WO2014053407A1 - N-thio-anthranilamide compounds and their use as pesticides - Google Patents

N-thio-anthranilamide compounds and their use as pesticides Download PDF

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WO2014053407A1
WO2014053407A1 PCT/EP2013/070162 EP2013070162W WO2014053407A1 WO 2014053407 A1 WO2014053407 A1 WO 2014053407A1 EP 2013070162 W EP2013070162 W EP 2013070162W WO 2014053407 A1 WO2014053407 A1 WO 2014053407A1
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alkyl
cio
cycloalkyl
compounds
spp
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PCT/EP2013/070162
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French (fr)
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Karsten KÖRBER
Florian Kaiser
Prashant Deshmukh
Matthias Pohlman
Jean-Yves WACH
Deborah L. Culbertson
W. David ROGERS
Koshi Gunjima
Michael David
Franz Josef Braun
Sarah Thompson
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Basf Se
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Publication of WO2014053407A1 publication Critical patent/WO2014053407A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings

Definitions

  • N-Thio-anthranilamide compounds and their use as pesticides Description
  • the present invention relates to N-Thio-anthranilamide compounds of formula (I)
  • R 1 is hydrogen; or Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, or Ca-Ce-cycloalkyl, each of which is unsubstituted or substituted with 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, Ci-Cio-alkoxy, Ci-Cio-alkylthio, Ci-Cio-alkylsulfinyl, C1-C10- alkylsulfonyl, C2-Cio-alkoxycarbonyl, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino and C3-C8- cycloalkylamino; or Ci-Cio-alkylcarbonyl, Ci-Cio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)amin
  • R 2 and R 3 each independently are R 6 or together with the sulfur atom to which they are
  • G is oxygen or sulfur
  • R 6 is Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, C3-Ce-cycloalkyl, C3-Ce-cycloalkenyl, C3-C8- cycloalkynyl, phenyl, naphthyl, biphenyl, or a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of these groups are unsubstituted or substituted by any combination of 1 to 6 groups R 8 ; is R 9 ; or two groups R 8 together with the atoms to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which may contain 1 to 4 heteroatoms /heterogroups selected from oxygen, nitrogen, sulfur, SO and SO2, and which ring system is unsubstituted or substituted with any combination of 1 to 6 groups
  • a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
  • a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
  • these aryl and these heterocyclic ringsystems are unsubstituted or substituted with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-Ce-cycloalkyl, Ci-C 4 -alkoxy, Ci-C4-haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, di(Ci-C4-alkyl)amino, Ci-C4-alkylamino, C 1 -C4- haloalkylamino, formyl and Ci-C4-alkylcarbonyl;
  • Q 1 and Q 2 each independently are hydrogen, halogen, cyano, SCN, nitro, hydroxy, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C 2 -Cio-alkenyl, C 2 -Cio-haloalkenyl, C 2 -Cio-alkynyl, C3-Cio-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci- Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, C1-C10- haloalkylsulfonyl, Ci-Cio-
  • Cio-alkylsulfonyl Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Cs-Cs-cycloalkylamino, C1-C10- alkyl-C3-C8-cycloalkylamino, Ci-Cio-alkylcarbonyl, CrCio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl and tri(Ci-Cio)-alkylsilyl; is halogen; or Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-C10- alkynyl, C3-Cio-haloalkynyl, Cs-Ce-cycloalkyl, C3-Cs-halo
  • R 14 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C 2 -Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Ce-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, Ci- C4-alkyl-C3-C8-cycloalkyl, C3-C8-halocycloalkyl-Ci-C4-alkyl, Ci-C4-haloalkyl-C3-C8- cycloalkyl, or Ci-Cio-haloalkylcarbonyl, each unsubstituted or substituted with 1 R 19 ;
  • R 15 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Ce-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl, Ci- C4-haloalkyl-C3-C8-cycloalkyl, or Ci-Cio-haloalkylcarbonyl, each unsubstituted or substituted with 1 R 19 ;
  • R 16 is hydrogen; or Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2- Cio-alkynyl, C3-Cio-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-C4-alkyl-C3-Ce- cycloalkyl, or Ci-C4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1
  • R 17 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl, or Ci- C4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1 R 19 ;
  • R 19 is cyano, nitro, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, Ci-Cio-alkoxycarbonyl, Ci-Cio-alkylamino, or di(Ci-Cio-alkyl)amino; or
  • R 19 is phenyl or a heteroaromatic 5- or 6-membered ring which contains 1 to 4
  • heteroatoms selected from oxygen, nitrogen, sulfur, the phenyl radical and the
  • heteroaromatic ring being unsubstituted or substituted with any combination of from 1 to 3 groups selected from halogen, cyano, nitro, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, Ca-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-Cio-alkoxy, Ci-Oo-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-alkylsulfinyl, Ci- Cio-alkylsulfonyl, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Ca-Cs-cycloalkylamino, C1-C10- alkyl-C
  • R 18 is the same or different: hydrogen, Ci-Oo-alkyl, or Ci-Cio-haloalkyl; q is 0, 1 or 2;
  • Q 4 is halogen, cyano, nitro, hydroxy, COOH, C(0)NH 2 , Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-C10- alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Ce-cycloalkyl, C3-C8- halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, CrCio-alkylthio, Ci-Cio-haloalkylthio, Cr Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, Ci-Cio-haloalkylsulfony
  • W is N, CH or CQ 4 ; n is O or l ; p is 0, 1 , 2, 3, or 4; or a stereoisomer, salt, tautomer, or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.
  • the invention especially relates to compositions comprising the compounds according to the invention.
  • the invention especially also relates to certain uses of the compounds according to the invention.
  • Invertebrate pests and in particular insects, arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new and more effective agents for combating invertebrate pests, in particular insects, arachnids and nematodes.
  • the compounds should show a broad activity spectrum against a large number of different invertebrate pests, in particular against difficult to control insects, arachnids, acarids and nematodes. It can also be advantageous if the compounds allow to control specific pests which are difficult to control, or if they allow the application on a certain crop.
  • the compounds should have properties which allow to prepare stable and active compositions therefrom.
  • a method for combating or controlling invertebrate pests comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound according to the invention, or a composition as defined herein.
  • a method for protecting growing plants from attack or infestation by invertebrate pests comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound according to the invention, or a composition as defined herein.
  • a method for the protection of plant propagation material, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propagation material respectively seeds before sowing and/or after pregermination with at least one compound according to the invention, or a composition as defined herein.
  • - seed comprising a compound according to the invention, in an amount of from 0.1 g to 10 kg per 100 kg of the plant propagation material.
  • a method for treating a non-human animal infested or infected by parasites or for preventing a non-human animal from getting infested or infected by parasites or for protecting a non- human animal against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the non-human animal a parasiticidally effective amount of a compound according to the invention, or a composition as defined in claim herein.
  • WO 2007/043677 describes a generic anthranilamide formula encompassing N-thio-anthranilamide compounds.
  • WO 03/016284 describes inter alia certain N-thio-anthranilamide compounds, in which the nitrogen of the benzoic acid amide is substituted by two substituents, one of which may be bound via a sulfur atom.
  • WO 2007/006670 describes N-thio-anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides.
  • PCT/EP2012/065650 describes N-thio-anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides.
  • the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • the invention provides both the pure enantiomers or pure diastereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures.
  • Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
  • Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double- bond, nitrogen-sulfur double bond or amide group.
  • stereoisomer(s) encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • N- oxide includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • N-oxides of compounds (I) can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the formula (I) of the present invention may form N-oxides.
  • the compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of formula (I), their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula (I), its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof.
  • co-crystal denotes a complex of the compounds according to the invention or a stereoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules ("partner molecule", preferably one molecule type), wherein usually the ratio of the compound according to the invention and the other molecule is a stoichiometric ratio.
  • solvate denotes a co-complex of the compounds according to the invention, or a stereoisomer, salt, tautomer or N-oxide thereof, with solvent molecules.
  • the solvent is usually liquid. Examples of solvents are methanol, ethanol, toluol, xylol.
  • a preferred solvent which forms solvates is water, which solvates are referred to as "hydrates".
  • a solvate or hydrate is usually characterized by the presence of a fixed number of n molecules solvent per m molecules compound according to the invention.
  • Co-crystals and solvates only differ by the nature of the partner molecule, i.e. in the case of co- crystals, the partner molecule is solid at room temperature, and in the case of solvates, the partner molecule is liquid at room temperature.
  • the invention relates to co-crystals and solvates of the compounds according to the invention, more preferably a compound of formula IA, also preferably a compound of formula IB, also preferably a compound of formula IC, also preferably a compound of formula ID; more preferably a compound selected from the compounds 1-1 to I- 41 as defined in Table C; more preferably a compound selected from compounds 1-1 1 , 1-16, I- 21 , I-26, 1-31 according to Table C/C as described below.
  • Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
  • Suitable agriculturally acceptable 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 pesticidal action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by d-Gi-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of the present invention with an acid of the corresponding anion, preferably with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Veterinarily acceptable salts of the compounds of the present invention encompass the salts of those cations or the acid addition salts 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 containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorides, sulfates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, e.g. the monoacid salts or diacid salts of maleic acid, dimaleic acid, fumaric acid, e.g. the monoacid salts or diacid salts of fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hydrochlorides, sulfates, phosphates, and nit
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n - Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • partially or fully halogenated will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine.
  • a partially or fully halogenated radical is termed below also "halo-radical”.
  • partially or fully halogenated alkyl is also termed haloalkyl.
  • alkyl as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 12 or 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms.
  • Ci-C4-alkyl examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl.
  • Ci-C6-alkyl are, apart those mentioned for Ci-C4-alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 , 3-d i methyl butyl, 2,2- dimethylbutyl, 2, 3-d i methyl butyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl and 1-ethy
  • Ci-Cio-alkyl are, apart those mentioned for Ci-C6-alkyl, n-heptyl, 1 -methylhexyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 -ethyl pentyl, 2-ethylpentyl, 3- ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1 ,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.
  • alkylene (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkyl as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms ("Ci-Cio-haloalkyl”), frequently from 1 to 6 carbon atoms (“C1-C6- haloalkyl”), more frequently 1 to 4 carbon atoms (“Ci-Cio-haloalkyl”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • haloalkyl as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g
  • haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-C2-haloalkyl, more preferably from halomethyl, in particular from Ci-C2-fluoroalkyl.
  • Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like.
  • Examples for C1-C2- fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
  • Ci-C2-haloalkyl examples are, apart those mentioned for Ci-C2-fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 2- chloroethyl, 2,2,-dichloroethyl, 2,2,2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 1-bromoethyl, and the like.
  • Ci-C4-haloalkyl are, apart those mentioned for Ci-C2-haloalkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1 ,1 ,1 -trifl uoroprop-2-yl , 3- chloropropyl, 4-chlorobutyl and the like.
  • cycloalkyl as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms (“C3-Cio-cycloalkyl”), preferably 3 to 8 carbon atoms (“C3-Cs-cycloalkyl”) or in particular 3 to 6 carbon atoms (“C3-C6- cycloalkyl").
  • Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Examples of monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicyclo[2.2.1 ]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and
  • cycloalkylene (or cycloalkanediyl) as used herein in each case denotes an cycloalkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • halocycloalkyi as used herein (and in the halocycloalkyi moieties of other groups comprising an halocycloalkyi group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms or in particular 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine.
  • Examples are 1- and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl and the like.
  • cycloalkyl-alkyl used herein denotes a cycloalkyl group, as defined above, which is bound to the remainder of the molecule via an alkylene group.
  • Cs-Cs-cycloalkyl-d- C4-alkyl refers to a C3-Cs-cycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above.
