates binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • F.II-1 C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusila- zole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;
  • DMI fungicides e.g. triazoles,
  • imidazoles imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
  • pyrimidines, pyridines and piperazines fenarimol, nuarimol, pyrifenox, triforine; F.II-2) Delta 14-reductase inhitors (Amines, e.g. morpholines, piperidines) morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
  • piperidines fenpropidin, piperalin;
  • spiroketalamines spiroxamine
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
  • isoxazoles and iosothiazolones hymexazole, octhilinone;
  • Tubulin inhibitors benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
  • benzamides and phenyl acetamides diethofencarb, ethaboxam, pencycuron, fluopi- colide, zoxamide;
  • Actin inhibitors benzophenones: metrafenone;
  • anilino-pyrimidines cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
  • F.V-2 Protein synthesis inhibitors (anilino-pyrimidines)
  • antibiotics blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildio- mycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • MAP / Histidine kinase inhibitors e.g. anilino-pyrimidines
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • phenylpyrroles fenpiclonil, fludioxonil;
  • F.VI-2 G protein inhibitors: quinolines: quinoxyfen;
  • organophosphorus compounds edifenphos, iprobenfos, pyrazophos;
  • dithiolanes isoprothiolane
  • aromatic hydrocarbons dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
  • cinnamic or mandelic acid amides dimethomorph, flumorph, mandiproamid, pyri- morph;
  • valinamide carbamates benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
  • Inorganic active substances Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
  • F.VIII-2 Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasul- phocarb, metiram, propineb, thiram, zineb, ziram;
  • Organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusul- famide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N- (4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
  • phthalimides e.g. phthalimides, sulfamides, chloronitriles
  • Guanidines guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
  • F.IX-1 Inhibitors of glucan synthesis: validamycin, polyoxin B; F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, di- cyclomet, fenoxanil;
  • phosphonates fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
  • bronopol chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclo- mezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusul- famide, flutianil, methasulfocarb, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl form
  • abscisic acid amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegu- lac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri io
  • Bacillus substilis strain with NRRL No. B-21661 e.g. RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest, Inc.,
  • Bacillus pumilus strain with NRRL No. B-30087 e.g. SONATA® and BALLAD® Plus from AgraQuest, Inc., USA
  • Ulocladium oudemansii e.g. the product BOTRY- ZEN from BotriZen Ltd., New Zealand
  • Chitosan e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand
  • the present invention 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 the present invention or a salt thereof or a composition as defined above.
  • the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention 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 preven- tive 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.
  • the invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of the present inven- tion or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
  • compositions may contain a single active compound of the present invention or a salt thereof or a mixture of several active compounds of the present invention or their salts according to the present invention.
  • the composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers.
  • the animal pest i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the compounds of the present in- vention or composition(s) 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).
  • the compounds of the present invention 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 pesticidally effective amount of compounds of the present invention.
  • crop refers both to growing and harvested crops.
  • the compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for ex- ample seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecti- cidally effective amount of the active compounds.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
  • the present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, culti- vated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one active compound of the present invention.
  • 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 the present invention.
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of the present invention 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 the present invention.
  • "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).
  • “Locus” means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
  • 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 lim- ited 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 Jul- Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc.
  • cultiva plants is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy- 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,
  • EPSPS enolpyruvylshikimate-3-phosphate synthase
  • GS glutamine synthetase
  • 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(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as blockers of sodium or calcium channels
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, trun- cated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ).
  • Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are 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.
  • 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).
  • 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 infestans 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 infestans 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 con- tent 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.
  • productivity e. g. bio mass production, grain yield, starch content, oil con- tent or protein content
  • 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).
  • 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).
  • 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 quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 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 .
  • Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
  • the 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 compounds of formula I and II are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • the compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • non-crop insect pests such as 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.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • the compounds of the present invention and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long- term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of formula I and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like.
  • Insecticidal 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 exam- pie are ⁇ , ⁇ -Diethyl-meta-toluamide (DEET), ⁇ , ⁇ -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 ex- tracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of aliphatic acids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and di-ethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
  • the compounds of the present invention 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 formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.
  • the compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects.
  • the protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
  • the present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula I or II or a salt thereof.
  • a method wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably aa method, wherein the plants shoots are protected from aphids.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the present invention also comprises seeds coated with or containing the active compound.
  • the term "coated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application.
  • the said propagation prod- uct When the said propagation prod- uct is (re)planted, it may absorb the active ingredient.
  • Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the active compound may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
  • the active compound can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO
  • the active compound can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the gen- eration of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
  • the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • compositions which are especially useful for seed treatment are e.g.:
  • a Soluble concentrates (SL, LS)
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Appli- cation to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • Seed Treatment formulations may additionally also 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 homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, poly- saccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Sol- vent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue
  • pigment blue 80 pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • Example of a gelling agent is carrageen (Satiagel ® ).
  • the application rates of the compounds I 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, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the formula I, or an agriculturally useful salt of I, as defined herein.
  • the amount of the compound I or the agriculturally useful salt thereof will in general vary 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 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of the present invention or the veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
  • An object of the present invention is therfore also to provide new methods to control 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. 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 the present invention or the veterinarily acceptable salts thereof or a composition comprising it.
  • the present invention also provides a non-therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises including a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof in a composition comprising it.
  • the invention relates further to the use of compounds of the present invention for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
  • the invention relates also to the use of a compound of the present invention, or a composition comprising it, for the manufacture of a medicament for the therapeutic treatment of animals against infections or infestions by parasites.
  • compounds of the present invention are suitable for combating endo- and ectoparasites in and on animals.
  • 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.
  • Compounds of the present invention 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.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals such as min
  • Compounds of the present invention 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, chiggers, gnats, mosquitoes and fleas.
  • the compounds of the present invention are especially useful for combating ectoparasites.
  • the compounds of the present invention are especially useful for combating endoparasites.
  • the compounds of the present invention are especially useful for combating para- sites 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,
  • mosquitoes e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chry- somya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea,
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovi- cola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g.
  • Bots Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma 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
  • Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Os- tertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp.,
  • Stephanurus dentatus Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globo- cephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongy- lus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, As- caridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, As- caridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi
  • Ascaridida e.g. Ascaris lumbricoides, Ascaris suum, As- caridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofi- lari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Ha- bronema 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., Di- crocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobil- harzia 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 present invention relates to the therapeutic and the non-therapeutic use of compounds of the present invention for controlling and/or combating parasites in and/or on animals.
  • the compounds of the present invention may be used to protect the animals from attack or infestation by parasites by contacting them with a parasitically effective amount of compounds of the present invention.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect contact (applying the compounds/compo- sitions to the locus of the parasite).
  • the contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of formula I.
  • “Locus” as defined above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
  • the compounds of the invention can also be applied preventively to places at which occurrence of the pests or parasites is expected.
  • the compounds of the present invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits).
  • the administration can be carried out prophylactically, therapeutically or non-therapeutally.
  • Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • 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 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.
  • the compounds the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and cap- sules.
  • the formula I compounds may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the compounds the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds the present invention may be formulated into an implant for subcutaneous ad- ministration.
  • the compound the present invention 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 active compound.
  • the compounds the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound the present invention.
  • the com- pounds the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers.
  • the solutions are filtered and filled sterile.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation.
  • examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
  • Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
  • Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
  • solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methyl- ethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether
  • ketons such as acetone, methyl- ethylketone
  • aromatic hydrocarbons such as acetone, methyl- ethylketone
  • vegetable and synthetic oils dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures
  • thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium mono- stearate, 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 ointmentlike 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 ac- tive 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 which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, di- ethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrroli- done, 2-pyr
  • 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, poly- acrylates, 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, viscos- ity-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 C8-C12 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, dipropy- lene 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, o
  • Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
  • Suitable emulsifiers are:
  • non-ionic surfactants e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, al- kylphenol 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.
  • 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.
  • auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the present invention.
  • Ready-to-use preparations contain the compounds acting against parasites, pref- erably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
  • the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
  • compositions comprising the compounds of the present invention them can be applied orally, parenterally or topically, respectively dermally.
  • topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the com- pounds of the present invention.
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • the active compounds can also be used as a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
  • the active compounds can be applied solely or in a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
  • the active compounds of the present invention can be applied in mixtures with synthetic coccidiosis compounds, polyetherantibiotics as Amprolium, Ro- benidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Sem- duramicin or with other pesticides which are described in the list M above.
  • synthetic coccidiosis compounds polyetherantibiotics as Amprolium, Ro- benidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Sem- duramicin or with other pesticides which are described in the list M above.
  • Step 1 4-Hydroxy-3-(3-trifluoromethylphenyl)pyrano[3,2-b]pyridin-2-one [1-13]
  • Step 2 Methyl 3- ⁇ methyl-[2-(2-trifluormethyl-phenyl)-acetyl]-amino ⁇ -pyridine-2- carboxylate
  • Step 3 4-Hydroxy-1 -methyl-3-(2-trifluormethyl-phenyl)-1 H-[1 ,5]naphthyridin-2-one
  • Step 1 Methyl 3-[2-(2-Trifluormethyl-phenyl)-acetylamino]-pyridine-2-carboxylate 0.60 g Triethylamine (TEA) were added to a solution of 0.45 g methyl 3-amino- pyridine-2-carboxylate and 0.66 g (2-trifluormethylphenyl)acetyl chloride in 50 mL CH2CI2. After stirring was maintained at 20-25°C for 6 h the solution was washed with water. The organic phase was dried and the solvent was removed under reduced pressure.
  • TAA Triethylamine
  • Step 2 4-Hydroxy-3-(2-trifluormethyl-phenyl)-1 H-[1 ,5]naphthyridin-2-one
  • HPLC High Performance Liquid Chromatography Mass Spectrometry
  • R c2 , R c3 and R c4 are hydrogen in the compound examples listed in
  • R c2 is O-benzoyl; in compound I-52, R c2 is OH;
  • R c2 is Br
  • R c2 is CH3
  • R C2 and R c4 are both Br
  • R c3 is CF 3 ;
  • R c3 is Br
  • R c3 is CI.
  • the pesticidal activity can be demonstrated in the following biological test examples.
  • the active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
  • Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
  • Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
  • Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. Ten to 1 1 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at at 25°C and 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.
  • the active compounds were formulated in cyclohexanone as a 10,0000 ppm solu- tion supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated elec- trostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer.
  • Kinetic® nonionic surfactant
  • Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced.
  • the insects were collected using an aspirator and 0.6 cm, nontoxic 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.
  • Cups were covered with a reusable screened lid (150-micron mesh polyester screen PeCap from Tetko, Inc.).
  • Test plants were maintained in a growth room at 25°C and 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
  • the active compounds were formulated in 50:50 (vohvol) acetone:water.
  • the test solution was prepared at the day of use.
  • Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours.
  • the active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.
  • a 6 cm leaf disk of cabbage leaves was dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper. The leaf disk was inoculated with 10 third instar larvae and kept at 25-27°C and 50- 60% humidity for 3 days. Mortality was assessed after 72 h of treatment.
  • the active compounds were formulated as a 50:50 (vohvol) acetone:water solution.
  • Surfactant Alkamuls EL 620
  • Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active corn-pounds were formulated in 50:50 acetone:water and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active compounds were formulated in 50:50 acetone:water, and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • the active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone.
  • the test solution is prepared at the day of use.
  • Potted cotton plants colonized with approximately 50 mites of various stages are sprayed after the pest population has been recorded. Population reduction (or increase) after 24, 72, and 120 hours is assessed.
  • the active compounds were formulated in 1 :3 (vohvol) DMSO : water with different concentrations of formulated compounds.
  • Bean leaf disks were placed into microtiter- plates filled with 0.8% agar-agar and 2.5 ppm OPUSTM. The leaf disks were sprayed with 2.5 ⁇ of the test solution and 5 to 8 adult aphids were placed into the microtiter- plates which were then closed and kept at 23 ⁇ 1 °C and 50 ⁇ 5% relative humidity under fluorescent light for 6 days. Mortality was assessed on the basis of vital, repro- Jerusalem aphids. Aphid mortality and fecundity was then visually assessed.
  • B.12 Activity against Green Peach Aphid (Myzus persicae, mixed life stages)
  • Myzus persicae For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated com- pounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 to 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
  • the active compounds were formulated in 1 :3 DMSO : water. 15 to 25 eggs were placed into microtiterplates filled with diet. The eggs were sprayed with 10 ⁇ of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility and of comparative feeding of the hatched larvae. Tests were replicated 2 times.
  • the compound I-65 at a concentration of the test solution of 800 mg/L showed a mortality of at least 50%.
  • test unit For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 20 ⁇ , using a custom built micro atomizer, at two replications.
  • microtiter plates were incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

Abstract

The present invention relates to new insecticidal methods of using compounds of formula (I) wherein A, E, G, M, Y, X, R1 and R2 are defined as in the description, and to their enantiomers, diastereomers and agriculturally and veterinary acceptable salts. The present invention relates to methods of administering and applying such Pyridine compounds of formula I for insecticidal use and purposes in agriculture and in the veterinary field. The invention relates also to new derivatives of Pyridine compounds of formula (I).

Description

Insecticidal methods using Pyridine compounds
The present invention relates to new insecticidal methods of using Pyridine compounds and salts thereof. The present invention relates also to new Pyridine derivatives and their uses in the agricultural field.
Animal pests destroy growing and harvested crops, as well as the seeds and attack wooden dwelling and commercial structures, causing damage in the agricultural field, large economic loss to the food supply and to the 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 animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.
It is therefore an object of the present invention to provide new methods and compounds having a good pesticidal activity. Moreover it is an object of the present inven- tion to provide methods and compounds specially against difficult to control insects and acaridae.
It has been found that these objects can be solved by Pyridine compounds of formula I:
Figure imgf000002_0001
wherein
A, E, G, M are N or C-Rc, wherein one of these groups being N,
and wherein
Rc is independently from one another hydrogen or selected from Rb,
and wherein
Rb is selected, independently from one another, from a group consisting of Z-CN, Z-OH, Z-N02, Z-halogen, C1-C8-alkyl, C1-C4-haloalkyl, C2-C8- alkenyl, C2-Cs-alkynyl, Z-C1-C8-alkoxy, Z-C1-Cs-haloalkoxy, Z-C3-C10- cycloalkyl, 0-Z-C3-Cio-cycloalkyl, Z-C(=0)-Ra, NR'R", Z-(tri-C1-C4- alkyl)silyl, Z-phenyl and S(0)nRbb,
wherein
is selected from hydrogen, OH, C1-Cs-alkyl, C1-C4-haloalkyl, Z- C3-C6-cycloalkyl, C2-Cs-alkenyl, Z-Cs-Ce-cycloalkenyl, C2-C8- alkynyl, Z-C1-C6-alkoxy, Z-C1-C4-haloalkoxy, Z-Cs-Cs-alkenyl- oxy, Z-Cs-Cs-alkynyloxy, NR'R", C1-C6-alkylsulfonyl, Z-(tri-C1- C4-alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino, a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic hetero- cycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1 , 2, 3 or 4 halogen atoms and/or groups Rbb, wherein
R', R" are independently of one another selected from hydrogen, C1- Ce-alkyl, C1-C4-haloalkyl, C3-C8-alkenyl, C3-C8-alkynyl, Z-C3-C6- cycloalkyl, Z-C1-C8-alkoxy, Z-C1-C8-haloalkoxy, Z-C(=0)-Rbb, Z- phenyl, a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic, saturated, unsaturated or aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, attached via Z,
or wherein
R' and R" together with the nitrogen atom to which they are attached to may also form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S; Rbb is C1-Ce-alkyl or d-C6-haloalkyl; and
Z is a covalent bond or C1-C4-alkylene chain;
or wherein
Rb together with the group Rb optionally attached to the adjacent carbon atom may also form a 5- or 6-membered saturated or partially or fully unsaturated ring which, which in addition to carbon atoms, may also contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;
X, Y are selected from O, S or N-R3;
R1 is selected from 0-RA- S(0)n-RA or OS(0)n-RA; wherein
n is 0, 1 or 2; and
RA is selected from hydrogen, C1-C4-alkyl, Z-C3-C6-cycloalkyl, C1-C4- haloalkyl, C2-C6-alkenyl, Z-C3-C6-cycloalkenyl, C2-C6-alkynyl, Z-(tri-C1-C4-- alkyl)silyl, Z-C(=0)-Ra, Z-P(=0)(Ra)2, Z-NRi-C(0)-N R'Rii, NR'R", a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic, saturated, unsaturated or aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, which may be attached via the carbon or nitrogen atom, and which may be partially or fully substituted by groups selected from Ra and/or Rb; R2 is selected from phenyl, naphthyl, a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S,
and wherein
the cyclic groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups Rb; R3 is selected from hydrogen, C1-C6-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C3- C6-alkynyl, Z-C3-Cio-cycloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-cyanoalkyl,
Z-phenyl, a 5- or 6 membered monocyclic heterocycle attached via Z, which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which may be attached via a carbon or a nitrogen atom of the heterocycle, Z-C(=O)-Ra2 or tri- C1-C4-a I kyl s i I yl , and wherein Ra2 is selected from C1-C6-alkyl, C1-C4-haloalkyl, Z-C1-C6-alkoxy, Z-C1-C4- haloalkoxy or NR'R";
and wherein
in the groups RA, R3 and their subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups Rb;
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.
The present invention relates to following insecticidal methods applying such compounds of formula I.
It was an object of the present invention to provide methods of combating and controlling animal pests which methods comprise contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;
It was further an object of the present invention to provide methods for protecting crops and growing plants from attack or infestation by animal pests, which methods comprise contacting a crop or a growing plant with a pesticidally effective amount of at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;
Another object of the present invention was to provide methods for protecting plant propargation material, especially seeds, from soil insects and seedlings' roots and shoots from soil and foliar insects, which methods comprise contacting the seeds before sowing and/or after pregermination with at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof; And another object of the present invention was to provide methods for treating, controlling, preventing or protecting animals against infestation or infection by parasites, which methods comprise administering or applying to the animals and/or to their enviroment a parasitically effective amount of at least one Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or a veterinary acceptable salt thereof.
Object of the invention are also methods of using at least one compound of the formula I and/or an N-oxide, enantiomer, diastereomer and/or a veterinary acceptable salts thereof, for combating parasites in and on animals by treating the parasites with an parasitical active amount thereof.
In this field it was further an object of the present invention to use Pyridine compound of formula I and/or an N-oxide, enantiomer, diastereomer or a veterinary acceptable salt thereof for the preparation of a medicament for treating animals against infestion and infection by parasites. Furthermore, the present invention relates also to new pyridine compounds of the general formulae II and III, their N-oxides, enantiomers, diastereomers or agricultural or veterinary useful salts thereof and to veterinary or agricultural compositions comprising them and at least one inert liquid and/or solid agronomically acceptable carrier, as well as to their uses as described above for compounds of formula I.
The present invention relates also to compounds of formula I, which are of formula II:
Figure imgf000005_0001
wherein
Y is S or O;
X is S or O;
R1 is selected from hydrogen, C1-C6-alkylcarbonyl or C1-C6-alkoxycarbonyl, and
Rc2, Rc3, Rc3', Rc4, c4' and Rc5' are selected independently from one another from the group consisting of hydrogen, OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy.
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof. The present invention relates also to compounds of formula I ,which are of formula III:
Figure imgf000005_0002
wherein
X is O or S;
R1 is selected from hydrogen, C1-C6-alkylcarbonyl or C1-C6-alkoxycarbonyl;
R2 is phenyl or pyridyl, which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxy and C1-C4-haloalkoxy;
Rc2, Rc3, Rc4 are selected independently from one another from the group consisting of hydrogen, OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;
and
R3 is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyridyl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl and isoxazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, wherein
Z is a covalent bond or C1-C4-alkylene chain, wherein the carbon chain may optionally carry one or more substituents selected from C1-C8-alkyl or C1-C4- haloalkyl;
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.
Substituted pyridine derivatives such as pyridopyrazines have been described in WO 2008/009908 and WO 2008/071918 for their herbicidal uses. Other pyridine compounds have been described in WO2009/090401 and WO2009/090402 also for herbicidal activity. Further herbicidal pyridine compounds are described in unpublished applications PCT/EP2009/063387 and PCT/EP2009/063386.
However, no insectidial uses and applications are to be found for such pyridine compounds of formula I. Neither the compounds of formula II and III, nor their insecti- cidal activity as well as methods of applications and uses thereof were described previously.
The compounds of the formula I, II and III, their N-oxides, enantiomers, diastereo- mers and their agriculturally or veterinary acceptable salts thereof are highly active against animal pest, i.e. harmful arthropodes and nematodes. They may be used against difficult to control insects and acaridae.
Thus, the present invention relates to and includes the following embodiments: agricultural and veterinary compositions comprising an amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
the use of a compound of formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof for combating or controlling animal pests;
a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
- a method for protecting crops from attack or infestation by animal pests, which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;
a method for the protection of plant propargation material, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propargation material, especially the seeds, before sowing and/or after pregermination with at least one compound of the formula I, II or III, or the N-oxide, enantiomers, diastereomers or salts thereof; seeds comprising a compound of the formula I ,11 or III, or an N-oxide, enanti- omer, diasteromer or salt thereof;
the use of compounds of formula 1,11 or III, or the N-oxide, enantiomers, di- astereomers or veterinary acceptable salts thereof for combating parasites in and on animals;
a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of an compound of formula I, II or III, or the N-oxide, enantiomers, diastereomers and/or veterinary acceptable salt thereof;
the use of compounds of formula I, II or III, or the N-oxide, enantiomers, diastereomers or veterinary acceptable salts thereof for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites, wherein the composition comprisess a parasiticidally effective amount of an compound of formula I, II or III, or the enantiomers, diastereomers and/or veterinary acceptable salt thereof.
Depending on the substitution pattern, the compounds of the present invention can contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures. Subject matter of this invention are not only compositions containing these mixtures but also those containing the pure enantiomers or diastereomers.
The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the formula I, II or III or as well mixtures of their different crystalline states.
Salts of the compounds of formulae I, II and III are preferably agriculturally and veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formulae I, II or III has a basic functionality or by reacting an acidic compound of formulae I, II or III 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. Suit-able 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 C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-alkoxy, C1-C4-alkoxy- C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammo-nium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy-drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of the present invention 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 the present invention con- taining a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
The prefix Cn-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 par- ticu-lar fluorine, chlorine or bromine.