  • Examples are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, and the like.
  • alkenyl denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 10 (“C 2 -Cio-alkenyl”), preferably 2 to 6 carbon atoms (“C 2 -C6-alkenyl”), in particular 2 to 4 carbon atoms (“C 2 -C4-alkenyl”), and a double bond in any position, for example C2-C4-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 - methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1-propenyl, 2-methyl-1 -propenyl, 1- methyl-2-propenyl or 2-methyl-2-propenyl; C 2 -C6-alkenyl, such as ethenyl, 1 -propenyl, 2- propenyl, 1-methyleth
  • alkenylene (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkenyl as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 ("C 2 -Cio-haloalkenyl") or 2 to 6 ("C 2 -C 6 -haloalkenyl”) or 2 to 4 (“C 2 -C 4 -haloalkenyl”) carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
  • alkynyl denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10 (“C2-Cio-alkynyl”), frequently 2 to 6 (“C2-C6-alkynyl”), preferably 2 to 4 carbon atoms (“C2-C4-alkynyl”) and one or two triple bonds in any position, for example C 2 - C4-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl and the like, C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- butynyl, 3-butynyl, 1-methyl-2-propynyl, 1 -pentynyl, 2-pentyn
  • alkynylene (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkynyl as used herein, which is also expressed as “alkynyl which may be substituted by halogen”, refers to unsaturated straight-chain or branched hydrocarbon radicals having iusually 3 to 10 carbon atoms (“C2-Cio-haloalkynyl”), frequently 2 to 6 (“C2-C6- haloalkynyl”), preferabyl 2 to 4 carbon atoms (“C2-C4-haloalkynyl”), and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • C2-Cio-haloalkynyl unsaturated straight-chain or branched hydrocarbon radicals having iusually 3 to 10 carbon atoms
  • C2-C6- haloalkynyl frequently 2 to 6
  • C2-C4-haloalkynyl preferabyl 2
  • alkoxy denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms ("Ci-Cio-alkoxy”), frequently from 1 to 6 carbon atoms (“Ci-C6-alkoxy”), preferably 1 to 4 carbon atoms (“Ci-C4-alkoxy”), which is bound to the remainder of the molecule via an oxygen atom.
  • Ci-C2-Alkoxy is methoxy or ethoxy.
  • C1-C4- Alkoxy is additionally, for example, n-propoxy, 1-methylethoxy (isopropoxy), butoxy,
  • Ci-C6-Alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3- methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethyl butoxy, 2-ethyl butoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1-ethyl-1 -methyl
  • Ci-Ce-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof.
  • haloalkoxy denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms ("Ci-Cio-haloalkoxy”), frequently from 1 to 6 carbon atoms (“Ci-C6-haloalkoxy”), preferably 1 to 4 carbon atoms (“C1-C4- haloalkoxy”), more preferably 1 to 3 carbon atoms (“Ci-C3-haloalkoxy”), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms.
  • Ci-C 2 -Haloalkoxy is, for example, OCH 2 F, OCHF 2 , OCF 3 , OCH2CI, OCHCI 2 , OCC , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC 2 F 5 .
  • Ci-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2- difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2- bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH 2 -C 2 F 5 , OCF2-C2F5, 1-(CH 2 F)-2-fluoroethoxy, 1-(CH 2 CI)-2-chloroethoxy, 1-(CH 2 Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy.
  • Ci-C6-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dod ecaf I uorohexoxy .
  • alkoxyalkyl denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above.
  • Ci-C6-Alkoxy-Ci-C6-alkyl is a Ci-C6-alkyl group, as defined above, in which one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above.
  • Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH 2 -OCH(CH 3 )2, n-butoxymethyl, (l -methylpropoxy)-methyl, (2- methylpropoxy)methyl, CH 2 -OC(CH 3 )3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2- (l -methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl,
  • haloalkoxy-alkyl denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an haloalkoxy radical as defined above, usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above.
  • Examples are fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 1 -fluoroethoxymethyl, 2-fluoroethoxymethyl,
  • alkylthio (also alkylsulfanyl or alkyl-S-)" as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 10 carbon atoms (“CrCio-alkylthio”), frequently comprising 1 to 6 carbon atoms (“Ci-C6-alkylthio”), preferably 1 to 4 carbon atoms (“Ci-C4-alkylthio”), which is attached via a sulfur atom at any position in the alkyl group.
  • Ci-C2-Alkylthio is methylthio or ethylthio.
  • Ci-C4-Alkylthio is additionally, for example, n-propylthio, 1-methylethylthio (isopropylthio), butylthio,
  • Ci-C6-Alkylthio is additionally, for example, pentylthio, 1 -methylbutylthio,
  • d-Cs-Alkylthio is additionally, for example, heptylthio, octylthio, 2-ethylhexylthio and positional isomers thereof.
  • Ci-Cio-Alkylthio is additionally, for example, nonylthio, decylthio and positional isomers thereof.
  • haloalkylthio refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-C 2 -Haloalkylthio is, for example, SCH 2 F, SCHF 2 , SCF 3 , SCH 2 CI, SCHCI 2 , SCCI 3 , chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-
  • Ci-C4-Haloalkylthio is additionally, for example,
  • Ci-C6-Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio,
  • alkylsulfinyl and “S(0) n -alkyl” are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • the term "Ci-C2-alkylsulfinyl” refers to a Ci-C2-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C4-alkylsulfinyl refers to a Ci-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C6-alkylsulfinyl refers to a 0-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C2-alkylsulfinyl is methylsulfinyl or ethylsulfinyl.
  • Ci-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1-methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl) or 1 ,1 -dimethylethyl sulfinyl (tert-butylsulfinyl).
  • alkylsulfonyl and “S(0) n -alkyl” are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • C1-C2- alkylsulfonyl refers to a Ci-C2-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C4-alkylsulfonyl refers to a Ci-C4-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C6-alkylsulfonyl refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group.
  • Ci-C2-alkylsulfonyl is methylsulfonyl or ethylsulfonyl.
  • Ci-C4-alkylsulfonyl is additionally, for example, n-propylsulfonyl,
  • Ci-C6-alkylsulfonyl is additionally, for example, pentylsulfonyl,
  • alkylamino denotes in each case a group -NHR, wherein R is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms (“C1-C6- alkylamino”), preferably 1 to 4 carbon atoms("Ci-C4-alkylamino").
  • Ci-C6-alkylamino examples include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso- butylamino, tert-butylamino, and the like.
  • dialkylamino denotes in each case a group-NRR', wherein R and R', independently of each other, are a straight-chain or branched alkyl group each usually having from 1 to 6 carbon atoms ("di-(Ci-C6-alkyl)-amino"), preferably 1 to 4 carbon atoms (“di-(Ci-C4- alkyl)-amino").
  • Examples of a di-(Ci-C6-alkyl)-amino group are dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl-propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl-amino, ethyl-isopropylamino, ethyl- butyl-amino, ethyl-isobutyl-amino, and the like.
  • cycloalkylamino denotes in each case a group -NHR, wherein R is a cycloalkyi group usually having from 3 to 8 carbon atoms ("Ca-Cs-cycloalkylamino"), preferably 3 to 6 carbon atoms("C3-C6-cycloalkylamino").
  • Examples of C3-C8-cycloalkylamino are cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, and the like.
  • alkylaminosulfonyl denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group.
  • alkylaminosulfonyl group examples include methylaminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl, n-butylaminosulfonyl, 2- butylaminosulfonyl, iso-butylaminosulfonyl, tert-butylaminosulfonyl, and the like.
  • dialkylaminosulfonyl denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group.
  • S(0)2 sulfonyl
  • haloalkylcarbonyl aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl.
  • aryl refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl.
  • heteroaryl refers to a mono-, bi- or tricyclic heteroaromatic hydrocarbon radical, preferably to a monocyclic heteroaromatic radical, such as pyridyl, pyrimidyl and the like.
  • a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, is a ring system wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system e.g.
  • a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur also is e.g. a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, such as pyridine, pyrimidine, (1 ,2,4)-oxadiazole, (1 ,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1 ,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxiran
  • a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 nitrogen atom and 0 to 2 further heteroatoms selected from oxygen, nitrogen and sulfur, preferably from oxygen and nitrogen, such as piperidine, piperazin and morpholine.
  • this ring system is a saturated, partially unsaturated or unsaturated 3- to 6- membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system.
  • this ring system is a radical of pyridine, pyrimidine, (1 ,2,4)-oxadiazol, 1 ,3,4- oxadiazol, pyrrol, furan, thiophen, oxazol, thiazol, imidazol, pyrazol, isoxazol, 1 ,2,4-triazol, tetrazol, pyrazin, pyridazin, oxazolin, thiazolin, tetrahydrofuran, tetrahydropyran, morpholin, piperidin, piperazin, pyrrolin, pyrrolidin, oxazolidin, thiazolidin, oxiran or oxetan.
  • the compounds according to the invention can be prepared analogously as described in WO 2007/006670, PCT/EP2012/065650 and PCT/EP2012/065651.
  • Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.
  • Preferred compounds according to the invention are compounds of formulae (I) or (1-1 ) or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally or veterinarily acceptable salt.
  • R 1 is hydrogen, Ci-C6-alkyl, cyano, C1-C6- alkylsulfonyl, or C 2 -C6-alkoxycarbonyl, preferably hydrogen or Ci-C4-alkyl, most preferably hydrogen.
  • R 2 and R 3 each independently are R 6 , or R 2 and R 3 together with the sulfur atom to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, which ring can be fused with one or two saturated, partially unsaturated or unsaturated 5- to 6-membered rings which may contain 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of the above rings are unsubstituted or substituted by any combination of 1 to 6 groups R 8 .
  • R 2 and R 3 each independently are R 6 , preferably hydrogen, Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Ca-Cs-cycloalkyl, C3-C8- cycloalkenyl, C3-Cs-cycloalkynyl, phenyl, naphthyl, biphenyl, or a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of these groups are unsubstituted or substituted by any combination of 1 to 6 groups R 9 .
  • R 2 and R 3 each independently are Ci- Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Cs-cycloalkyl, or phenyl, wherein these groups are unsubstituted or substituted by any combination of 1 to 6 groups selected from R 10 or R 11 , and R 10 is Ci-Cio-alkyl, C 3 -C 8 -cycloalkyl, Ci-Cio-alkyl-C 3 -C 8 -cycloalkyl or
  • R 11 is halogen, cyano, nitro, hydroxy, mercapto, amino, formyl, Ci-Cio-alkylcarbonyl, C1-C10- alkoxy, C2-Cio-alkenyloxy, C2-Cio-alkynyloxy, Ci-Cio-haloalkoxy, Cs-Ce-cycloalkoxy, C3-C8- halocycloalkoxy, Ci-Cio-alkoxycarbonyl, C 3 -C8-cycloalkoxycarbonyl, Ci-Cio-alkylcarbonyloxy, C3-Ce-cyclo alkylcarbonyloxy, Ci-Cio-haloalkoxycarbonyl, Ci-Cio-haloalkylcarbonyloxy, C1-C10- alkanamido, Cs-Cs-cycloalkanamido, Ci-Cio-alkylthio, C2-Cio-alkenylthi
  • a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
  • these aryl and these heterocyclic ringsystems are unsubstituted or substituted with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, di(Ci-C4-alkyl) amino and Ci-C4-alkylamino.