Examples of other meanings are:
The term "C1-C6-alkyl" as used herein and in the alkyl moieties of C1-C6-alkoxy, C1-C6-alkylamino, di(C1-C6-alkyl)amino, C1-C6-alkylthio, C1-C6-alkylcarbonyl, C1-C6-alk- oxycarbonyl, C1-C6-alkylaminocarbonyl and di(C1-C6-alkyl)aminocarbonyl refers to a saturated straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 3 carbon groups (= C1-C3-alkyl). Examples for C1-C3-alkyl are methyl, ethyl, propyl and 1 -methylethyl (isopropyl). Examples for C1-C6 alkyl further encompass, butyl, 1 -methylpropyl (sec-butyl, 2-butyl), 2-methylpropyl (iso-butyl), 1 ,1 -dimethyl- ethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3 methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, 1 ,1 -dimethylpropyl, 1 ,2 dimethylpropyl, 1 -methylpentyl, 2-methyl- pentyl, 3 methylpentyl, 4-methylpentyl, 1 ,1 dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-di- methylbutyl, 2,2-dimethylbutyl, 2,3 dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, 1 -ethyl- 2-methylpropyl.
The term "C1-C6-haloalkyl" as used herein and in the haloalkyl moieties of C1-C6- haloalkoxy, C1-C6-haloalkylthio, C1-C6-haloalkylcarbonyl and C1-C6-haloalkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C1-C3-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoro- methyl, chloro-fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromoethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chlo- ro-2-fluoroethyl, 2 chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloro- ethyl, pentafluoroethyl and the like.
The term "C1-C6-alkoxy" as used herein and in the term C1-C6-alkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, pref- erably 1 to 3 carbon atoms (= C1-C3-alkoxy) which is attached via an oxygen atom. Examples for C1-C3-alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy) and
OCH(CH3)2 (isopropoxy). Examples for C1-C6-alkoxy further encompass n-butoxy, OCH(CH3)C2H5 (sec-butoxy), OCH2CH(CH3)2 (isobutoxy), OC(CH3)3 (tert-butoxy), n- pentoxy, 1 methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2- dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, n-hexoxy, 1 methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethyl- butoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbut- oxy, 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 "C1-C6-haloalkoxy" as used herein and in the term C1-C6-haloalkoxy- carbonyl refers to a C1-C6-alkoxy group as men-tioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are C1-C3-haloalkoxy groups, i.e. C1-C3-alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bro- mine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2- iodoethoxy,
2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro- ethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoro- propoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3- chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoro- propoxy, 3,3,3 trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, 1 - (fluoromethyl)-2-fluoroethoxy, 1 -(chloromethyl)-2-chloroethoxy and 1 (bromomethyl)-2- bromoethoxy. Examples for C1-C6-haloalkoxy further encompass 4-fluorobutoxy, 4- chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoro-1 -pentoxy, 5-chloro-1 -pent- oxy, 5 bromo-1 -pentoxy, 5-iodo-1 -pentoxy, 5,5,5-trichloro-1 -pentoxy, undecafluoropen- toxy, 6-fluoro-1 -hexoxy, 6-chloro-1 -hexoxy, 6-bromo-1 -hexoxy, 6-iodo-1 -hexoxy, 6,6,6 trichloro-1 -hexoxy and dodecafluorohexoxy. Particularly preferred are chloromethoxy, fluorometh-oxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2 chloroethoxy and 2,2,2-trifluoroethoxy.
The term "C1-C6-alkylcarbonyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkylcarbonyl) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group. Examples for C1-C4-alkylcarbonyl include C(=0)CH3, C(0)C2H5, n-propylcarbonyl, 1 -methylethylcarbonyl, n-butylcarbonyl, 1 -methylpropylcarbonyl, 2-methylpropylcarbonyl and 1 ,1 -dimethylethylcarbonyl. Examples for C1-C6-alkylcar- bonyl further encompass n-pentylcarbonyl, 1 -methylbutylcarbonyl, 2-methylbutylcar- bonyl, 3-methylbutylcarbonyl, 1 ,1 -dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl,
2.2- dimethylpropylcarbonyl, 1 -ethylpropylcarbonyl, n-hexylcarbonyl, 1 -methylpentyl- carbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1 ,1 - dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethylbutylcarbonyl, 2,2-di- methylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1 -ethylbutyl- carbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2 trimethylpropylcarbonyl, 1 ,2,2-trimethylpropyl- carbonyl, 1 -ethyl-1 -methylpropylcarbonyl or 1 -ethyl-2-methylpropylcarbonyl and the like.
The term "C1-C6-alkoxycarbonyl" as used herein refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkoxycarbonyl) attached via the carbon atom of the carbonyl group
(R-O-C(O)-; R = alkyl). Examples for C1 -C4-alkoxycarbonyl include -C(0)OCH3, -C(0)OC2H5, -C(0)0-CH2-C2H5, -C(0)OCH(CH3)2, n-butoxycarbonyl, -C(0)OCH(CH3)- C2H5, -C(0)-OCH2CH(CH3)2 and C(0)OC(CH3)3. Examples for C1 -C6-alkoxycarbonyl further encompass n-pentoxycarbonyl, 1 -methylbutoxycarbonyl, 2-methylbutoxycar- bonyl, 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-tri- methylpropoxycarbonyl, 1 ,2,2-trimethylpropoxycarbonyl, 1 -ethyl-1 -methylpropoxy- carbonyl or 1 -ethyl-2-methylpropoxycarbonyl.
The term "C1-C6-alkylthio "(C1-C6-alkylsulfanyl: C1-C6-alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (= C1 -C3-alkylthio) which is attached via a sulfur atom. Examples for C1 -C3-alkylthio include methylthio, ethylthio, propylthio and 1 methyl- ethylthio. Examples for C1-C6-alkylthio further encompass butylthio, 1 -methylpropylthio, 2-methylpropylthio and 1 ,1 -dimethylethylthio. n-pentylthio, 1 -methylbutylthio, 2-methyl- butylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1 -ethylpropylthio, n-hexylthio, 1 ,1 - dimethylpropylthio, 1 ,2-dimethylpropylthio, 1 -methylpentylthio, 2-methylpentylthio, 3- methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3- dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 - ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1 - ethyl-1 -methylpropylthio and 1 -ethyl-2-methylpropylthio.
In analogy to the above, the term "C1-C6-alkylsulfonyl" (C1-C6-alkyl-S02-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (= C1-C3-alkylthio) which is attached via a sul- fonyl group SO2.
In case when in the term "NR'R"" one of R' or R" is C1-C6-alkyl or d-Ce-alkylcarbo- nyl, this is represented by the term "C1-C6-alkylamino" or the term "C1-C6-alkylamino- carbonyl", or when both of R' and R" are C1-C6-alkyl or C1-C6-alkylcarbonyl this represented by the term "di(C1-C6-alkyl)amino)" or the term "di(C1-C6-alkylamino)-carbonyl".
In such cases the term "C1-C6-alkylamino" as used herein and the term "C1-C6-al- kylaminocarbonyl" refers to a secondary amino group carrying one alkyl group as defined above, e.g. methylamino, ethylamino, propylamino, 1 -methylethylamino, butyl- amino, 1 -methylpropylamino, 2-methylpropylamino, 1 ,1 -dimethylethylamino, pentyl- amino, 1 -methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethyl- propylamino, 1 -ethylpropylamino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethyl- propylamino, 1 -methylpentylamino, 2-methylpentylamino, 3-methylpentylamino, 4- methylpentylamino, 1 ,1 -dimethylbutylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethyl- butylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1 -ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2-trimethylpropylamino, 1 ,2,2-trimethyl- propylamino, 1 -ethyl-1 -methylpropylamino or 1 -ethyl-2-methylpropylamino.
And the term "di(C1-C6-alkyl)amino)" as used herein and the term "di(C1-C6-alkyl- amino)-carbonyl" refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g. dimethylamino, diethylamino, di-n-propylamino, diiso-propylamino, N-ethyl- N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)- N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)- N-methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)-N ethylamino, N-(isopropyl)- N-ethylamino, N-(n-butyl)-N-ethylamino, N-(n-pentyl)-N ethylamino, N-(2-butyl)-N-ethyl- amino, N-(isobutyl)-N-ethylamino and the like.
The term "C2-C6-alkenyl" as used herein and in the alkenyl moieties of C2-C6-al- kenyloxy, C2-C6-alkenylamino and C2-C6-alkenylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1 -methyl-ethenyl, 1 -bu- tenyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2 methyl-1 -propenyl, 1 -methyl-2-pro- penyl, 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-but- enyl, 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-but- enyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-di- methyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-but- enyl, 2,3-dimethyl-3-butenyl, 3,3 dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 - butenyl, 1 -ethyl-2-butenyl, 1 ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2- ethyl-3-butenyl, 1 ,1 ,2 trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2- methyl-1 -propenyl and 1 -ethyl-2-methyl-2-propenyl.
The term, "C2-C6-alkenyloxy" as used herein refers to a straight-chain or branched al-kenyl group having 2 to 6 carbon atoms which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy and the like.
The term "C2-C6-alkynyl" as used herein and in the alkynyl moieties of
C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio and C2-C6-alkynylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1 -yn-1 -yl, prop-2-yn-1 -yl, n-but-1 -yn-1 -yl, n-but-1 -yn-3-yl, n-but-1 -yn-4-yl, n-but-2-yn-1 -yl, n-pent- 1 -yn-1 -yl, n-pent-1 -yn-3-yl, n-pent-1 -yn-4-yl, n-pent-1 -yn-5-yl, n-pent-2-yn-1 -yl, n-pent-
2- yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1 -yn-3-yl, 3-methylbut-1 -yn-4-yl, n-hex-1 -yn-1 - yl, n-hex-1 -yn-3-yl, n-hex-1 yn-4-yl, n-hex-1 -yn-5-yl, n-hex-1 -yn-6-yl, n-hex-2-yn-1 -yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1 -yl, n-hex-3-yn-2-yl,
3- methylpent-1 -yn-1 -yl, 3 methylpent-1 -yn-3-yl, 3-methylpent-1 -yn-4-yl, 3-methylpent-1 - yn-5-yl, 4-methylpent-1 -yn-1 -yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl and the like.
The term, "C2-C6-alkynyloxy" as used herein refers to a straight-chain or branched al-kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, butyn-4-yloxy and the like.
The term "C3-Ci2-cycloalkyl" as used herein refers to a mono- or bi- or polycyclic hydrocarbon radical having 3 to 12 (= C3-Ci2-cycloalkyl), frequently 3 to 8 carbon atoms (= Cs-Cs-cycloalkyI), in particular 3 to 6 carbon atoms (= C3-C6-cycloalkyl). Examples of monocyclic radicals comprise cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. Phenyl fused to benzene is naphthyl.
Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl,
2,3-dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like. Examples for phenyl fused to a 5- or 6-membered aromatic heterocyclic ring (= fused to a 5- or 6-membered heteroaromatic ring) are given below.
The term "saturated or (partially) unsaturated heterocycle" comprises nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms as ring members. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Examples for non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3- dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4- dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxa- zolidin-2-onyl, thiazolidin-2-onyl and the like.