  • R 2 and R 3 each independently are C1-C10- alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, Cs-Cs-cycloalkyl, or phenyl, wherein these groups are unsubstituted or substituted by any combination of 1 to 6 groups selected from R 11 , and R 11 is halogen, cyano, nitro, hydroxy, mercapto, amino, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, C3-C8- cycloalkoxy, Ci-Cio-alkoxycarbonyl, Ci-Cio-alkylcarbonyloxy, Ci-Cio-alkanamido, C1-C10- alkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-alkylsulfonyl, di(Ci-Cio-alkyl)amino
  • r is 0 or 1 ;
  • D is a direct bond, branched or straight Ci-C4-alkylene, O, S(0)o,i,2 or NR, preferably CH 2 , O, or N R;
  • R 9 is as defined above for compounds of formula I;
  • R j is hydrogen, CrC4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, C1-C4- alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, or Ci-C4-alkylsulfonyl;
  • a,b are the same or different 0, 1 , 2, 3 or 4, preferably 0, 1 , or 2.
  • Q 1 is hydrogen, halogen, cyano, SCN, nitro, hydroxy, CrCio-alkyl, Ci-Cio-haloalkyl, Cs-Cs-cycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci- Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfonyl, Ci-Cio-alkylsulfonyloxy, C1-C10- alkylamino or di(Ci-Cio-alkyl)amino, most preferably hydrogen, halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl.
  • Q 2 is halogen, cyano, SCN , nitro, hydroxy, Cr Cio-alkyl, Ci-Cio-haloalkyl, Ca-Cs-cycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfonyl, Ci-Cio-alkylsulfonyloxy, Ci-Cio-alkylamino or di(Ci- Cio-alkyl)amino, most preferably halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl.
  • Q 3 is halogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2- Cio-alkynyl, Cs-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, each unsubstituted or independently substituted with 1 to 2 groups selected from cyano, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy or C1-C10- alkylthio, or
  • R 14 is Ci-Cio-alkyl or Ca-Ce-cycloalkyl unsubstituted or substituted with 1 R 19 ;
  • R 15 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, each unsubstituted or substituted with 1 R 19 ;
  • R 16 is hydrogen, CrCio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C 2 -Cio-alkynyl, each
  • R 17 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, Ca-Ce-cycloalkyl, each unsubstituted or substituted with 1 R 19 ;
  • R 18 is hydrogen, Ci-Cio-alkyl, or Ci-Cio-haloalkyl
  • R 19 is cyano, nitro, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, or Ci-Cio-haloalkylthio.
  • both V and V are CH.
  • N-thio-anthranilamid compounds of formula I wherein
  • W is N
  • R 1 is hydrogen
  • Q 1 is hydrogen, halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl;
  • Q 2 is halogen, cyano, CrC4-alkyl or Ci-C 4 -haloalkyl
  • Q 3 is halogen, Ci-C4-haloalkyl or Ci-C4-haloalkoxy
  • Q 4 is halogen or Ci-C4-haloalkyl and is in the ortho-position
  • R 2 and R 3 each independently are phenyl, Ci-C6-alkyl, C2-C6-alkenyl, or C2-C6-alkynyl, which are unsubstituted or substituted with any combination of 1 to 6 groups selected from halogen and cyano.
  • R 2 and R 3 each independently are C1-C4- alkyl, phenylmethyl, allylmethyl, propargylmethyl, or together with the sulfur atom to which they are attached form a 3- to 6-membered saturated ring which contains 1 to 3 heteroatoms selected from sulfur and oxygen.
  • the compound I of formula (I) is a compound of formula (I-0)
  • Q 2 is selected from the group consisting of halogen, methyl and halomethyl
  • Q 1 is selected from the group consisting of hydrogen, halogen, halomethyl and cyano;
  • R 1 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkinyl, C2-C6-haloalkinyl, C3-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl,
  • Q 4 is hydrogen or halogen
  • R 2 , R 3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Ca-Ce-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R e , and phenyl, which is unsubstituted or carries 1 to 5 substituents R f ; or
  • R 2 and R 3 together represent a C2-C7-alkylene, C2-C7-alkenylene or
  • Ci-C6-alkyl Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, (C1-C6- alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino, is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3- Ce-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals
  • phenyl, benzyl, pyridyl and phenoxy wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (O- C6-alkoxy)carbonyl; d are, independently from one another and independently of each occurrence, selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Ca-Cs-cycloalkyl, wherein one or more CH 2 groups of the
  • Q 1 is selected from the group consisting of bromo, chloro, cyano;
  • Q 3 is selected from the group consisting of bromo, chloro, trifluoromethyl. OCHF 2 , and wherein the variables Q 1 , Q 3 , R 2 , R 3 and n are as defined herein.
  • Q 2 is selected from the group consisting of halogen and halomethyl
  • Q 1 is selected from the group consisting of bromo, chloro and cyano
  • Q 2 is selected from the group consisting of halogen, methyl and halomethyl
  • Q 1 is selected from the group consisting of bromo, chloro and cyano
  • R 2 , R 3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, C3-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents
  • R 2 , R 3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, C3-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents R e .
  • Q 3 is selected from the group consisting of bromo, difluoromethyl, trifluoromethyl, cyano, OCH F2, OCH2F and OCH2CF3,
  • R 2 and R 3 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl.
  • R 2 and R 3 are identical.
  • the compounds according to the invention comprise least one compound of form
  • Q 2 is selected from the group consisting of CI, Br, and methyl
  • Q 1 is selected from the group consisting of bromo and chloro
  • R 2 , R 3 are selected independently of one another from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
  • Q 3 is selected from the group consisting of difluoromethyl, trifluoromethyl.
  • Examples of especially preferred anthranilamide compounds I of the present invention are of formula (IA-1 )
  • Examples of preferred compounds of formula I as compounds I or in mixtures according to the invention are compiled in tables 1 to 60 below. Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
  • Table 1 Compounds of the formula (IA-1 ) in which Q 2 is F, Q 1 is CI, Q 3 is CF3 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 2 Compounds of the formula (IA-1 ) in which Q 2 is Br, Q 1 is CI, Q 3 is CF3 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 3 Compounds of the formula (IA-1 ) in which Q 2 is CI, Q 1 is CI, Q 3 is CF 3 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 4 Compounds of the formula (IA-1 ) in which Q 2 is methyl, Q 1 is CI, Q 3 is CF3 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 5 Compounds of the formula (IA-1
  • Table 52 Compounds of the formula (IA-1 ) in which Q 2 is methyl, Q 1 is CI, Q 3 is OCH F2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 53 Compounds of the formula (IA-1 ) in which Q 2 is F, Q 1 is Br, Q 3 is OCHF 2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 54 Compounds of the formula (IA-1 ) in which Q 2 is Br, Q 1 is Br, Q 3 is OCHF 2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 55 Compounds of the formula (IA-1 ) in which Q 2 is CI, Q 1 is Br, Q 3 is OCHF 2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 56 Compounds of the formula (IA
  • Table 57 Compounds of the formula (IA-1 ) in which Q 2 is F, Q 1 is cyano, Q 3 is OCHF2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 58 Compounds of the formula (IA-1 ) in which Q 2 is Br, Q 1 is cyano, Q 3 is OCH F2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 59 Compounds of the formula (IA-1 ) in which Q 2 is CI, Q 1 is cyano, Q 3 is OCH F2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A;
  • Table 60 Compounds of the formula (IA-1 ) in which Q 2 is methyl, Q 1 is cyano, Q 3 is OCH F2 and the combination of R 2 and R 3 for a compound corresponds in each case to one row of Table A.
  • A- 178 CH CH 2 CH 2 CH(CH 3 ) 2 A-220 c-C 6 Hii CH(CH 3 )CH 2 CH 3
  • A-203 CH CH 2 CH(CH 3 )CH 2 CH 3
  • A-245 c-CeHu CH 2 CH CH 2
  • A-260 CH 2 CH CH 2 CH 2 C ⁇ CH A-302 C 2 H5 CHF 2
  • A-300 C6H5 CH(CH 3 )CH CH 2 A-342 C-C3H5 CH 2 CI R 2 R 3 R 2 R 3
  • A-460 CH 2 CH CH 2 C-C5H9 A-502 C2H5 CH 2 -c-C 3 H 5
  • A-610 CH 2 CH CH 2 C6H5 A-652 C2H5 CH 2 CH 2 -c-C 3 H 5
  • A-628 CH CH 2 CH2-C-C4H7
  • A-670 C-CeHu CH 2 CH 2 -c-C 3 H 5
  • A-636 CH 2 C ⁇ CH CH2-C-C4H7
  • c-C 3 H 5 cyclopropyl; C-C4H7: cyclobutyl; 0C5H9: cyclopentyl; c-CeHu: cyclohexyl;
  • CH 2 -c-C3H 5 cyclopropylmethyl
  • CH(CH 3 )-c-C 3 H 5 1-cyclopropylethyl
  • CH 2 -c-C 5 H 9 cyclopentylmethyl
  • CH 2 -C-C 5 H9 cyclopentylmethyl
  • CeH 5 phenyl
  • CH2CH2-C-C3H5 2-cyclopropylethyl
  • CH 2 -c-C 4 H 7 2-cyclobutylmethyl
  • 2-EtHex 2-etHex
  • a group of especially preferred compounds of formula I are compounds 1-1 to I-40 of formula IA-1 which are listed in the table C in the example section.
  • a compound selected from the compounds 1-1 to I-40 as defined in Table C in the Example Section at the end of the description is preferred as compound according to the invention, and is also preferred in the methods and uses according to the invention.
  • a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 is the compound I according to the invention, and as compound I in the methods and uses according to the invention, wherein said compounds are defined in accordance with Table C of the example section:
  • 1-1 1 is a preferred compound I, and is preferred in the methods and uses according to the invention.
  • 1-16 is a preferred compound I, and is preferred in the methods and uses according to the invention.
  • 1-21 is a preferred compound I, and is preferred in the methods and uses according to the invention.
  • I-26 is a preferred compound I, and is preferred in the methods and uses according to the invention.
  • 1-31 is a preferred compound I, and is preferred in the methods and uses according to the invention.
  • one embodiment of the invention relates to co-crystals and solvates of the compounds of the formula I, and more preferably a compound selected from compounds I- 1 1 , 1-16, 1-21 , I-26, 1-31 according to Table C/C.
  • the solvates are preferably with water, or also preferably with organic solvents, preferably with aromatic hydrocarbons. It was surprisingly found that the compound of formula 1-21 forms stable crystals with toluene in a stoichiometric ratio, i.e. a solvate. Especially, two forms (form A and form B) are obtained. Form B can be identified as a monosolvate.
  • the compounds and mixtures according to the invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • the compounds and mixtures according to the invention are especially suitable for efficiently combating the following pests: insects from the order of the lepidopterans (Lepidoptera), for example Acronicta major, Adoxophyes orana, Aedia leucomelas, Agrotis spp.
  • Chilo suppressalis such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp.
  • Feltia subterranean such as Feltia subterranean; Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp. such as Heliothis armigera, Heliothis virescens, Heliothis zea; Hellula undalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homona magnanima, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma spp.
  • Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkella, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mocis repanda, Mythimna separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp.
  • Pseudoplusia includens, Pyrausta nubilalis, hyacionia frustrana, Scrobipalpula absolutea, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp.
  • Atomaria linearis such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as Bruchus lentis, Bruchus pisorum, Bruchus rufimanus; Byctiscus betulae, Callosobruchus chinensis, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp.
  • Leptinotarsa decemlineata such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolontha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp.
  • Phyllotreta chrysocephala such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., hizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais; Sphenophorus spp. such as Sphenophorus levis; Sternechus spp.
  • Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp.
  • Anopheles albimanus such as Anopheles albimanus, Anopheles crucians, Anopheles freeborni, Anopheles gambiae, Anopheles leucosphyrus, Anopheles maculipennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp.
  • Chrysomya bezziana such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochliomyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp.
  • Lucilia caprina such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetiola destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabulans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp.
  • Phorbia antiqua Phorbia brassicae, Phorbia coarctata
  • Prosimulium mixtum Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis cerasi, Rhagoletis pomonella
  • Sarcophaga spp. such as Sarcophaga haemorrhoidalis
  • Simulium vittatum Stomoxys spp. such as Stomoxys calcitrans
  • thrips such as Tabanus atratus, Tabanus bovinus, Tabanus lineola, Tabanus similis; Tannia spp., Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp., thrips (Thysanoptera), e.g. Basothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp.
  • Thisanoptera e.g. Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp.
  • Calotermes flavicollis Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis, cockroaches (Blattaria - Blattodea), e.g.
  • Aphis fabae such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp.
  • Dysaphis plantaginea such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cingulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster integriceps; Euscelis bilobatus, Euschistus spp.
  • Euschistuos heros such as Euschistuos heros, Euschistus impictiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp.
  • Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbiae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia costalis, Monelliopsis pecanis, Myzus spp.
  • Nezara spp. such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp.
  • Pseudococcus comstocki such as Pseudococcus comstocki; Psylla spp. such as Psylla mali, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp.
  • Rhopalosiphum pseudobrassicas such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp.
  • Thyanta perditor such as Thyanta perditor; Tibraca spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii, ants, bees, wasps, sawflies (Hymenoptera), e.g.
  • Atta capiguara Atta cephalotes, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Bombus spp., Camponotus floridanus, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Hoplocampa spp. such as Hoplocampa minuta, Hoplocampa testudinea; Lasius spp.
  • Amblyomma spp. e.g. Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum
  • Argas spp. e.g. Argas persicus
  • Boophilus spp. e.g. Boophilus annulatus, Boophilus decoloratus, Boophilus microplus
  • Dermacentor silvarum, Dermacentor andersoni Dermacentor variabilis
  • Hyalomma spp. e.g. Hyalomma truncatum
  • Ixodes spp. e.g.
  • Sarcoptes spp. e.g. Sarcoptes scabiei
  • Eriophyidae spp. such as Acaria sheldoni, Aculops spp. (e.g. Aculops pelekassi) Aculus spp. (e.g. Aculus
  • Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp.
  • Eotetranychus spp. such as Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae; Bryobia praetiosa, Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligonychus pratensis), Vasates lycopersici; Araneida, e.g.
  • Geophilus spp. Scutigera spp. such as Scutigera coleoptrata; millipedes (Diplopoda), e.g. Blaniulus guttulatus, Narceus spp., Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp.
  • Linognathus vituli such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp., springtails (Collembola ), e.g. Onychiurus ssp. such as Onychiurus armatus,
  • nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiy
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Di
  • pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caenorhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalocrosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cyclocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furcatus, Dicladispa armigera , Diloboderus spp. such
  • Leptocorsia oratorius Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Maladera matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipterus, Microtheca spp., Mocis latipes, Murgantia spp., Mythemina separata ,
  • Neocapritermes opacus Neocapritermes parvus, Neomegalotomus spp., Neotermes spp., Nymphula depunctalis, Oebalus pugnax, Orseolia spp. such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Rachiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp.
  • Scirpophaga incertulas such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinophara coarctata; Sesamia spp. such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis,
  • insects preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, and chewing-biting pests such as insects from the genera of
  • Thysanoptera Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, Diptera, e.g.
  • Calliphora vicina Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops siiacea, Chrysops atianticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripaipus, Culex quinquefasciatus, Culex tarsaiis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina mors
  • 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
  • Perkinsiella saccharicida Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii.
  • Lepidoptera in particular: Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea
  • the compounds and mixtures of the present invention are particularly useful for controlling insects from the order of Coleoptera, in particular Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus 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 speciosa Diabrotica virgifera, Epilachna 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
  • the compounds and mixtures of the present invention are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Hemiptera and Thysanoptera.
  • the compounds and mixtures of the present invention are especially suitable for efficiently combating pests like insects from the order of the lepidopterans (Lepidoptera), beetles (Coleoptera), flies and mosquitoes (Diptera), thrips (Thysanoptera), termites (Isoptera), bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), ants, bees, wasps, sawflies (Hymenoptera), crickets, grasshoppers, locusts (Orthoptera), and also Arachnoidea, such as arachnids
  • the compounds and mixtures of the present invention are particularly useful for controlling insects of the order Lepidoptera, especially Lepidoptera selected from Agrotis, Chilo,
  • Cnaphalocerus Crocidolomia, Cydia, Heliothis, Manduca, Pieris, Plutella, Pyrausta, Sesamia , Spodoptera, Thermesia, Trichloplusia, Tuta.
  • the compounds and mixtures of the present invention are particularly useful for controlling Thysanoptera, especially Thysanoptera selected from Franklinella.
  • the compounds and mixtures of the present invention are particularly useful for controlling True Bugs, especially True Bugs selected from Lygus, Murgantia.
  • the compounds and mixtures of the present invention are particularly useful for controlling Diptera, especially Diptera selected from Delia, Liriomyza.
  • the compounds and mixtures of the present invention are particularly useful for controlling Beetles, especially Beetles selected from Agriotes, Cyclocephala, Diabrotica, Epitrix,
  • the compounds and mixtures according to the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compounds and mixtures according to the invention. Therefore the invention also relates to agrochemical compositions comprising an auxiliary and compound or a mixture according to the invention, i.e. a mixture of at least one compound I of formula I and of at least one compound II according to the present invention.
  • An agrochemical composition comprises a pesticidally effective amount of a pesticidal compound or mixture according to the invention.
  • the term "effective amount” denotes an amount of the composition or of the mixture, which is sufficient for controlling harmful pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the animal pests species to be con-trolled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, gran-ules, pressings, capsules, and mixtures thereof.
  • composition types are suspen-sions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pes-ticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac- tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalen
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides e.g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and am- photeric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl- polyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers.
  • polybases are polyvinylamines or poly- ethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I or the mixture according to the invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I or a mixture according to the invention 10-60 wt% of a compound I or a mixture according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%.
  • the active substance dissolves upon dilution with water.
  • a compound I or a mixture according to the invention 5-25 wt% of a compound I or a mixture according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I or a mixture according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium
  • lignosulfonate and alcohol ethoxylate 0, 1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • wt% binder e.g.
  • polyvinylalcohol is added.
  • Water-dispersible granules and water-soluble granules (WG, SG) 50-80 wt% of a compound I or a mixture according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound lor a mixture according to the invention are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound lor a mixture according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. carboxymethylcellulose
  • wt% of a compound I or a mixture according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alkohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I or a mixture according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
  • diphenylmethene-4,4'-diisocyanatae are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • a protective colloid e.g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of a polyurea microcapsules.
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • 1 -10 wt% of a compound I or a mixture according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of a compound I or a mixture according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • solid carrier e.g. silicate
  • a compound I or a mixture according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • organic solvent e.g. aromatic hydrocarbon.
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
  • auxiliaries such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • a suspoconcentration is preferred for the application in crop protection.
  • the SC agrochemical composition comprises between 50 to 500 g/L (grams per Litre), or between 100 and 250 g/L, or 100 g/L or 150g/L or 200g/L or 250 g/L.
  • the granules according to formulation type xii are especially preferred for the application in rice.
  • Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water- soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating compound I or a mixture according to the invention and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.001 to 1 kg per ha, more preferably from 0.005 to 0.9 kg per ha, in particular from 0.005 to 0.5 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 0.1 to 300 g, more preferably from 0.1 to 100 g and most preferably from 0.25 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • the compounds and mixtures according to the invention may be used for controlling invertebrate pests.
  • the compounds I and their mixtures can be applied simultaneously, that is jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in-situ" on the desired location, as e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • the compounds I and their mixtures are usually applied in a weight ratio of from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, preferably from 625:1 to 1 :625, preferably 500:1 to 1 :100, preferably from 100:1 to 1 :100 preferably from 20:1 to 1 :50, preferably from 20:1 to 1 :20, preferab,y from 10:1 to 1 :10, in particular from 5:1 to 1 :20, in particular from 5:1 to 1 :10, in particular from 5:1 to 1 :5.
  • the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 0.5 g/ha to 1000 g/ha, preferably from 1 to 750 g/ha, in particular from 5 to 500 g/ha.
  • the compounds and mixtures according to the invention are effective through both contact and ingestion.
  • the compounds and mixtures according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive compounds and mixtures or of compositions comprising them.
  • the mixtures according to the invention are used in crop protection, especially for the protection of living plants.
  • the mixtures according to the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.
  • the mixtures according to the present invention are prepared into a bait preparation.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • the animal pest also referred to as "invertebrate pest"
  • insect pest i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing
  • contacting includes both direct contact (applying the compounds/mixtures/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the
  • the compounds and mixtures according to the 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 the compounds and mixtures according to the invention.
  • crop refers both to growing and harvested crops.
  • the compounds and mixtures according to the 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 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.
  • Particularly preferred is the application of the compounds and mixtures according to the invention and the compositions comprising them on rice. Particularly preferred is the application of the mixtures according to the invention and the compositions comprising them on soybeans. Particularly preferred is the application of the mixtures according to the invention and the compositions comprising them on corn (maize).
  • the application of the compounds and mixtures according to the invention especially the compounds as individualized herein, e.g. in Table AP-T, on specialty crops like fruits and vegetables.
  • the application is on fruiting vegetables, and especially on tomato, on pepper or on eggplant.
  • the application is on leafy vegetables, and especially on cabbage or on lettuce.
  • the application is on tubers (tuber vegetables), and especially on potato or on onion.
  • tubers tubers
  • the compounds and mixtures according to the invention and the compositions comprising them on fruit and vegetables especially fruit and vegetables selected from apple, tomato, broccoli, pepper, cucumber, eggplant, potato, cabbage, onion, leek, radish, squash, lettuce, bean, spinach.
  • compositions comprising them on a crop selected from chickpea, sunflower, alfalfa, canola (oil seed rape), cotton, peanut.
  • the compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show good efficacy on lepidoptera, coleoptera, diptera and true bugs.
  • the compounds and mixtures according to the invention and the compositions comprising them especially the compounds shown in Table C show high efficacy on lepidoptera: Chilo suppressalis, Cnaphalocerus medinalis, Spodoptera sp. Plutella xylostella, Tuta absoluta and others.
  • the compounds and mixtures according to the invention and the compositions comprising them show high efficacy on coleoptera: Leptinotarsa decemlineata and others.
  • the compounds and mixtures according to the invention and the compositions comprising them show excellent efficacy in control of the following pests: Cnaphalocerus medinalis, Chilo suppressalis, Spodoptera frugiperda, Spodoptera exigua, Spodoptera sp., Plutella xylostella, Plutella xylostella , Tuta absolutea , Leptinotarsa decemlineata, Lygus hesperus.
  • the compounds and mixtures according to the invention and the compositions comprising them especially the compounds shown in Table C, show excellent efficacy in control of the following pests in the following crops:
  • the invention relates to methods and uses, wherein a compound of fomula IA as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of fomula IA-1 as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of fomula IB as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of fomula IC as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of fomula ID as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound selected from the compounds 1-1 to I-40 as defined in Table C in the Example Section, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of formula 1-1 1 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C. In some embodiments, the invention relates to methods and uses, wherein a compound of formula 1-16, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of formula 1-21 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of formula I-26, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • the invention relates to methods and uses, wherein a compound of formula 1-31 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
  • SPC specialty crops
  • SPC-FV fruiting vegetable
  • SPC-LV leafy vegetable
  • SPC-T tubers
  • ST seed treatment
  • the compounds and mixtures according to the invention and the compositions comprising them show excellent efficacy in control of the following pests in the following crops:
  • P-C-1 13 Meligethes aeneus vegetables
  • P-C-1 15 Meligethes aeneus Brassica
  • the application types are understood to include several applications per crop season, so as to control first and second and higher generations of pests.