The term "aromatic heterocycle" or "heteroaryl" ("mono or bicyclic 5- to 10- membered") as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyclic or heterocyclic 5, 6 or 7 mem- bered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heteraryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The carbocyclic or heterocyclic fused ring is selected from C5-C7-cycloalkyl, 5 to 7 membered heterocyclyl and phenyl.
Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxa- zolyl.
Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring (or for benzene fused to a 5- to 6-membered heteroaromatic ring) are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl,
benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl. Examples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.
The term "linear or branched C1-C6-alkanediyl" as used herein and in the term
C1-C6-alkanediyloxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms
(= C1-C4-alkanediyl), where one of the hydrogen atoms in these groups is replaced by a further bonding position. Examples for linear C1-C6-alkanediyl comprise methyldiyl, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl. Examples for branched C1-C6-alkanediyl comprise ethyl-1 ,1 -diyl, propyl-1 ,1 -diyl, butyl- 1 ,1 -diyl, 1 -methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1 -ethylethane-1 ,2 diyl, 1 -methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like. With respect to the different methods and uses according to the invention, particular preference is given to the following meanings of the substituents and variables of the Pyridine compounds of formula I used, in each case on their own or in combination.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that R1 is selected from hydrogen, C1-C6-alkyl- carbonyl or C1-C6-alkoxycarbonyl.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that Y is O. In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that Y is S.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that Y is N-R3, and R3 is selected from hydrogen, C1-C6-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, C1- Ce-alkoxy-d-Ce-alkyl, C1-C6-cyanoalkyl, Z-phenyl, Z-C(=0)-Ra2 or tri-C1-C4-alkylsilyl; wherein Ra2 is selected from C1-C6-alkyl, C1-C4-haloalkyl, Z-C1-C6-alkoxy, Z-C1-C4- haloalkoxy or NR'R".
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that Y is N-R3, and wherein R3 is a 5- or 6- membered monocyclic heterocycle attached via Z and selected from the group consisting of pyrimidyl, pyridyl, thienyl, furyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, quinolinyl, isoquinolinyl, indolyl, benzofuryl, benzthienyl, ben- zoxazolyl, benzthiazolyl and benzimidazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle or Z may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that X is O.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that X is S.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that A is N and E, G and M are C-Rc, wherein Rc is independently from one another hydrogen or selected from Rb as defined above.
In the methods and uses according to present invention, preferably the compounds of formula (I) used are characterized in that A is N, X is O, Y is O or S and E, G and M are C-Rc, and wherein Rc is independently from one another hydrogen or selected from Rb as defined as above.
In the methods and uses according to present invention, preferably the compounds used are characterized in that the pyridine compound is of formula I. A
Figure imgf000014_0001
wherein Y, R1, and Rb are as defined for formula (I) above, Rc2, Rc3 and Rc4 are selected independently from one another from Rc as defined above, and m is 0, 1 , 2, 3 or 4.
The above embodiments preferred for formula I apply also to compounds of formulae II, and III, resp., insofar applicable to formulae II, and III, resp.
In particular with view to the compounds themselves and their use as insecticides, preference is given to the compounds of the formula II compiled in the examples below, wherein the compounds corresponds to the formula ll-A below:
Figure imgf000015_0001
wherein Y, R1, Rc2, Rc3 and Rc4 are defined as in table II below, and Rc3', R04' and Rc5' are defined as in tables lla to tables Mm thereinafter.
The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000015_0002
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Figure imgf000026_0001
Figure imgf000027_0001
Table Ma:
Compounds II.1 a to ll.494a of the formula ll-A, in which Rc3' is CI, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II.
Table lib:
Compounds 11.1 b to 11.494b of the formula ll-A, in which Rc3' is F, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table lie:
Compounds 11.1 c to 11.494c of the formula ll-A, in which Rc3' is Br, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table lid:
Compounds 11.1 d to ll.494d of the formula ll-A, in which Rc3' is CF3, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table lie:
Compounds 11.1 e to ll.494e of the formula ll-A, in which Rc3' is CHF2, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table I If:
Compounds II.1f to ll.494f of the formula ll-A, in which Rc3' is OCF3, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table 11
Table llg:
Compounds 11.1 g to ll.494g of the formula ll-A, in which Rc3' is H, Rc4' is CI, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table llh:
Compounds 11.1 h to ll.494h of the formula ll-A, in which Rc3' is H, Rc4' is F Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table IN:
Compounds 11.1 i to ll.494i of the formula ll-A, in which Rc3' is H, Rc4' is Br Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table llj:
Compounds II.1j to ll.494j of the formula ll-A, in which Rc3' is H, Rc4' is CF3, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table Ilk:
Compounds 11.1 k to 11.494k of the formula ll-A, in which Rc3' is H, Rc4' is CHF2, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 for a compound corresponds in each case to one row of Table II
Table III:
Compounds 11.11 to 11.4941 of the formula for ll-A, in which Rc3' is H, Rc4' is OCF3, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 a compound corresponds in each case to one row of Table II
Table Mm:
Compounds 11.1 m to 11.494m of the formula for ll-A, in which Rc3' is H, Rc4' is H, Rc5' is H and the combination of Y, R1, Rc2, Rc3 and Rc4 a compound corresponds in each case to one row of Table II In particular with view to the compounds themselves and their use as insecticides, preference is given to the compounds of the formula III compiled in the examples below, wherein the compounds corresponds to the formula lll-A below:
Figure imgf000029_0001
wherein R1, Rc2', Rc3' and Rc4' are defined as in table III below, and R3 is defined as in tables Ilia to lllp thereinafter.
The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question.
Figure imgf000029_0002
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0004
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corre-
Figure imgf000036_0003
sponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table 1Mb:
Compounds 111.1 b to lll.286b of the formula lll-A, in which R3 is
Figure imgf000036_0001
3 and the combination of R1, Rc2', Rc3' and Rc4' for a compound corre- sponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllc:
Compounds 111.1 c to III.286c of the formula lll-A, in which R3 is
Figure imgf000036_0002
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corre- sponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table llld:
Compounds lll.l d to lll.286d of the formula lll-A, in which R3 is F
Figure imgf000037_0001
3 and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table llle:
Compounds lll.l e to lll.286e of the formula lll-A, in which R3 is
Figure imgf000037_0002
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllf:
Compounds lll.lf to lll.286f of the formula lll-A, in which R3 is
Figure imgf000037_0003
3 and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllg:
Compounds lll.l g to lll.286g of the formula lll-A, in which R3 is and the combination of R1, Rc2', Rc3' and Rc4' for a compound corre
Figure imgf000037_0004
sponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllh:
Compounds lll.l h to lll.286h of the formula lll-A, in which Rc3 is
Figure imgf000037_0005
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table llli:
Compounds lll.l i to lll.286i of the formula lll-A, in which R3 is
Figure imgf000037_0006
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllj:
Compounds lll.lj to lll.286j of the formula lll-A, in which R3 is
S
and the combination of R1, Rc2', Rc3' and Rc4' for a compound cor-
Figure imgf000037_0007
responds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table Nik:
k to lll.286k of the formula lll-A, in which R3 is
Figure imgf000038_0001
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table Nil:
Compounds 111.11 to 111.2861 of the formula for lll-A, in which R3 is
Figure imgf000038_0002
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllm:
Compounds 111.1 m to III.286m of the formula lll-A , in which R3 is
Figure imgf000038_0005
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table llln:
Compounds 111.1 η to lll.286n of the formula lll-A, in which R3 is
Figure imgf000038_0006
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table I Mo:
Compounds 111.1 ο to lll.286o of the formula lll-A, in which R3 is
Figure imgf000038_0003
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.
Table lllp:
Compounds lll.l p to lll.286p of the formula lll-A, in which R3 is
Figure imgf000038_0004
and the combination of R1, Rc2', Rc3' and Rc4' for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule. The compounds according to the invention can be prepared analogously to the synthesis routes described in WO 2008/009908 and WO 2008/071918 or as described in unpublished PCT/EP2009/063387 and PCT/EP2009/063386 and according to standard processes of organic chemistry, for example according to the following synthesis route:
Pyridine carboxylic acids of the formula IV can be reacted with carbonyl compounds of the formula V to give compounds of the formula VI. In the formulae IV and V, the variables have the meaning given for formula I. The group Hal is a halogen atom or another suitable nucleophilic leaving group, such as alkoxy or phenoxy.
Figure imgf000039_0001
This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chem- istry 1994, 37(3), 273-282) or other known coupling agents.
Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclo- hexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p- xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to tertiary amines such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
The starting materials are generally reacted with one another in equimolar amounts.
The compounds of the formula VI are activated by introducing a leaving group L1. Suitable leaving groups L1 are, in general, groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluorophenoxy.
Figure imgf000040_0001
This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chemistry 1994, 37(3), 273-282) or other known coupling agents.
Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably methylene chloride and toluene. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alka- line earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potas- sium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
The starting materials are generally reacted with one another in equimolar amounts.
Suitable agents H-L1 are alcohols, optionally subst. phenols, Ν,Ο-dialkylhydroxyl- amine, in particular pentafluorophenol or Ν,Ο-dimethylhydroxylamine.
The compounds of the formula VII are cyclized to give the compounds of the formula I.
Figure imgf000041_0001
This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf. Silverman, Richard B. J. Am. Chem. Soc. 1981 , 103(13), 3910].
Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile and dimethylformamide. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometal- lic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethyl- amine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bi- cyclic amines. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.
The starting materials are generally reacted with one another in equimolar amounts. Alternatively, the compounds of the formula I can also be obtained via a reverse reaction sequence, i.e. the reaction of the compounds of the formula IV with compounds
H-L1 gives the activated derivatives of the formula VIII.
OH
Ε"Αγ^Ο H-L.1
M YH
Figure imgf000042_0001
IV VIII
Per se, this reaction is carried out under the conditions mentioned for the reaction of the formula VI with H-L1.
The compounds of the formula VIII can then be reacted with compounds V to give the derivatives of the formula IX.
Figure imgf000042_0002
Per se, this reaction is carried out under the conditions mentioned for the reaction of the formula IV with V.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from vola- tile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, the purification can also be carried out by recrystallization or digestion.
If individual compounds of formula I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds of formula I.
Same applies to compounds of formula II or of formula III.
If the synthesis yields mixtures of isomers, a separation is generally however not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after application, for example in the case of the treatment of plants in the treated plant or in the harmful plant to be controlled.
In order to obtain salts, which are suitable for agricutural or veterinary use, the Pyridine compounds of formula I, II and III can be reacted with conventional salt builders as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, benzene sulfonic acid, p-toluol-sulfonic acid, dode- cylbenzene sulfonic acid, methyl bromide, dimethyl sulfate or diethyl sulfate in temperature range of 0 to 150°C, preferably 20 to 120 °C. The formation of the salt is usually conducted in a dissolving or diluting agent. Suitable are e.g. aliphatic hydrocarbons as n-pentane, n-hexane or petrol ether, aromatic hydrocarbons, as benzole, toluole or xylole, benzine or ethers as diethyl ether, methyl- tert. -butyl ether, tetrahydrofurane or dioxane, further ketones, as acetone, methyl-ethyl- ketone or methyl-isopropyl-ketone, as well as halogenated hydrocarbons as chloroben- zole, methylene chloride, ethylenen chloride, chloroform or tetrachlor ethylene. Also mixtures of those solvents can be used.