  • the compounds and mixtures according to the 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 an insecticidally 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 habitat, breeding ground, food supply, cultivated 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 I and at least one active compound II.
  • 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 a mixture according to the 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 and mixtures according to the invention can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds and mixtures according to the 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 and mixtures according to the 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 and mixtures according to the invention /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.

Abstract

N-Thio-anthranilamide compounds of formula (I) wherein A is A1 formula (A1) and stereoisomers, salts, tautomers and N-oxides, and polymorphic crystalline forms, co-crystals or solvates of the compounds or a stereoisomer, salt, tautomer or N-oxide thereof, wherein the variables and the indices are as defined per the description, processes for preparing the compounds I, pesticidal compositions comprising compounds I, use of compounds I for the control of insects, acarids or nematodes, and compounds and compositions for treating, controlling, preventing or protecting animals against infestation or infection by parasites by use of compounds of formula I.

Description

N-Thio-anthranilamide compounds and their use as pesticides Description The present invention relates to N-Thio-anthranilamide compounds of formula (I)
Figure imgf000002_0001
wherein R1 is hydrogen; or Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, or Ca-Ce-cycloalkyl, each of which is unsubstituted or substituted with 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, Ci-Cio-alkoxy, Ci-Cio-alkylthio, Ci-Cio-alkylsulfinyl, C1-C10- alkylsulfonyl, C2-Cio-alkoxycarbonyl, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino and C3-C8- cycloalkylamino; or Ci-Cio-alkylcarbonyl, Ci-Cio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl;
A is
Figure imgf000002_0002
wherein # denotes the binding site;
R2 and R3 each independently are R6 or together with the sulfur atom to which they are
attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, which ring can be fused with one or two saturated, partially unsaturated or unsaturated 5- to 6-membered rings which may contain 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of the above rings are unsubstituted or substituted by any combination of 1 to 6 groups R8;
G is oxygen or sulfur;
R6 is Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, C3-Ce-cycloalkyl, C3-Ce-cycloalkenyl, C3-C8- cycloalkynyl, phenyl, naphthyl, biphenyl, or a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of these groups are unsubstituted or substituted by any combination of 1 to 6 groups R8; is R9; or two groups R8 together with the atoms to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which may contain 1 to 4 heteroatoms /heterogroups selected from oxygen, nitrogen, sulfur, SO and SO2, and which ring system is unsubstituted or substituted with any combination of 1 to 6 groups Rs. is R10, R11, -C(=G)R10, -C(=NOR10)R10, -C(=NNR 0 2)R10 , -C (=G)OR10, -C(=G)NR10 2, - OC(=G) R10, -OC(=G)OR10, -NR10C(=G)R10, -N[C(=G)R10]2, -NR10C(=G)OR10, -
Figure imgf000003_0001
NR 0-N[C(=G)R10]2, -N[(C=G)R10]-NR10 2, -NR 0-NR 0[(C=G)GR10], -NR10[(C=G)NR10 2, -
Figure imgf000003_0002
NR 0SO2R10, -S02OR10, -OS02R10, -OR10, -NR10 2, -SR10, -SiR10 3, -PR10 2, -P(=G)R10, - SOR10, -SO2R10, -PG2R102, -PG3R102, or two groups R9 together are (=G), (=N-R10), (=CR1¾), (=CHR10), or (=CH2); is Ci-Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Ce-cycloalkyl, C4-C8-cycloalkenyl, C3-C8 cycloalkyl- Ci-C4-alkyl, C4-C8-cycloalkenyl-Ci-C4-alkyl, C3-Cs-cycloalkyl-C2-C4-alkenyl, C4- Cs-cycloalkenyl-C2-C4-alkenyl, Ci-Cio-alkyl-C3-C8-cycloalkyl, C2-Cio-alkenyl-C3-Cs- cycloalkyl, C2-Cio-alkynyl-C3-C8-cycloalkyl, Ci-Cio-alkyl-C4-C8-cycloalkenyl, C2-Cio-alkenyl C4-C8-cycl oal kenyl , C2-C1 o-a lkynyl-C4-C8-cycloal kenyl ,
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
wherein the above groups are unsubstituted or substituted with any combination of from 1 to 6 groups R11; is halogen, cyano, nitro, hydroxy, mercapto, amino, formyl, Ci-Cio-alkylcarbonyl, C1-C10- alkoxy, C2-Cio-alkenyloxy, C2-Cio-alkynyloxy, Ci-Cio-haloalkoxy, C3-Cio-haloalkenyloxy, C3-Cio-haloalkynyloxy, C3-Ce-cycloalkoxy, C4-Ce-cycloalkenyloxy, C3-Ce-halocycloalkoxy, C4-Cs-halocycloalkenyloxy, C3-Cs-cycloalkyl- Ci-C4-alkoxy, C4-Cs-cycloalkenyl-Ci-C4- alkoxy, C3-Cs-cycloalkyl- C2-C4-alkenyloxy, C4-C8-cycloalkenyl-C2-C4-alkenyloxy, C1-C10- alkyl-C3-C8-cycloalkoxy, Ci-Cio-alkenyl-C3-Cs-cycloalkoxy, Ci-Cio-alkynyl-C3-Cs- cycloalkoxy, Ci-Cio-alkyl-C3-C8-cycloalkenyloxy, Ci-Cio-alkenyl-C3-C8-cycloalkenyloxy, C C4-alkoxy-Ci-Cio-alkoxy, Ci-C4-alkoxy-C2-Cio-alkenyloxy, mono- or di(Ci-Cio- alkyl)carbamoyl, mono- or di(Ci-Cio-haloalkyl)carbamoyl, mono- or di(C3-Cs- cycloalkyl)carbamoyl,
Ci-Cio-alkoxycarbonyl, Cs-Cs-cycloalkoxycarbonyl, Ci-Cio-alkylcarbonyloxy, C3-Ce-cyclo alkylcarbonyloxy, Ci-Cio-haloalkoxycarbonyl, Ci-Cio-haloalkylcarbonyloxy, C1-C10- alkanamido, Ci-Cio-haloalkanamido, C2-Cio-alkenamido, C3-Ce-cycloalkanamido, C3-C8- cycloalkyl-Ci-C4-alkanamido,
Ci-Cio-alkylthio, C2-Cio-alkenylthio, C2-Cio-alkynylthio, Ci-Cio-haloalkylthio, C2-C10- haloalkenylthio, C2-Cio-haloalkynylthio, Cs-Cs-cycloalkylthio, Ca-Cs-cycloalkenylthio, C3-C8 halocycloalkylthio, Cs-Ce-halocycloalkenylthio, Cs-Ce-cycloalkyl- Ci-C4-alkylthio, C4-C8- cycloalkenyl-Ci-C4-alkylthio, C3-Ce-cycloalkyl- C2-C4-alkenylthio, C4-Ce-cycloalkenyl-C2-C4- alkenylthio, Ci-Cio-alkyl-C3-C8-cycloalkylthio, Ci-Cio-alkenyl-C3-C8-cycloalkylthio, C1-C10- alkynyl-C3-Ce-cycloalkylthio, Ci-Cio-alkyl-C3-C8-cycloalkenylthio, Ci-Cio-alkenyl-C3-Ce- cycloalkenylthio, Ci-Cio-alkylsulfinyl, C2-Cio-alkenylsulfinyl, C2-Cio-alkynylsulfinyl, C1-C10- haloalkylsulfinyl, C2-Cio-haloalkenylsulfinyl, C2-Cio-haloalkynylsulfinyl, C3-C8- cycloalkylsulfinyl, Cs-Ce-cycloalkenylsulfinyl, Cs-Ce-halocycloalkylsulfinyl, C3-C8- halocycloalkenylsulfinyl, Cs-Cs-cycloalkyl- C 1 -C4-a I ky I s u If i ny I , C4-Cs-cycloalkenyl-Ci-C4- alkylsulfinyl, C3-Cs-cycloalkyl- C2-C4-alkenylsulfinyl, C4-C8-cycloalkenyl-C2-C4- alkenylsulfinyl, Ci-Cio-alkyl-C3-C8-cycloalkylsulfinyl, Ci-Cio-alkenyl-C3-C8-cycloalkylsulfinyl, Ci-Cio-alkynyl-C3-Cs-cycloalkylsulfinyl, Ci-Cio-alkyl-C3-C8-cycloalkenylsulfinyl, C1-C10- alkenyl-C3-C8-cycloalkenylsulfinyl, Ci-Cio-alkylsulfonyl, C2-Cio-alkenylsulfonyl, C2-C10- alkynylsulfonyl, Ci-Cio-haloalkylsulfonyl, C2-Cio-haloalkenylsulfonyl, C2-C10- haloalkynylsulfonyl, Cs-Cs-cycloalkylsulfonyl, Cs-Cs-cycloalkenylsulfonyl, C3-C8- halocycloalkylsulfonyl, Cs-Cs-halocycloalkenylsulfonyl, C3-Cs-cycloalkyl- C1-C4- alkylsulfonyl, C4-C8-cycloalkenyl-Ci-C4-alkylsulfonyl, Cs-Cs-cycloalkyl- C2-C4- alkenylsulfonyl, C4-C8-cycloalkenyl-C2-C4-alkenylsulfonyl, Ci-Cio-alkyl-C3-Cs- cycloalkylsulfonyl, Ci-Cio-alkenyl-C3-C8-cycloalkylsulfonyl, Ci-Cio-alkynyl-Cs-Ce- cycloalkylsulfonyl, Ci-Cio-alkyl-C3-Cs-cycloalkenylsulfonyl, Ci-Cio-alkenyl-C3-C8- cycloalkenylsulfonyl, di(Ci-Cio-alkyl)amino, Ci-Cio-alkylamino, C2-Cio-alkenylamino, C2- Cio-alkynylamino, Ci-Cio-alkyl-C2-Cio-alkenylamino, Ci-Cio-alkyl-C2-Cio-alkynylamino, Ci- Cio-haloalkylamino, C2-Cio-haloalkenylamino, C2-Cio-haloalkynylamino, C3-C8- cycloalkylamino, Cs-Ce-cycloalkenylamino, Cs-Ce-halocycloalkylamino, C3-C8- halocycloalkenylamino, Cs-Ce-cycloalkyl- Ci-C4-alkylamino, C4-C8-cycloalkenyl-Ci-C4- alkylamino, Ca-Ce-cycloalkyl- C2-C4-alkenylamino, C4-C8-cycloalkenyl-C2-C4-alkenylamino, Ci-Cio-alkyl-C3-C8-cycloalkylamino, Ci-Cio-alkenyl-C3-C8-cycloalkylamino, Ci-Cio-alkynyl- C3-C8-cycloalkylamino, Ci-Cio-alkyl-C3-C8-cycloalkenylamino, Ci-Cio-alkenyl-C3-Cs- cycloalkenylamino, tri(Ci-Cio-alkyl)silyl, aryl, aryloxy, arylthio, arylamino, aryl-Ci-C4-alkoxy, aryl-C3-C4-alkenyloxy, aryl-Ci-C4-alkylthio, aryl-C2-C4-alkenylthio, aryl-Ci-C4-alkylamino, aryl-C3-C4-alkenylamino, aryl-di(Ci-C4-alkyl)silyl, triarylsilyl, wherein aryl is phenyl, naphthyl or biphenyl, or
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
wherein these aryl and these heterocyclic ringsystems are unsubstituted or substituted with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-Ce-cycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, di(Ci-C4-alkyl)amino, Ci-C4-alkylamino, C1-C4- haloalkylamino, formyl and Ci-C4-alkylcarbonyl;
Q1 and Q2 each independently are hydrogen, halogen, cyano, SCN, nitro, hydroxy, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, C3- Cs-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci- Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, C1-C10- haloalkylsulfonyl, Ci-Cio-alkylsulfonyloxy, Ci-Cio-haloalkylsulfonyloxy, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Cs-Cs-cyclalkylamino, alkylcarbonyl, Ci-Cio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl, or tri(Ci-Cio)-alkylsilyl, or Q and Q2 are each independently phenyl, benzyl or phenoxy, wherein each ring is
unsubstituted or substituted with any combination of from 1 to 3 substituents independently selected from the group halogen, cyano, nitro, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-C10- alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, Cs-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-alkylsulfinyl, Ci-
Cio-alkylsulfonyl, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Cs-Cs-cycloalkylamino, C1-C10- alkyl-C3-C8-cycloalkylamino, Ci-Cio-alkylcarbonyl, CrCio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl and tri(Ci-Cio)-alkylsilyl; is halogen; or Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-C10- alkynyl, C3-Cio-haloalkynyl, Cs-Ce-cycloalkyl, C3-Cs-halocycloalkyl, Ci-Cio-alkyl-C3-C8- cycloalkyl, Ci-Cio-haloalkyl-C3-Cs-cycloalkyl, each unsubstituted or independently substituted with 1 to 2 groups selected from cyano, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci- Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, CrCio-haloalkylsulfinyl, C1-C10- alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, and Ci-Cio-alkoxycarbonyl; or is OR14, S(0)qR14, NR15R16, OS(0)2R17, NR16S(0)2R17, C(S)NH2, C(R18)=NOR18, C3-C8- cycloalkyl-Ci-C4-alkyl, Ci-Cio-alkylaminothiocarbonyl, or di(Ci-Cio-alkyl)aminothiocarbonyl;
R14 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Ce-cycloalkyl, Cs-Cs-halocycloalkyl, C3-C8-cycloalkyl-Ci-C4-alkyl, Ci- C4-alkyl-C3-C8-cycloalkyl, C3-C8-halocycloalkyl-Ci-C4-alkyl, Ci-C4-haloalkyl-C3-C8- cycloalkyl, or Ci-Cio-haloalkylcarbonyl, each unsubstituted or substituted with 1 R19;
R15 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Ce-cycloalkyl, Cs-Cs-halocycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl, Ci- C4-haloalkyl-C3-C8-cycloalkyl, or Ci-Cio-haloalkylcarbonyl, each unsubstituted or substituted with 1 R19;
R16 is hydrogen; or Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2- Cio-alkynyl, C3-Cio-haloalkynyl, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, Ci-C4-alkyl-C3-Ce- cycloalkyl, or Ci-C4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1
R19;
R17 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3- Cio-haloalkynyl, Cs-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, Ci-C4-alkyl-C3-C8-cycloalkyl, or Ci- C4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1 R19;
R19 is cyano, nitro, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, Ci-Cio-alkoxycarbonyl, Ci-Cio-alkylamino, or di(Ci-Cio-alkyl)amino; or
R19 is phenyl or a heteroaromatic 5- or 6-membered ring which contains 1 to 4
heteroatoms selected from oxygen, nitrogen, sulfur, the phenyl radical and the
heteroaromatic ring being unsubstituted or substituted with any combination of from 1 to 3 groups selected from halogen, cyano, nitro, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, Ca-Cs-cycloalkyl, C3-C8- halocycloalkyl, Ci-Cio-alkoxy, Ci-Oo-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-alkylsulfinyl, Ci- Cio-alkylsulfonyl, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Ca-Cs-cycloalkylamino, C1-C10- alkyl-C3-C8-cycloalkylamino, Ci-Cio-alkylcarbonyl, Ci-Cio-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl and tri(Ci-Cio)-alkylsilyl;
R18 is the same or different: hydrogen, Ci-Oo-alkyl, or Ci-Cio-haloalkyl; q is 0, 1 or 2;
Q4 is halogen, cyano, nitro, hydroxy, COOH, C(0)NH2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-C10- alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, C3-Ce-cycloalkyl, C3-C8- halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, CrCio-alkylthio, Ci-Cio-haloalkylthio, Cr Cio-alkylsulfinyl, Ci-Cio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, Ci-
Cio-alkylamino, di(Ci-Cio-alkyl)amino, Cs-Ce-cycloalkylamino, Ci-Cio-alkylcarbonyl, Ci- Cio-alkoxycarbonyl Ci-Cio-alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl or tri(Ci-Cio)- alkylsilyl; or Q4 is phenyl, benzyl, benzyloxy, phenoxy, a 5- or 6-membered heteroaromatic ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein each of the above ring systems is unsubstituted or substituted with any combination of from 1 to 3 groups selected from halogen, cyano, nitro, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-C10- haloalkynyl, C3-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci- Cio-alkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-alkylamino, di(Ci-Cio- alkyl)amino, C3-Ce-cycloalkylamino, Ci-Cio-alkyl-C3-Ce-cycloalkylamino, C1-C10- alkylcarbonyl, Ci-Cio-alkoxycarbonyl, Ci-Cio-alkylaminocarbonyl, di(Ci-Cio- alkyl)aminocarbonyl and tri(Ci-Cio)-alkylsilyl;
X and Y are each independently oxygen or sulfur; V and V are each independently N or CQ2;
W is N, CH or CQ4; n is O or l ; p is 0, 1 , 2, 3, or 4; or a stereoisomer, salt, tautomer, or N-oxide, or a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof. The invention relates to the compounds of formula (I), their stereoisomers, salts (in particular their agriculturally or veterinarily acceptable salts), tautomers, and N-oxides (= hereinafter defined as "compounds according to the invention") which are particularly useful for controlling invertebrate pests, in particular for controlling arthropods and nematodes and especially insects. Furthermore, the invention relates to processes for the synthesis of compounds according to the invention and to intermediate compounds for the synthesis of compounds of formula (I) and the compounds according to the invention.
The invention especially relates to compositions comprising the compounds according to the invention.
The invention especially also relates to certain uses of the compounds according to the invention.
Invertebrate pests and in particular insects, arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new and more effective agents for combating invertebrate pests, in particular insects, arachnids and nematodes.
It is an object of the present invention to provide further compounds having a high pesticidal activity against invertebrate pests, in particular against insect, arachnid or nematode pest. The compounds should show a broad activity spectrum against a large number of different invertebrate pests, in particular against difficult to control insects, arachnids, acarids and nematodes. It can also be advantageous if the compounds allow to control specific pests which are difficult to control, or if they allow the application on a certain crop. The compounds should have properties which allow to prepare stable and active compositions therefrom.
Furthermore, there is a desire for pesticide compounds or combination of compounds, which when applied improve plants, which may result in "plant health", "vitality of plant propagation material" or "increased plant yield".
It is therefore an object of the present invention to provide agricultural combinations
which solves one or more than one of the discussed problems as
- reducing the dosage rate,
- enhancing the spectrum of activity,
- combining knock-down activity with prolonged control,
- improving resistance management,
- Improved plant health;
- Improved vitality of plant propagation material, also termed seed vitality;
- Increased plant yield.. It has been found that the above objectives can be achieved by certain N-thio-anthranilamide compounds of the general formula (I), as defined herein, including their stereoisomers, salts (in particular their agriculturally or veterinarily acceptable salts), tautomers and N-oxides.
Moreover, the present invention also relates to and includes the following embodiments: - an agricultural or veterinary composition comprising at least one compound of formula (I) or a stereoisomer, salt (in particular an agriculturally or veterinarily acceptable salts), tautomer, or N-oxide thereof (= compound according to the invention), and at least one liquid and/or solid carrier.
- a method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound according to the invention, or a composition as defined herein.
- a method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound according to the invention, or a composition as defined herein.
- a method for the protection of plant propagation material, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propagation material respectively seeds before sowing and/or after pregermination with at least one compound according to the invention, or a composition as defined herein.
- seed comprising a compound according to the invention, in an amount of from 0.1 g to 10 kg per 100 kg of the plant propagation material.
- use of a compound according to the invention, or a composition as defined herein for combating or controlling invertebrate pests of the group of insects, arachnids or nematodes. - use of a compound according to the invention, or a composition as defined herein for protecting growing plants from attack or infestation by invertebrate pests.
- use of a compound according to the invention or a composition as defined herein for combating or controlling invertebrate parasites in and on animals.
- a method for treating a non-human animal infested or infected by parasites or for preventing a non-human animal from getting infested or infected by parasites or for protecting a non- human animal against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the non-human animal a parasiticidally effective amount of a compound according to the invention, or a composition as defined in claim herein.
- a compound according to the invention for use as a medicament.
- a compound according to the invention for use in the treatment, control, prevention or protection of animals against infestation or infection by parasites.
Anthranilamide compounds have been described in a number of patent applications (e.g. WO 01/70671 , WO 03/015518, WO 03/024222, WO 2006/000336, WO 2006/068669,
WO 2007/043677, WO 2008/130021 , WO 03/015519, WO 2004/046129). WO 03/016300 describes a generic anthranilamide formula encompassing N-thio-anthranilamide compounds. WO 03/016284 describes inter alia certain N-thio-anthranilamide compounds, in which the nitrogen of the benzoic acid amide is substituted by two substituents, one of which may be bound via a sulfur atom. WO 2007/006670, describes N-thio-anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides. PCT/EP2012/065650,
PCT/EP2012/065651 , and the unpublished applications US 61/578267, US 61/593897 and US 61/651050 describe certain N-Thio-anthranilamide compounds and their use as pesticides. Depending on the substitution pattern, the compounds of the formula (I) may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. The invention provides both the pure enantiomers or pure diastereomers of the compounds of formula (I), and their mixtures and the use according to the invention of the pure enantiomers or pure diastereomers of the compound of formula (I) or its mixtures. Suitable compounds of the formula (I) also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double- bond, nitrogen-sulfur double bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
The compounds of the formula (I) may be present in the form of their N-oxides. The term "N- oxide" includes any compound of the present invention which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. N-oxides of compounds (I) can in particular be prepared by oxidizing the ring nitrogen atom(s) of the pyridine ring and/or the pyrazole ring with a suitable oxidizing agent, such as peroxo carboxylic acids or other peroxides. The person skilled in the art knows if and in which positions compounds of the formula (I) of the present invention may form N-oxides. The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of formula (I), their enantiomers or diastereomers, mixtures of different crystalline states of the respective compound of formula (I), its enantiomers or diastereomers, as well as amorphous or crystalline salts thereof.
The term "co-crystal" denotes a complex of the compounds according to the invention or a stereoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules ("partner molecule", preferably one molecule type), wherein usually the ratio of the compound according to the invention and the other molecule is a stoichiometric ratio.
The term "solvate" denotes a co-complex of the compounds according to the invention, or a stereoisomer, salt, tautomer or N-oxide thereof, with solvent molecules. The solvent is usually liquid. Examples of solvents are methanol, ethanol, toluol, xylol. A preferred solvent which forms solvates is water, which solvates are referred to as "hydrates". A solvate or hydrate is usually characterized by the presence of a fixed number of n molecules solvent per m molecules compound according to the invention.
Co-crystals and solvates only differ by the nature of the partner molecule, i.e. in the case of co- crystals, the partner molecule is solid at room temperature, and in the case of solvates, the partner molecule is liquid at room temperature.