For the preparation of salts of compounds of the present invention the educts are employed usually in a stoichiometric ratio. The excess of one or the other component can be useful.
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 compounds of the present invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
Animal pests controlled by the compounds of the present invention include for example:
Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsi- lon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia con- jugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia 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, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes ob- scurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epila- chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sito- philus granaria;
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis,
Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phor- bia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Sto- moxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frank- liniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis;
bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acros- ternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysder- cus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyl- lopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nastur- tii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum so- lani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosi- pha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plan- taginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rho- palomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus;
ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa,
Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica,
Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroc- canus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hiero- glyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminif- era, and Locustana pardalina;
arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambry- omma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Orni- thodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Pso- roptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyl- locoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panony- chus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,
millipedes (Diplopoda), e.g. Narceus spp.,
Earwigs (Dermaptera), e.g. forficula auricularia,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovi- cola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. Collembola (springtails), e.g. Onychiurus ssp..
They are also suitable for controlling Nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne ja- vanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- chiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Hete- rodera 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 nemato- des, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocrico- nema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species;
Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longi- dorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Bur- rowing 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, Paratri- chodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species. The compounds of the present invention are also useful for controlling arachnids (Arachnoidea), such as acarians (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.
Compounds of the present invention are particularly useful for controlling insects, preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species:
Thysanoptera : Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scir- tothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
Diptera, e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens,
Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gam- biae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chryso- mya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia an- thropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefascia- tus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radi- cum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachin- oides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Maye- tiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomo- nella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;
Hemiptera, in particular aphids: 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, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosi- phum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae,
Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rho- palomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
Compounds of the present invention are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.
For use in a method according to the present invention, the compounds of the present invention can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions. The use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the present 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", Chemi- cal 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 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998, for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, antifoaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Solvents/carriers, which are suitable, are e.g.:
solvents such as water, aromatic solvents (for example Solvesso products, xy- lene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexa- none, gamma-butyrolactone), pyrrolidones (N-metyhl-pyrrolidone (NMP),N- octylpyrrolidone NOP), acetates (glycol diacetate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modified oils such as alkylated plant oils. In principle, solvent mixtures may also be used,
carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and 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.
Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants 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, polyoxy- ethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, al- kylphenyl 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 polyoxy- propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters,
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.
Suitable preservatives are for example dichlorophen und benzyl alcohol hemiformal Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Mention may be made, in this context, for example, of commercial thickeners based on polysaccharides, such as Xanthan Gum® (Kelzan® from Kelco), Rhodopol®23 (Rhone Poulenc) or Veegum® (from R.T. Vanderbilt), or organic phyllosilicates, such as Atta- clay® (from Engelhardt). Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon® SRE, Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trademarks Proxel® from Avecia (or Arch) or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas. Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound com- position. If appropriate, the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.
Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nut- shell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from
0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold lead- ing 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 compound of formula I or formula II can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention. The following are examples of formulations:
1 . Products for dilution with water. 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 is 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 dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound is obtained. B) Dispersible concentrates (DC)
20 parts by weight of the active compound is dissolved in 70 parts by weight of cyclo- hexanone 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 compounds is obtained.
C) Emulsifiable concentrates (EC)
15 parts by weight of the active compounds is 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 compounds is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound is 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 is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound is 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 suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound is 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 is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound 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, whereby a formulation with 75% (w/w) of active compound is obtained.
H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound is 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 suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound 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 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.
J) Granules (GR, FG, GG, MG)
0.5 part by weight of the active compound is ground finely and associated with 95.5 parts by weight of 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 is dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound, which is applied undiluted for foliar use.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wet- table 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 emul- sifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.
The active ingredients may also be used successfully in the ultra-low-volume proc- ess (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.
Formulations of compounds of the present invention as aerosols (e.g in spray cans),
011 sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used. For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
In the method of this invention compounds of the present invention may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxi- cants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
The following list 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)phosphate compounds: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fam- phur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, mono- crotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phen- thoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, pro- fenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion;
M.2. Carbamate compounds: aldicarb, alanycarb, bendiocarb, benfuracarb, buto- carboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobu- carb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; M.3. Pyrethroid compounds: acrinathrin, allethrin, d-cis-trans allethrin, d-trans al- lethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cyclo- prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cyper- methrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpro- pathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), res- methrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin;
M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, niten- pyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiaclo- prid, thiocyclam, 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, le- pimectin;
M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, te- bufenpyrad, tolfenpyrad, flufenerim, rotenone;
M.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;
M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
M.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbutatin 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, novif- lumuron, teflubenzuron, triflumuron;
M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
M.20. Octapaminergic agonsits: amitraz;
M.21 . Ryanodine receptor modulators: flubendiamide and the phtalamid compound (R)-, (S)- 3- Chloro-N1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid (M21 .1 )
M.22. Isoxazoline compounds: 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5- dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide (M22.1 ),
4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N- (2,2,2-trifluoro-ethyl)-benzamide (M22.2), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl- 4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-benz- amide (M22.3), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]- naphthalene-1 -carboxylic acid [(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-amide (M22.4), 4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-N-[(methoxy- imino)methyl]-2-methylbenzamide (M22.5), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)-5- trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)- methyl]-benzamide (M22.6), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)-5-trifluoromethyl- 4,5-dihydro-isoxazol-3-yl]-naphthalene-1 -carboxylic acid [(2,2,2-trifluoro-ethylcarb- amoyl)-methyl]-amide (M22.7) and 5-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-trifluoromethyl- 4,5-dihydro-isoxazol-3-yl]-2-[1 ,2,4]triazol-1 -yl-benzonitrile (M22.8);
M.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole, 5-Bromo-2- (3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 -cyclopropyl-ethyl- carbamoyl)-6-methyl-phenyl]-amide (M23.1 ), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H- pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]- amide (M23.2), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bro- mo-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M23.3), 5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6-(1 -cyclopropyl- ethylcarbamoyl)-phenyl]-amide(M23.4), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole- 3-carboxylic acid [2,4-dichloro-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide
(M23.5), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2- (1 -cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide (M23.6), N'-(2-{[5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-hy- drazinecarboxylic acid methyl ester (M23.7), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)- 2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N'-methyl-hydrazine- carboxylic acid methyl ester (M23.8), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H- pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N,N'-dimethyl-hydrazine- carboxylic acid methyl ester (M23.9), N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin- 2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-hydrazinecarboxylic acid methyl ester (M23.10), N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-car- bonyl]-amino}-benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.1 1 ) and N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.12);
M.24. Malononitrile compounds: 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3- trifluoro-propyl)malononitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF3) (M24.1 ) and 2-(2,2,3, 3,4,4, 5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF2-CF3) (M24.2);
M.25. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaeri- cus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
M.26. Aminofuranone compounds:
4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.1 ), 4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.2),
4-{[(2-Chloro1 ,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.3), 4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.4), 4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.5), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.6), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.7),
4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.8), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.9) and 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.10);
M.27. Various compounds: aluminium phosphide, amidoflumet, benclothiaz, ben- zoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor, N-R'-2,2-dihalo-1 -R"cyclo-pro- panecarboxamide-2-(2,6-dichloro-a ,a ,a -trifluoro-p-tolyl)hydrazone or N-R'-2,2- di(R"')propionamide-2-(2,6-dichloro-a ,a ,a -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, 4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1 -yl)-2-fluoro-pyrimidine (M27.1 ), Cyclopropaneacetic acid , 1 ,1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopropyl- acetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-tri- methyl-1 1 -oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl] es- ter(M27.2) and
8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3- yl)-3-aza-bicyclo[3.2.1 ]octane(M27.3).
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.
Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001 . Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. AKD 1022 and its preparation have been described in US 6300348. The anthranilamides M23.1 to M23.6 have been described in WO 2008/72743 and WO 200872783, those M23.7 to M23.12 in WO2007/043677. The phthalamide M 21.1 is known from WO 2007/101540. -The al- kynylether compound M27.1 is described e.g. in JP 2006131529. Organic sulfur com- pounds have been described in WO 2007060839. The isoxazoline compounds M 22.1 to M 22.8 have been described in e.g. WO2005/085216, WO 2007/079162, WO 2007/026965, WO 2009/126668 and WO2009/051956. The aminofuranone compounds M 26.1 to M 26.10 have been described eg. in WO 2007/1 15644. The pyripy- ropene derivative M 27.2 has been described in WO 2008/66153 and WO
2008/108491. The pyridazin compound M 27.3 has been described in JP 2008/1 15155. Malononitrile compounds as those (M24.1 ) and (M24.2) 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. The following list of fungicidal active substances which, in combination with the compounds of the present invention, can be used in pesticidal mixtures is intended to illustrate the possible combinations, but does not limit them:
F.I) Respiration Inhibitors
F.I-1 ) Inhibitors of complex III at Qo site (e.g. strobilurins)
strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picox- ystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyri- carb/chlorodincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3- methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl- allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;
oxazolidinediones and imidazolinones: famoxadone, fenamidone;
F.I-2) Inhibitors of complex II (e.g. carboxamides): carboxanilides: benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flu- opyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5- carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyra- zole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H- pyrazole-4 carboxamide;
F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom;
F.I-4) Other respiration inhibitors (complex I, uncouplers)
diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam;
nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
F.ll) Sterol biosynthesis inhibitors (SBI fungicides)
F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusila- zole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;
imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine; F.II-2) Delta 14-reductase inhitors (Amines, e.g. morpholines, piperidines) morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
piperidines: fenpropidin, piperalin;
spiroketalamines: spiroxamine;
F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;
F.lll) Nucleic acid synthesis inhibitors
F.III-1 ) RNA, DNA synthesis
phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
isoxazoles and iosothiazolones: hymexazole, octhilinone;
F.III-2) DNA topisomerase inhibitors: oxolinic acid;
F.III-3) Nucleotide metabolism (e.g. adenosin-deaminase)
hydroxy (2-amino)-pyrimidines: bupirimate;
F.IV) Inhibitors of cell division and or cytoskeleton
F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;
triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine F.IV-2) Other cell division inhibitors
benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopi- colide, zoxamide;
F.IV-3) Actin inhibitors: benzophenones: metrafenone;
F.V) Inhibitors of amino acid and protein synthesis
F.V-1 ) Mmethionine synthesis inhibitors (anilino-pyrimidines)
anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
F.V-2) Protein synthesis inhibitors (anilino-pyrimidines)
antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildio- mycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors
F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines)
dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;
phenylpyrroles: fenpiclonil, fludioxonil;
F.VI-2) G protein inhibitors: quinolines: quinoxyfen;
F.VI I) Lipid and membrane synthesis inhibitors
F.VI 1-1 ) Phospholipid biosynthesis inhibitors
organophosphorus compounds: edifenphos, iprobenfos, pyrazophos;
dithiolanes: isoprothiolane;
F.VN-2) Lipid peroxidation
aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
F.VII-3) Carboxyl acid amides (CAA fungicides)
cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyri- morph;
valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F.VII-4) Compounds affecting cell membrane permeability and fatty acides carbamates: propamocarb, propamocarb-hydrochlorid
F.VIII) Inhibitors with Multi Site Action
F.VIII-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasul- phocarb, metiram, propineb, thiram, zineb, ziram;
F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusul- famide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N- (4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
F.VIII-4) Guanidines: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);
F.VIII-5) Ahtraquinones: dithianon;
F.IX) Cell wall synthesis inhibitors
F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B; F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, di- cyclomet, fenoxanil;
F.X) Plant defence inducers
F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl;
F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium;
phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclo- mezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusul- famide, flutianil, methasulfocarb, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]- piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1 -yl)- amide, 2-{1 -[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]-piperidin-4-yl}-thiazole- 4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1 -yl-amide, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-Methyl-2-{1 -[(5-methyl- 3-trifluoromethyl-1 H-pyrazol-1 -yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydro- naphthalen-1 -yl]-4-thiazolecarboxamide, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazoli- din-3 yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyris- oxazole), 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1 carbothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5- chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro- phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
F.XI) Growth regulators:
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegu- lac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri iodobenzoic acid , trinexapac-ethyl and uniconazole;
F.XII) Biological control agents
antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest, Inc.,
USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. SONATA® and BALLAD® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product BOTRY- ZEN from BotriZen Ltd., New Zealand), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand).