In one embodiment of the invention, the invention relates to co-crystals and solvates of the compounds according to the invention, more preferably a compound of formula IA, also preferably a compound of formula IB, also preferably a compound of formula IC, also preferably a compound of formula ID; more preferably a compound selected from the compounds 1-1 to I- 41 as defined in Table C; more preferably a compound selected from compounds 1-1 1 , 1-16, I- 21 , I-26, 1-31 according to Table C/C as described below.
An example for this embodiment of the invention is represented by the toluene solvates of compound 1-21 , as described below, which is a specific embodiment of the invention herewith. Salts of the compounds of the present invention are preferably agriculturally and veterinarily acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid if the compound of the present invention has a basic functionality or by reacting the compound with a suitable base if the compound of the present invention has an acidic functionality.
Suitable agriculturally acceptable 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 pesticidal action of the compounds according to the present invention. Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NhV) and substituted ammonium in which one to four of the hydrogen atoms are replaced by d-Gi-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci- C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of the present invention with an acid of the corresponding anion, preferably with hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
Veterinarily acceptable salts of the compounds of the present invention encompass the salts of those cations or the acid addition salts 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 containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorides, sulfates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, e.g. the monoacid salts or diacid salts of maleic acid, dimaleic acid, fumaric acid, e.g. the monoacid salts or diacid salts of fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn- Cm indicates in each case the possible number of carbon atoms in the group.
The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine. The term "partially or fully halogenated" will be taken to mean that 1 or more, e.g. 1 , 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by a halogen atom, in particular by fluorine or chlorine. A partially or fully halogenated radical is termed below also "halo-radical". For example, partially or fully halogenated alkyl is also termed haloalkyl.
The term "alkyl" as used herein (and in the alkyl moieties of other groups comprising an alkyl group, e.g. alkoxy, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 12 or 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of Ci-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl (sec-butyl), isobutyl and tert-butyl. Examples for Ci-C6-alkyl are, apart those mentioned for Ci-C4-alkyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 , 3-d i methyl butyl, 2,2- dimethylbutyl, 2, 3-d i methyl butyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl and 1-ethyl-2-methylpropyl.
Examples for Ci-Cio-alkyl are, apart those mentioned for Ci-C6-alkyl, n-heptyl, 1 -methylhexyl, 2- methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1 -ethyl pentyl, 2-ethylpentyl, 3- ethylpentyl, n-octyl, 1-methyloctyl, 2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1 ,2-dimethylhexyl, 1-propylpentyl, 2-propylpentyl, nonyl, decyl, 2-propylheptyl and 3-propylheptyl.
The term "alkylene" (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term "haloalkyl" as used herein (and in the haloalkyl moieties of other groups comprising a haloalkyl group, e.g. haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms ("Ci-Cio-haloalkyl"), frequently from 1 to 6 carbon atoms ("C1-C6- haloalkyl"), more frequently 1 to 4 carbon atoms ("Ci-Cio-haloalkyl"), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-C2-haloalkyl, more preferably from halomethyl, in particular from Ci-C2-fluoroalkyl. Halomethyl is methyl in which 1 , 2 or 3 of the hydrogen atoms are replaced by halogen atoms. Examples are bromomethyl, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl and the like. Examples for C1-C2- fluoroalkyl are fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl,
2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like. Examples for Ci-C2-haloalkyl are, apart those mentioned for Ci-C2-fluoroalkyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 2- chloroethyl, 2,2,-dichloroethyl, 2,2,2-trichloroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 1-bromoethyl, and the like. Examples for Ci-C4-haloalkyl are, apart those mentioned for Ci-C2-haloalkyl, 1-fluoropropyl, 2-fluoropropyl, 3-fluoropropyl, 3,3-difluoropropyl, 3,3,3-trifluoropropyl, heptafluoropropyl, 1 ,1 ,1 -trifl uoroprop-2-yl , 3- chloropropyl, 4-chlorobutyl and the like.
The term "cycloalkyl" as used herein (and in the cycloalkyl moieties of other groups comprising a cycloalkyl group, e.g. cycloalkoxy and cycloalkylalkyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms ("C3-Cio-cycloalkyl"), preferably 3 to 8 carbon atoms ("C3-Cs-cycloalkyl") or in particular 3 to 6 carbon atoms ("C3-C6- cycloalkyl"). Examples of monocyclic radicals having 3 to 6 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of monocyclic radicals having 3 to 8 carbon atoms comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicyclo[2.2.1 ]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and
bicyclo[3.2.1]octyl.
The term "cycloalkylene" (or cycloalkanediyl) as used herein in each case denotes an cycloalkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term "halocycloalkyi" as used herein (and in the halocycloalkyi moieties of other groups comprising an halocycloalkyi group, e.g. halocycloalkylmethyl) denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms or in particular 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine. Examples are 1- and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl and the like.
The term "cycloalkyl-alkyl" used herein denotes a cycloalkyl group, as defined above, which is bound to the remainder of the molecule via an alkylene group. The term "Cs-Cs-cycloalkyl-d- C4-alkyl" refers to a C3-Cs-cycloalkyl group as defined above which is bound to the remainder of the molecule via a Ci-C4-alkyl group, as defined above. Examples are cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclobutylpropyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylpropyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, and the like.
The term "alkenyl" as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 10 ("C2-Cio-alkenyl"), preferably 2 to 6 carbon atoms ("C2-C6-alkenyl"), in particular 2 to 4 carbon atoms ("C2-C4-alkenyl"), and a double bond in any position, for example C2-C4-alkenyl, such as ethenyl, 1 -propenyl, 2-propenyl, 1 - methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1-propenyl, 2-methyl-1 -propenyl, 1- methyl-2-propenyl or 2-methyl-2-propenyl; C2-C6-alkenyl, such as ethenyl, 1 -propenyl, 2- propenyl, 1-methylethenyl, 1 -butenyl, 2-butenyl, 3-butenyl, 1 -methyl-1-propenyl, 2-methyl-1- propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1-methyl-1 -butenyl, 2-methyl-1 -butenyl, 3-methyl-1-butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3- butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 - propenyl, 1-ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-
1- pentenyl, 2-methyl-1 -pentenyl, 3-methyl-1-pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2- pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1 -methyl-3-pentenyl,
2- methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl- 4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3- butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 - butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 - butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3, 3-dimethyl-1 -butenyl, 3,3-dimethyl-2- butenyl, 1 -ethyl-1 -butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1 -butenyl,
2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 - ethyl-2-methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl and the like, or C2-Cio-alkenyl, such as the radicals mentioned for C2-C6-alkenyl and additionally 1 -heptenyl, 2-heptenyl, 3-heptenyl, 1 - octenyl, 2-octenyl, 3-octenyl, 4-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 1 -decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl and the positional isomers thereof.
The term "alkenylene" (or alkenediyl) as used herein in each case denotes an alkenyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term "haloalkenyl" as used herein, which may also be expressed as "alkenyl which may be substituted by halogen", and the haloalkenyl moieties in haloalkenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 10 ("C2-Cio-haloalkenyl") or 2 to 6 ("C2-C6-haloalkenyl") or 2 to 4 ("C2-C4-haloalkenyl") carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
The term "alkynyl" as used herein denotes unsaturated straight-chain or branched hydrocarbon radicals having usually 2 to 10 ("C2-Cio-alkynyl"), frequently 2 to 6 ("C2-C6-alkynyl"), preferably 2 to 4 carbon atoms ("C2-C4-alkynyl") and one or two triple bonds in any position, for example C2- C4-alkynyl, such as ethynyl, 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1-methyl-2- propynyl and the like, C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- butynyl, 3-butynyl, 1-methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1- methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1 -butynyl, 1 ,1 -dimethyl-2- propynyl, 1-ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2- pentynyl, 1 -methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3- methyl-1 -pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1 ,1 -dimethyl- 2-butynyl, 1 ,1 -dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1- butynyl, 1 -ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl, 1 -ethyl-1 -methyl-2-propynyl and the like.
The term "alkynylene" (or alkynediyl) as used herein in each case denotes an alkynyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
The term "haloalkynyl" as used herein, which is also expressed as "alkynyl which may be substituted by halogen", refers to unsaturated straight-chain or branched hydrocarbon radicals having iusually 3 to 10 carbon atoms ("C2-Cio-haloalkynyl"), frequently 2 to 6 ("C2-C6- haloalkynyl"), preferabyl 2 to 4 carbon atoms ("C2-C4-haloalkynyl"), and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups are replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine. The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group usually having from 1 to 10 carbon atoms ("Ci-Cio-alkoxy"), frequently from 1 to 6 carbon atoms ("Ci-C6-alkoxy"), preferably 1 to 4 carbon atoms ("Ci-C4-alkoxy"), which is bound to the remainder of the molecule via an oxygen atom. Ci-C2-Alkoxy is methoxy or ethoxy. C1-C4- Alkoxy is additionally, for example, n-propoxy, 1-methylethoxy (isopropoxy), butoxy,
1- methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1 ,1 -dimethylethoxy (tert-butoxy). Ci-C6-Alkoxy is additionally, for example, pentoxy, 1 -methylbutoxy, 2-methylbutoxy, 3- methylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 - dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3- dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethyl butoxy, 2-ethyl butoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1-ethyl-1 -methylpropoxy or 1-ethyl-2-methylpropoxy. Ci-Ce-Alkoxy is additionally, for example, heptyloxy, octyloxy, 2-ethylhexyloxy and positional isomers thereof. Ci-Cio-Alkoxy is additionally, for example, nonyloxy, decyloxy and positional isomers thereof. The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group, as defined above, having from 1 to 10 carbon atoms ("Ci-Cio-haloalkoxy"), frequently from 1 to 6 carbon atoms ("Ci-C6-haloalkoxy"), preferably 1 to 4 carbon atoms ("C1-C4- haloalkoxy"), more preferably 1 to 3 carbon atoms ("Ci-C3-haloalkoxy"), wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Ci-C2-Haloalkoxy is, for example, OCH2F, OCHF2, OCF3, OCH2CI, OCHCI2, OCC , chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2- chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy or OC2F5. Ci-C4-Haloalkoxy is additionally, for example, 2-fluoropropoxy, 3-fluoropropoxy, 2,2- difluoropropoxy, 2,3-difluoropropoxy, 2-chloropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2- bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH2-C2F5, OCF2-C2F5, 1-(CH2F)-2-fluoroethoxy, 1-(CH2CI)-2-chloroethoxy, 1-(CH2Br)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy. Ci-C6-Haloalkoxy is additionally, for example, 5-fluoropentoxy, 5-chloropentoxy, 5-brompentoxy, 5-iodopentoxy, undecafluoropentoxy, 6-fluorohexoxy, 6-chlorohexoxy, 6-bromohexoxy, 6-iodohexoxy or dod ecaf I uorohexoxy .
The term "alkoxyalkyl" as used herein denotes in each case alkyl usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. "Ci-C6-Alkoxy-Ci-C6-alkyl" is a Ci-C6-alkyl group, as defined above, in which one hydrogen atom is replaced by a Ci-C6-alkoxy group, as defined above. Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (l -methylpropoxy)-methyl, (2- methylpropoxy)methyl, CH2-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl, 2- (l -methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)-ethyl, 2-(2-methylpropoxy)-ethyl,
2- (1 ,1 -dimethylethoxy)-ethyl, 2-(methoxy)-propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl, 2-(1 - methylethoxy)-propyl, 2-(n-butoxy)-propyl, 2-(1-methylpropoxy)-propyl, 2-(2-methylpropoxy)- propyl, 2-(1 ,1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl, 3-(n-propoxy)- propyl, 3-(1-methylethoxy)-propyl, 3-(n-butoxy)-propyl, 3-(1-methylpropoxy)-propyl, 3-(2- methylpropoxy)-propyl, 3-(1 ,1 -dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl, 2-(n- propoxy)-butyl, 2-(1 -methylethoxy)-butyl, 2-(n-butoxy)-butyl, 2-(1 -methylpropoxy)-butyl, 2-(2- methyl-propoxy)-butyl, 2-(1 ,1-dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl, 3-(n- propoxy)-butyl, 3-(1 -methylethoxy)-butyl, 3-(n-butoxy)-butyl, 3-(1 -methylpropoxy)-butyl, 3-(2- methylpropoxy)-butyl, 3-(1 ,1-dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl, 4-(n- propoxy)-butyl, 4-(1 -methylethoxy)-butyl, 4-(n-butoxy)-butyl, 4-(1 -methylpropoxy)-butyl, 4-(2- methylpropoxy)-butyl, 4-(1 ,1-dimethylethoxy)-butyl and the like.