Accordingly, the present invention 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 the present invention or a salt thereof or a composition as defined above.
Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention 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 preven- tive 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.
The invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of the present inven- tion or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may contain a single active compound of the present invention or a salt thereof or a mixture of several active compounds of the present invention or their salts according to the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers.
The animal pest, i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the compounds of the present in- vention or composition(s) 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).
The compounds of the present invention 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 pesticidally effective amount of compounds of the present invention. The term "crop" refers both to growing and harvested crops.
The compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for ex- ample seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecti- cidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.
The present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, culti- vated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mixture of at least one active compound of the present invention.
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 the present invention. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of the present invention 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 the present invention. 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).
"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest or parasite is growing or may grow.
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 lim- ited 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 Jul- Aug;17(4):720-8., Protein Eng Des Sel. 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 hydroxy- 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(bl ) or Cry9c; 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 blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, trun- cated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are 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 infestans 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 con- tent 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).
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.
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 20 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.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
For use in 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.
The compounds of formula I and II are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, 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.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
The compounds of the present invention and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long- term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula I and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal 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 exam- pie are Ν,Ν-Diethyl-meta-toluamide (DEET), Ν,Ν-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 ex- tracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l -epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets. The compounds of the present invention 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 formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
The compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.
The compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.
The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general formula I or II or a salt thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably aa method, wherein the plants shoots are protected from aphids.
The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
The present invention also comprises seeds coated with or containing the active compound.
The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation prod- uct is (re)planted, it may absorb the active ingredient.
Suitable seed is seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens. In addition, the active compound may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods. For example, the active compound can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A-0242236, EP-A-242246) (WO
92/00377) (EP-A-0257993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cotton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A-0142924, EP-A-0193259), Furthermore, the active compound can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the gen- eration of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/1 1376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).
The seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
Compositions which are especially useful for seed treatment are e.g.:
A Soluble concentrates (SL, LS)
D Emulsions (EW, EO, ES)
E Suspensions (SC, OD, FS)
F Water-dispersible granules and water-soluble granules (WG, SG)
G Water-dispersible powders and water-soluble powders (WP, SP, WS)
H Gel-Formulations (GF)
I Dustable powders (DP, DS)
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Appli- cation to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1 -800 g/l of active ingredient, 1 -200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
Seed Treatment formulations may additionally also 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 homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, poly- saccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Sol- vent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue
15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Example of a gelling agent is carrageen (Satiagel®).
In the treatment of seed, the application rates of the compounds I 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, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the formula I, or an agriculturally useful salt of I, as defined herein. The amount of the compound I or the agriculturally useful salt thereof will in general vary 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 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
The compounds of the present invention or the veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
An object of the present invention is therfore also to provide new methods to control 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. 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 the present invention or the veterinarily acceptable salts thereof or a composition comprising it.
The present invention also provides a non-therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises including a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof in a composition comprising it.
The invention relates further to the use of compounds of the present invention for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
The invention relates also to the use of a compound of the present invention, or a composition comprising it, for the manufacture of a medicament for the therapeutic treatment of animals against infections or infestions by parasites.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly it has now been found that compounds of the present invention are suitable for combating endo- and ectoparasites in and on animals. 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.
Compounds of the present invention 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 the present invention 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, chiggers, gnats, mosquitoes and fleas.
The compounds of the present invention are especially useful for combating ectoparasites.
The compounds of the present invention are especially useful for combating endoparasites.
The compounds of the present invention are especially useful for combating para- sites 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, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chry- somya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea,
Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Cu- liseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gastero- philus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phle- botomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga 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, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovi- cola 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 ander- soni, 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) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma 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,
Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Os- tertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp.,
Stephanurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globo- cephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongy- lus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, As- caridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofi- lari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Ha- bronema 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., Di- crocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobil- harzia 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 present invention relates to the therapeutic and the non-therapeutic use of compounds of the present invention for controlling and/or combating parasites in and/or on animals.
The compounds of the present invention may be used to protect the animals from attack or infestation by parasites by contacting them with a parasitically effective amount of compounds of the present invention. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect contact (applying the compounds/compo- sitions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of formula I.
"Locus" as defined above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal. The compounds of the invention can also be applied preventively to places at which occurrence of the pests or parasites is expected.
The compounds of the present invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits).
The administration can be carried out prophylactically, therapeutically or non- therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
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.
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.
For oral administration to warm-blooded animals, the compounds the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and cap- sules. In addition, the formula I compounds may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds the present invention may be formulated into an implant for subcutaneous ad- ministration. In addition the compound the present invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compound.
The compounds the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound the present invention. In addition, the com- pounds the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:
- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
- Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
- Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
- Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile. Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methyl- ethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium mono- stearate, 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 ointmentlike 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 ac- tive 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 which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, di- ethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrroli- done, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, poly- acrylates, 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, viscos- ity-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 C8-C12 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, dipropy- lene 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 monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, al- kylphenol 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.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the present invention.
Ready-to-use preparations contain the compounds acting against parasites, pref- erably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
The compositions comprising the compounds of the present invention them can be applied orally, parenterally or topically, respectively dermally. For example, optionally the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the com- pounds of the present invention. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
The active compounds can also be used as a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
The active compounds can be applied solely or in a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.
For example, the active compounds of the present invention can be applied in mixtures with synthetic coccidiosis compounds, polyetherantibiotics as Amprolium, Ro- benidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Sem- duramicin or with other pesticides which are described in the list M above.
Examples
The present invention is now illustrated in further details by the following examples. S. Synthesis examples
Example S.1 : Preparation of 4-hydroxy-3-(3-trifluoromethoxyphenyl)pyrano[3,2- b]pyridin-2-one [I-4]
Step 1 : Pentafluorophenyl 3-hydroxypyridine-2-carboxylate
At 20-25°C 13 g of Ν,Ν' -diisopropylcarbodiimide (DIC) were added dropwise to a solution of 14 g of 3-hydroxypyridine-2-carboxylic acid and 18.5 g of pentafluorophenol in 700 ml. of CH2CI2. After the reaction had ended (about 40 min), the solution was allowed to stand at 20-25°C for about 12 hours. The solvent was removed, and the residue formed was then taken up in water and the solution was extracted with CH2CI2. The organic phase gave, after drying and removal of the solvent, 29 g of the title compound.
Step 2: 4-Hydroxy-3-(3-trifluoromethoxyphenyl)pyrano[3,2-b]pyridin-2-one
3.5 g of K2CO3 were added to a solution of 0.64 g of pentafluorophenyl 3-hydroxy- pyridine-2-carboxylate (from step 1 ) and 0.5 g of (3-trifluoromethoxyphenyl)acetyl chloride in 150 ml. of acetonitrile, and the mixture was stirred at 20-25°C under an atmosphere of nitrogen for about 12 hours. After filtration, the solvent was removed from the filtrate and the residue obtained was taken up in water and, after acidification to pH < 4, extracted with CH2CI2. The organic phase was dried and the solvent was evaporated. The residue gave, after preparative HPLC [column: Luna (2), from Phenomenex, 300*50 mm 10 μηη; mobile phase: water (+ 0.0375% trifluoroacetic acid) and acetonitrile in mixing ratios of 80:20 and 50:50; flow rate 80 ml/min; detection at 220 and 254 nm), 20-25°C], 300 mg of the title compound.
Example S.2: Preparation of 4-Hydroxy-3-(2-trifluoromethyl-phenyl)-thiopyrano[3,2- b]pyridin-2-one [I-22]
To a mixture of 0.32 g 3-mercapto-pyridine-2-carboxylic acid in 30 ml. CH2CI2 was added 0.37 g (2-trifluoromethyl-phenyl)acetyl chloride followed by slow addition of 0.48 g triethylamine (TEA). The mixture was stirred at r.t. for 5 h, then 0.2 g,
Ν,Ν' -diisopropylcarbodiimide (DIC) and 0.29 g of pentafluorophenol were added successively. After stirring at r.t. for 0.5 h, the solvent was evaporated under reduced pressure. The residue was redissolved in acetonitrile, and 2.2 g of K2CO3 were added. The reaction mixture was stirred at r.t. overnight, then acidified with diluted hydrochloric acid, and purified by preparative HPLC, to give 90 mg of the title compound as a yellow solid.
Example S.3: Preparation of acetic acid 2-oxo-3-(2-trifluoromethyl-phenyl)-2H- pyrano[3,2-b]pyridin-4-yl ester [1-39]
Step 1 : 4-Hydroxy-3-(3-trifluoromethylphenyl)pyrano[3,2-b]pyridin-2-one [1-13]
3.7 g K2CO3 was added under ISb-atmosphere to a solution of 0.69 g pentafluorophenyl 3-hydroxypyridine-2-carboxylate (from example 2, step 1 ) and 0.50 g (3-trifluoromethyl- phenyl)acetyl chloride in 150 ml. acetonitrile. The resulting mixture was stirred at r.t. overnight. After filtration, the filtrate was concentrated under reduced pressure and the residue thus obtained was taken up in water and, after acidification to pH < 4, extracted with CH2CI2. The organic phase was dried with anhydrous Na2S04 and concentrated in vacuum. The crude product was purified by preparative HPLC to give 0.3 g of the title compound.
Step 2: Acetic acid 2-oxo-3-(2-trifluoromethyl-phenyl)-2H-pyrano[3,2-b]pyridin-4-yl ester
A mixture of 0.20 g hydroxypyridinone from step 1 , 0.21 g of pyridine, and 0.1 g acetyl chloride in 10 mL toluene was heated to 100°C for 4 h. The solvent was evaporated and the residue was extracted with CH2CI2. The organic layer was washed with an aqueous NaHCC"3 solution and brine, dried with anhydrous Na2S04 and concentrated in vacuum. The residue was purified by preparative HPLC to give 80 mg of the title compound.
Example S.4: Preparation of 4-hydroxy-1 -methyl-3-(2-trifluormethyl-phenyl)-1 H- [1 ,5]naphthyridin-2-one [I-80]
Step 1 : Methyl 3-methylamino-pyridine-2-carboxylate
A mixture of 1.6 g (2-chloropyridine-3-yl)methylamine, 0.2 g [1 ,1 '-bis(diphenyl- phosphino)ferrocene]dichloropalladium(ll) and 3.1 mL triethylamine (TEA) in 30 mL of methanol was stirred at 50°C for 48 h under a 50 PSI CO-atmosphere. Chromatographic purification on silica (mobile phase: petroleum ether/ethyl acetate 10:1 - 3:1 ) gave 0.36 g of the title compound as a colorless oil.
Step 2: Methyl 3-{methyl-[2-(2-trifluormethyl-phenyl)-acetyl]-amino}-pyridine-2- carboxylate
A mixture of 0.36 g of the ester from step 1 in 30 mL CH2CI2 was treated with 0.49 g (2-trifluoromethyl-phenyl)-acetyl chloride, then 0.37 ml TEA were slowly added. The resulting mixture was heated at reflux for 24 h. The residue gave, after preparative HPLC, 0.24 g of the title compound as a yellow oil.
Step 3: 4-Hydroxy-1 -methyl-3-(2-trifluormethyl-phenyl)-1 H-[1 ,5]naphthyridin-2-one
0.24 g of the ester from step 2, dissolved in 10 mL THF, were treated with 27 mg NaH. The mixture was stirred at 20-25°C for about 30 min. The residue gave, after preparative HPLC, 60 mg of the title compound as a yellow crystalline solid. Example 5: Preparation of 4-Hydroxy-3-(2-trifluormethyl-phenyl)-1 H-[1 ,5]naphthyri- din-2-one [I-84]
Step 1 : Methyl 3-[2-(2-Trifluormethyl-phenyl)-acetylamino]-pyridine-2-carboxylate 0.60 g Triethylamine (TEA) were added to a solution of 0.45 g methyl 3-amino- pyridine-2-carboxylate and 0.66 g (2-trifluormethylphenyl)acetyl chloride in 50 mL CH2CI2. After stirring was maintained at 20-25°C for 6 h the solution was washed with water. The organic phase was dried and the solvent was removed under reduced pressure. The residue gave, after preparative HPLC (column: Luna 100*21 ,2 mm C18; mo- bile phase: water [+ 0,1 % trifluoroacetic acid {TFA}] and methanol 70:30 - 40:60 gradient within 10 min), 0.80 g of the title compound.
Step 2: 4-Hydroxy-3-(2-trifluormethyl-phenyl)-1 H-[1 ,5]naphthyridin-2-one
4.8 mL of a 1 .0 molar KHMDS-solution was added under a IS -atmosphere at -40 °C to 0.80 g of the ester from step 1 , dissolved in 50 mL THF. Stirring was maintained at 20-25°C for about 15 h. The resulting mixture was diluted with water and extracted with CH2CI2. The combined organic phases were dried and the solvents were removed under reduced pressure. The residue gave, after preparative HPLC (s. example 1 ), 0.20 g of the title compound. Compounds of the present invention are listed in the following table C.1 with their physical data and illustrate examples without imposing any limitation.
The compounds were characterized by 1H-NMR spectroscopy or HPLC (High Performance Liquid Chromatography Mass Spectrometry). HPLC was carried out using an analytic RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany) which was operated at 40°C. Acetonitrile with 0.1 % by volume of a trifluoroacetic acid/water mixture and 0.1 % by volume of trifluoroacetic acid served as mobile phase; flow rate: 1 .8 ml/min and injection volume: 2 μΙ.
The compound examples in table C.1 are of the following formula l-A:
Figure imgf000079_0001
wherein Rc2, Rc3 and Rc4 are hydrogen in the compound examples listed in
C.1 , with the the following exceptions:
in compound I-33, Rc2 is O-benzoyl; in compound I-52, Rc2 is OH;
in compound I-65, Rc2 is Br; in compound 1-154, Rc2 is CH3, in compound 1-142, RC2 and Rc4 are both Br; in compound 1-190, Rc3 is CF3;
in compound I-200, Rc3 is Br and
in compounds 1-151 , 1-163, 1-174, 1-175, 1-177, 1-191 and 1-195, Rc3 is CI.
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
B. Biological examples
The pesticidal activity can be demonstrated in the following biological test examples.
B.1 Activity against Cotton aphid (aphis gossypii, mixed life stages)
The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, the compounds I-6, I-22, I-27, I-39, 1-1 17, 1-1 18 and 1-120 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.2 Activity against Green Peach Aphid (Myzus persicae, mixed life stages) The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, the compounds I-2, I-5.I-6, I-7, 1-16, 1-17, I-24, I-26, I-27, 1-31 , 1-41 , I-48, I-57, I-59, I-64, I-72, I-82, I-99, 1-1 13, 1-1 17, 1-120, 1-129, 1-131 , 1-143, 1-145, 1-148, I- 149, 1-151 , 1-152, 1-156, 1-163 and 1-165 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.3 Activity against Southern Armyworm (Spodoptera eridania, 2nd instar larvae) The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. Ten to 1 1 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at at 25°C and 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.
In this test compound 1-51 , 1-1 12 and 1-177 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.4 Activity against Silverleaf Whitefly (Bemisia argentifolii, adult)
The active compounds were formulated in cyclohexanone as a 10,0000 ppm solu- tion supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated elec- trostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and 0.6 cm, nontoxic 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. Cups were covered with a reusable screened lid (150-micron mesh polyester screen PeCap from Tetko, Inc.). Test plants were maintained in a growth room at 25°C and 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
In this test, compound I-5, I-6, I-7, 1-17, I-20, I-22, I-28, I-29, I-39, 1-41 , I-43, I-45, I- 51 , I-57, 1-61 , I-64, I-65, I-72, I-76, I-77, 1-107, 1-1 12, 1-1 13, 1-1 14, 1-1 15, 1-1 17, 1-1 18, I- 120, 1-121 , 1-129, 1-130, 1-131 , 1-133, 1-145, 1-154, 1-167 and 1-176 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls. B.5 Activity against Cowpea Aphid (aphis craccivora)
The active compounds were formulated in 50:50 (vohvol) acetone:water. The test solution was prepared at the day of use.
Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours.
In this test, the compounds I-7, 1-1 1 , I-22, I-27, I-28, I-29, I-39, I-50, 1-1 14, 1-1 15, I- 1 18, 1-120, 1-121 , 1-129, 1-130, 1-131 , 1-143, 1-145, 1-158, 1-167, 1-168, 1-170, 1-171 and I- 199 of table C.1 at 500 ppm showed a mortality of at least 50 % in comparison with untreated controls.
B.6 Activity against Diamondback moth (Plutella xylostella)
The active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant. A 6 cm leaf disk of cabbage leaves was dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper. The leaf disk was inoculated with 10 third instar larvae and kept at 25-27°C and 50- 60% humidity for 3 days. Mortality was assessed after 72 h of treatment.
In this test, the compounds I-4, I-5, I-6, 1-19, I-20, I-22, I-29, I-36, I-40, I-43, I-56, I- 63, I-64, I-65, I-66, I-77, I-99, 1-101 , 1-103, 1-1 12, 1-1 17, 1-120, 1-121 , 1-122, 1-132, 1-134, 1-145, 1-151 , 1-153, 1-154, 1-156, 1-157, 1-158, 1-159, 1-163, 1-164, 1-165, 1-166, 1-168, I- 170, 1-171 , 1-174, 1-175, 1-179, 1-180, 1-186, 1-187 and 1-191 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.7 Activity against Orchid thrips (Dichromothrips corbetti)
The active compounds were formulated as a 50:50 (vohvol) acetone:water solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1 % (vol/vol). Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compounds I-4, I-5, I-6, I-7, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, I-20, I-24, I-26, I-27, 1-31 , I-33, I-38, I-39, I-40, I-43, I-48, I-49, I-56, I-57, I-60, I-63, I-64, I-66, I-67, I-79, 1-101 , 1-103, 1-107, 1-1 12, 1-1 14, 1-1 17, 1-120, 1-121 , 1-123, 1-129, 1-131 , 1-134, I- 143, 1-145, 1-146, 1-148, 1-149, 1-152, 1-154, 1-155, 1-156, 1-157, 1-158, 1-159, 1-163, I- 164, 1-165, 1-166, 1-167, 1-175, 1-177, 1-186, 1-187, 1-190, 1-191 , 1-194 and I-200 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.8 Rice plant hopper (Nilaparvata lugens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active corn-pounds were formulated in 50:50 acetone:water and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, compounds I-2, I-5, I-6, I-7, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, I-22, I-24, I-
25, I-26, I-27, I-28, I-29, 1-31 , 1-38,1-39, 1-45, 1-48, 1-49, 1-51 , I-56, I-57, I-59, I-60, 1-61 , I- 64, I-70, I-72, I-76, I-79, I-92, I-99, 1-100, 1-101 , 1-103, 1-107, 1-1 12, 1-1 14, 1-1 15, 1-1 17, I-
1 18, 1-120, 1-123, 1-129, 1-130, 1-131 , 1-133, 1-134, 1-143, 1-145, 1-146, 1-149, 1-151 , I- 152, 1-1-156, 1-158, 1-159, 1-163, 1-164, 1-165, 1-167, 1-170, 1-178, 1-187, 1-190, 1-199 and I-200 of table C.1 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.9 Rice green leafhopper (Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 50:50 acetone:water, and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, compounds I-2, I-5, I-6, I-7, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, I-24, I-25, I-
26, I-27, I-28, I-29, 1-31 , I-38, I-39, I-45, I-48, I-56, I-57, I-59, I-60, 1-61 , I-63, I-64, I-72, I-76, I-86, I-92, I-95, I-99, 1-100, 1-101 , 1-103, 1-104, 1-1 12, 1-1 14, 1-1 15, 1-1 17, 1-1 18, I- 120, 1-122, 1-129, 1-130, 1-133, 1-134, 1-143, 1-145, 1-146, 1-149, 1-151 , 1-152, 1-156, I- 158, 1-163, 1-164, 1-165, 1-167, 1-170, 1-187, 1-190, 1-199 and I-200 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.10 Spider Mite (Tetranychus spp.)
The active compound is dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. The test solution is prepared at the day of use.
Potted cotton plants colonized with approximately 50 mites of various stages are sprayed after the pest population has been recorded. Population reduction (or increase) after 24, 72, and 120 hours is assessed.
In this test, compounds I-39, 1-1 17, 1-120, 1-198 and 1-199 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.
B.1 1 Activity against Vetch aphid (Megoura viciae)
The active compounds were formulated in 1 :3 (vohvol) DMSO : water with different concentrations of formulated compounds. Bean leaf disks were placed into microtiter- plates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 μΙ of the test solution and 5 to 8 adult aphids were placed into the microtiter- plates which were then closed and kept at 23 ± 1 °C and 50 ± 5% relative humidity under fluorescent light for 6 days. Mortality was assessed on the basis of vital, repro- duced aphids. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds I-2, I-5, I-6, 1-15, 1-16, 1-17, 1-18, 1-19, I-24, I-25, I-26, I-
27, I-28, 1-31 , I-34, I-38, I-39, I-43, I-45, I-47, I-48, I-49, I-59, I-60, 1-61 , I-62, I-64, I-75, I-76, 1-81 , I-92, I-99, 1-100, 1-101 , 1-103, 1-104, 1-107, 1-1 10, 1-1 14, 1-1 15, 1-1 16, 1-1 17, I- 1 18, 1-1 19, 1-120, 1-123, 1-127, 1-130, 1-131 , 1-133, 1-140, 1-141 , 1-144, 1-145, 1-146, I- 152, 1-153, 1-156, 1-157, 1-158, 1-159, 1-167, 1-171 , 1-173, 1-178, 1-190, 1-191 , 1-192 and I- 195 at 800 ppm showed a mortality of at least 50%. B.12 Activity against Green Peach Aphid (Myzus persicae, mixed life stages) For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated com- pounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 to 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds I-2, I-4, I-5, I-6, 1-14, 1-15, 1-16, 1-18, 1-19, I-20, I-24, I-25, I-26, I-27, I-28, 1-31 , I-38, I-40, I-43, I-45, I-47, I-48, I-53, I-59, I-60, I-63, I-64, I-66, I-67, I-77, I-79, I-86, I-96, I-97, 1-101 , 1-104, 1-106, 1-1 12, 1-1 13, 1-1 14, 1-1 15, 1-1 17, 1-1 18, I- 120, 1-129, 1-130, 1-131 , 1-132, 1-133, 1-134, 1-145, 1-146, 1-152, 1-156, 1-159, 1-162, I- 163, 1-164, 1-165, 1-166, 1-167, 1-168, 1-170, 1-174, 1-175, 1-180, 1-183, 1-186, 1-187, I- 190, 1-191 and 1-194 at 800 ppm showed a mortality of at least 50%.
B.13 Activity against Tobacco budworm (Heliothis virescens)
The active compounds were formulated in 1 :3 DMSO : water. 15 to 25 eggs were placed into microtiterplates filled with diet. The eggs were sprayed with 10 μΙ of the test solution, the plates were sealed with pierced foils and kept at 27-29°C and 75-85% humidity under fluorescent light for 6 days. Mortality was assessed on the basis of the agility and of comparative feeding of the hatched larvae. Tests were replicated 2 times.
In this test, the compound I-65 at a concentration of the test solution of 800 mg/L showed a mortality of at least 50%.
B.14 Activity against Mexican Boll Weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 20 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test the compounds 1-1 12, 1-170, 1-171 , 1-190, 1-196, 1-197 in table C.1 at 2500 ppm showed a mortality of at least 50%.

Claims

Claims:
1 . A method for combating or controlling insects, arachnids or nematodes comprising contacting an insect, arachnid or nematode or their food supply, habitat or breeding grounds with a compound of formula I or a composition comprising at least one compound of formula I
Figure imgf000101_0001
A, E, G, M are N or C-Rc, wherein one of these groups being N,
and wherein
Rc is independently from one another hydrogen or selected from Rb, and wherein
Rb is selected, independently from one another, from Z-CN, Z-OH, Z-N02, Z-halogen, C1-C8-alkyl, C1-C4-haloalkyl, C2- Cs-alkenyl, C2-Cs-alkynyl, Z-C1-C8-alkoxy, Z-C1-C8-halo- alkoxy, Z-C3-Cio-cycloalkyl, 0-Z-C3-Cio-cycloalkyl, Z- C(=0)-Ra, NR'R", Z-(tri-C1-C4-alkyl)silyl, Z-phenyl and S(0)nRbb,
wherein
Ra is selected from hydrogen, OH, C1-Cs-alkyl, C1-C4- haloalkyl, Z-C3-C6-cycloalkyl, C2-Cs-alkenyl, Z-C5- C6-cycloalkenyl, C2-Cs-alkynyl, Z-C1-C6-alkoxy, Z- C1-C4-haloalkoxy, Z-Cs-Cs-alkenyloxy, Z-C3-C8- alkynyloxy, NR'R", C1-C6-alkylsulfonyl, Z-(tri-C1-C4- alkyl)silyl, Z-phenyl, Z-phenoxy, Z-phenylamino, a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 het- eroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1 , 2, 3 or 4 halogen atoms and/or groups Rbb, wherein
R', R" are independently of one another selected from hydrogen, C1-Cs-alkyl, C1-C4-haloalkyl, C3-C8-alkenyl, Cs-Cs-alkynyl, Z-C3-C6-cycloalkyl, Z-C1-C8-alkoxy, Z- C1-C8-haloalkoxy, Z-C(=0)-Rbb, Z-phenyl, a 3- to 7- membered monocyclic or 9- or 10-membered bicyclic, saturated, unsaturated or aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, attached via Z,
or wherein
R' and R" together with the nitrogen atom to which they are attached to may also form a 5- or 6- membered monocyclic or 9- or 10-membered bicyclic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;
Rbb is d-Cs-alkyl or C1-C6-haloalkyl; and
Z is a covalent bond or C1-C4-alkylene chain;
or wherein
Rb together with the group Rb optionally attached to the adjacent carbon atom may also form a 5- or 6-membered saturated or partially or fully unsaturated ring which, which in addition to carbon atoms, may also contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;
X, Y are selected from O, S or N-R3;
R is 0-RA' S(0)n-RA or OS(0)n-RA; wherein
n is 0, 1 or 2; and
RA is selected from hydrogen, C1-C4-alkyl, Z-C3-C6-cycloalkyl, C1-C4- haloalkyl, C2-C6-alkenyl, Z-C3-C6-cycloalkenyl, C2-C6-alkynyl, Z-(tri-C1-C4-- alkyl)silyl, Z-C(=0)-Ra, Z-P(=0)(Ra)2, Z-NRi-C(0)-NR'Rii, NR'R", a 3- to 7-membered monocyclic or 9- or 10-membered bicyclic, saturated, unsaturated or aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, which may be attached via the carbon or nitrogen atom, and which may be partially or fully substituted by groups selected from Ra and/or Rb; R2 is selected from phenyl, naphthyl, a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S,
and wherein
the cyclic groups are unsubstituted or substituted by 1 , 2, 3 or 4 groups Rb; R3 is selected from hydrogen, C1-C6-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C3- C6-alkynyl, Z-C3-Cio-cycloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6-cyanoalkyl,
Z-phenyl, a 5- or 6 membered monocyclic heterocycle attached via Z, which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle my be fully or partially sub- stitiuted by R , Z-C(=0)-Ra2 or tri-C1-C4-alkylsilyl,
wherein Ra2 is selected from C1 -C6-alkyl, C1 -C4-haloalkyl, Z-C1 -C6-alkoxy, Z-C1 -C4- haloalkoxy or NR'R";
and wherein
in the groups RA, R3 and their subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by groups Rb;
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.
A method for protecting crops and growing plants from attack or infestation by insects, arachnids or nematodes comprising contacting a plant, or soil or water in which the plant is growing, with an compound of formula I or a composition comprising at least one compound of formula I as defined in claim 1.
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally acceptable salt thereof.
A method for protecting plant propagation material, especially seeds, from soil insects and seedlings' roots and shoots from soil and foliar insects comprising contacting the plant proagation material, especially the seeds, before sowing and/or after pregermination with at least one compound of formula I or a composition comprising at least one compound of formula I as defined in claim 1 , and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally acceptable salt thereof.
A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites by administering or applying orally, topically or parenterally to the animals an compound of formula I or a composition comprising at least one compound of formula I as defined in claim 1 ,
and/or at least an N-oxide, an enantiomer, diastereomer or veterinary acceptable salt thereof.
A method according to any of the preceeding claims, characterized in that in formula I RA is selected from hydrogen, C1-C6-alkylcarbonyl or C1-C6-alkoxy- carbonyl.
A method according to any one of claim 1 to 5, characterized in that in formula I Y is O.
7. A method according to any one of claims 1 to 5 , characterized in that in formula I Y is S.
8. A method according to any one of the claims 1 to 5, characterized in that in formula I Y is N-R3, wherein
R3 is selected from hydrogen, C1-C6-alkyl, C1-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, C1-C6-alkoxy-C1-C6-alkyl, C1-C6- cyanoalkyl, Z-phenyl, Z-C(=0)-Ra2 or tri-C1-C4-alkylsilyl,
Ra2 is selected from C1-C6-alkyl, C1-C4-haloalkyl, Z-C1-C6-alkoxy, Z-C1-C4-haloalkoxy or NR'R";
9. A method according to any of claims 1 to 5, characterized in that in formula I Y is N-R3, and wherein
R3 is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyrimidyl, pyridyl, thienyl, furyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxa- zolyl, quinolinyl, isoquinolinyl, indolyl, benzofuryl, benzthienyl, ben- zoxazolyl, benzthiazolyl and benzimidazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle may carry one or more substitutents selected from the group consisting of OH, CN, N02, halogen, C1-C4- alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy.
A method according to any one of claims 1 to 9, characterized in that in formula I X is O.
1 1 . A method according to any one of claims 1 to 9, characterized in that in formula I X is S.
12. A method according to any of claims 1 to 1 1 , characterized in that in formula I A is N; and
E, G, M are C-Rc, wherein
Rc is hydrogen or selected from Rb as defined in claim 1 .
13. A method according to any of claims 1 to 5, characterized in that in formula I A is N;
X is O;
Y is O or S; and
E, G, M is C-Rc, and wherein
Rc is hydrogen or selected from Rb as defined in claim 1 .
14. A method according to claim 13, characterized in that the compound of formula I is of formula I. A
Figure imgf000105_0001
wherein
Y, R1, and Rb are as defined for formula (I) in claim 1 ,
Rc2, Rc3 and Rc4 are selected independently from one another from Rc as defined in claim 1 , and
m is 0, 1 , 2, 3 or 4.
15. A compound of formula I, which is of formula II:
Figure imgf000105_0003
wherein
Y is S or O;
X is S or O;
R1 is as defined for formula I in claim 5; and
Rc2, Rc3, Rc3', Rc4, Rc4' and Rc5' are selected independently from one another from the group consisting of hydrogen, OH, CN, N02, halogen, C1-C4-alkyl, C1-C4-halo- alkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.
A compound of formula I, which is of formula III:
Figure imgf000105_0002
wherein
X is as defined for formula I in claiml ;
R is as defined for formula I in claim 5;
R2 is phenyl or pyridyl, which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; Rc2, Rc3, Rc4 are selected independently from one another from the group consisting of hydrogen, OH, CN, NO2, halogen, C1-C4-alkyl, C1- C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy; and
R3 is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyridyl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl and isoxazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and which may carry one or more substitutents selected from the group consisting of OH, CN, NO2, halogen, C1- C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy, Z is a covalent bond or C1-C4-alkylene chain, wherein the carbon chain may optionally carry one or more substitu- ents selected from C1-Cs-alkyl or C1-C4-haloalkyl;
and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.
17. An agricultural or verterinary composition comprising at least one compound of the formula I according to any one of claims 1 or 5 to 16, or an N-oxide, enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof and at least one inert liquid and/or solid carrier.
18. The method according to claim 3, wherein the compound of the formula I as defined in any one of claim 3 or claims 5 to 16 is applied in an amount of from 100 mg to 10 kg per 100 kg of seeds.
19. A method according to claim 3, wherein of the resulting plant's roots and shoots are protected.
20. Seed comprising at least one compound of the formula I, II or III according to any one of claims 1 or 5 to 16, or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
A method according to claim 4 which comprises orally, topically or parenterally administering or applying to the animals an compound of formula I, or the enantiomer, diastereomer or veterinary acceptable salt thereof, as defined in any one of claim 4 or claims 5 to 16.
22. Use of a compound of formula I as defined in any one of claims 4 or claims 5 to 16 for the preparation of an orally, topically or parenterally applicable or adminis- trable veterinary medicament for treating, controlling, preventing or protecting animals against infestation or infection by parasites.
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