The term "haloalkoxy-alkyl" as used herein denotes in each case alkyl as defined above, usually comprising 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein 1 carbon atom carries an haloalkoxy radical as defined above, usually comprising 1 to 10, frequently 1 to 6, in particular 1 to 4, carbon atoms as defined above. Examples are fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 1 -fluoroethoxymethyl, 2-fluoroethoxymethyl,
1.1- difluoroethoxymethyl, 1 ,2-difluoroethoxymethyl, 2,2-difluoroethoxymethyl, 1 ,1 ,2- trifluoroethoxymethyl, 1 ,2,2-trifluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl,
pentafluoroethoxymethyl, 1-fluoroethoxy-1 -ethyl, 2-fluoroethoxy-1 -ethyl, 1 ,1-difluoroethoxy-1- ethyl, 1 ,2-difluoroethoxy-1 -ethyl, 2,2-difluoroethoxy-1 -ethyl, 1 ,1 ,2-trifluoroethoxy-1 -ethyl, 1 ,2,2- trifluoroethoxy-1 -ethyl, 2,2, 2-trifluoroethoxy-1 -ethyl, pentafluoroethoxy-1 -ethyl, 1 -fluoroethoxy-2- ethyl, 2-fluoroethoxy-2-ethyl, 1 ,1 -difluoroethoxy-2 -ethyl, 1 ,2-difluoroethoxy-2-ethyl, 2,2- difluoroethoxy-2-ethyl, 1 ,1 ,2-trifluoroethoxy-2-ethyl, 1 ,2,2-trifluoroethoxy-2-ethyl, 2,2,2- trifluoroethoxy-2-ethyl, pentafluoroethoxy-2-ethyl, and the like.
The term "alkylthio"(also alkylsulfanyl or alkyl-S-)" as used herein denotes in each case a straight-chain or branched saturated alkyl group as defined above, usually comprising 1 to 10 carbon atoms ("CrCio-alkylthio"), frequently comprising 1 to 6 carbon atoms ("Ci-C6-alkylthio"), preferably 1 to 4 carbon atoms ("Ci-C4-alkylthio"), which is attached via a sulfur atom at any position in the alkyl group. Ci-C2-Alkylthio is methylthio or ethylthio. Ci-C4-Alkylthio is additionally, for example, n-propylthio, 1-methylethylthio (isopropylthio), butylthio,
1-methylpropylthio (sec-butylthio), 2-methylpropylthio (isobutylthio) or 1 ,1 -dimethylethylthio (tert- butylthio). Ci-C6-Alkylthio is additionally, for example, pentylthio, 1 -methylbutylthio,
2-methylbutylthio, 3-methylbutylthio, 1 ,1-dimethylpropylthio, 1 ,2-dimethylpropylthio,
2.2- dimethylpropylthio, 1 -ethylpropylthio, hexylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2-dimethylbutylthio,
1.3- dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio,
1- ethylbutylthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1 -ethyl-1 - methylpropylthio or 1-ethyl-2-methylpropylthio. d-Cs-Alkylthio is additionally, for example, heptylthio, octylthio, 2-ethylhexylthio and positional isomers thereof. Ci-Cio-Alkylthio is additionally, for example, nonylthio, decylthio and positional isomers thereof.
The term "haloalkylthio" as used herein refers to an alkylthio group as defined above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Ci-C2-Haloalkylthio is, for example, SCH2F, SCHF2, SCF3, SCH2CI, SCHCI2, SCCI3, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 2-fluoroethylthio, 2- chloroethylthio, 2-bromoethylthio, 2-iodoethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio,
2,2,2-trichloroethylthio or SC2F5. Ci-C4-Haloalkylthio is additionally, for example,
2-fluoropropylthio, 3-fluoropropylthio, 2,2-difluoropropylthio, 2,3-difluoropropylthio,
2- chloropropylthio, 3-chloropropylthio, 2,3-dichloropropylthio, 2-bromopropylthio,
3- bromopropylthio, 3,3,3-trifluoropropylthio, 3,3,3-trichloropropylthio, SCH2-C2F5, SCF2-C2Fs, 1- (CH2F)-2-fluoroethylthio, 1 -(CH2CI)-2-chloroethylthio, 1 -(CH2Br)-2-bromoethylthio,
4- fluorobutylthio, 4-chlorobutylthio, 4-bromobutylthio or nonafluorobutylthio. Ci-C6-Haloalkylthio is additionally, for example, 5-fluoropentylthio, 5-chloropentylthio, 5-brompentylthio,
5- iodopentylthio, undecafluoropentylthio, 6-fluorohexylthio, 6-chlorohexylthio, 6-bromohexylthio,
6- iodohexylthio or dodecafluorohexylthio.
The terms "alkylsulfinyl" and "S(0)n-alkyl" (wherein n is 1 ) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfinyl [S(O)] group. For example, the term "Ci-C2-alkylsulfinyl" refers to a Ci-C2-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C4-alkylsulfinyl" refers to a Ci-C4-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. The term "Ci-C6-alkylsulfinyl" refers to a 0-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Ci-C2-alkylsulfinyl is methylsulfinyl or ethylsulfinyl. Ci-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1-methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl) or 1 ,1 -dimethylethyl sulfinyl (tert-butylsulfinyl). Ci -C6-a I kyI s u If i nyI is additionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl,
1.1- dimethylpropylsulfinyl, 1 ,2-dimethylpropylsulfinyl, 2,2-dimethylpropylsulfinyl,
1-ethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl,
3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1 , 1 -d imethyl butylsulf i nyl , 1 ,2-dimethylbutylsulfinyl, 1 ,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3- dimethylbutylsulfinyl, 1 -ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1 ,1 ,2-trimethylpropylsulfinyl, 1 ,2,2- trimethylpropylsulfinyl, 1-ethyl-1 -methylpropylsulfinyl or 1-ethyl-2-methylpropylsulfinyl.
The terms "alkylsulfonyl" and "S(0)n-alkyl" (wherein n is 2) are equivalent and, as used herein, denote an alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "C1-C2- alkylsulfonyl" refers to a Ci-C2-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C4-alkylsulfonyl" refers to a Ci-C4-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. The term "Ci-C6-alkylsulfonyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfonyl [S(0)2] group. Ci-C2-alkylsulfonyl is methylsulfonyl or ethylsulfonyl. Ci-C4-alkylsulfonyl is additionally, for example, n-propylsulfonyl,
1-methylethylsulfonyl (isopropylsulfonyl), butylsulfonyl, 1 -methylpropylsulfonyl (sec- butylsulfonyl), 2-methylpropylsulfonyl (isobutylsulfonyl) or 1 ,1 -dimethylethylsulfonyl (tert- butylsulfonyl). Ci-C6-alkylsulfonyl is additionally, for example, pentylsulfonyl,
1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 1 ,1-dimethylpropylsulfonyl,
1.2- dimethylpropylsulfonyl, 2,2-dimethylpropylsulfonyl, 1 -ethylpropylsulfonyl, hexylsulfonyl, 1- methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl,
1.1- dimethylbutylsulfonyl, 1 ,2-dimethylbutylsulfonyl, 1 ,3-dimethylbutylsulfonyl,
2.2- dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl,
1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1 ,1 ,2-trimethylpropylsulfonyl,
1 ,2,2-trimethylpropylsulfonyl, 1 -ethyl-1 -methylpropylsulfonyl or 1 -ethyl-2-methylpropylsulfonyl. The term "alkylamino" as used herein denotes in each case a group -NHR, wherein R is a straight-chain or branched alkyl group usually having from 1 to 6 carbon atoms ("C1-C6- alkylamino"), preferably 1 to 4 carbon atoms("Ci-C4-alkylamino"). Examples of Ci-C6-alkylamino are methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, 2-butylamino, iso- butylamino, tert-butylamino, and the like.
The term "dialkylamino" as used herein denotes in each case a group-NRR', wherein R and R', independently of each other, are a straight-chain or branched alkyl group each usually having from 1 to 6 carbon atoms ("di-(Ci-C6-alkyl)-amino"), preferably 1 to 4 carbon atoms ("di-(Ci-C4- alkyl)-amino"). Examples of a di-(Ci-C6-alkyl)-amino group are dimethylamino, diethylamino, dipropylamino, dibutylamino, methyl-ethyl-amino, methyl-propyl-amino, methyl-isopropylamino, methyl-butyl-amino, methyl-isobutyl-amino, ethyl-propyl-amino, ethyl-isopropylamino, ethyl- butyl-amino, ethyl-isobutyl-amino, and the like.
The term "cycloalkylamino" as used herein denotes in each case a group -NHR, wherein R is a cycloalkyi group usually having from 3 to 8 carbon atoms ("Ca-Cs-cycloalkylamino"), preferably 3 to 6 carbon atoms("C3-C6-cycloalkylamino"). Examples of C3-C8-cycloalkylamino are cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, and the like.
The term "alkylaminosulfonyl" as used herein denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group. Examples of an alkylaminosulfonyl group are methylaminosulfonyl, ethylaminosulfonyl, n-propylaminosulfonyl, isopropylaminosulfonyl, n-butylaminosulfonyl, 2- butylaminosulfonyl, iso-butylaminosulfonyl, tert-butylaminosulfonyl, and the like.
The term "dialkylaminosulfonyl" as used herein denotes in each case a straight-chain or branched alkylamino group as defined above, which is bound to the remainder of the molecule via a sulfonyl [S(0)2] group. Examples of an dialkylaminosulfonyl group are
dimethylaminosulfonyl, diethylaminosulfonyl, dipropylaminosulfonyl, dibutylaminosulfonyl, methyl-ethyl-aminosulfonyl, methyl-propyl-aminosulfonyl, methyl-isopropylaminosulfonyl, methyl-butyl-aminosulfonyl, methyl-isobutyl-aminosulfonyl, ethyl-propyl-aminosulfonyl, ethyl- isopropylaminosulfonyl, ethyl-butyl-aminosulfonyl, ethyl-isobutyl-aminosulfonyl, and the like. The suffix„-carbonyl" in a group denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C=0 group. This is the case e.g. in alkylcarbonyl,
haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl.
The term "aryl" as used herein refers to a mono-, bi- or tricyclic aromatic hydrocarbon radical such as phenyl or naphthyl, in particular phenyl.
The term "het(ero)aryl" as used herein refers to a mono-, bi- or tricyclic heteroaromatic hydrocarbon radical, preferably to a monocyclic heteroaromatic radical, such as pyridyl, pyrimidyl and the like.
A saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, is a ring system wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system e.g. thiophen, furan, pyrrol, thiazol, oxazol, imidazol, isothiazol, isoxazol, pyrazol, 1 ,3,4-oxadiazol, 1 ,3,4-thiadiazol, 1 ,3,4-triazol, 1 ,2,4-oxadiazol, 1 ,2,4-thiadiazol, 1 ,2,4- triazol, 1 ,2,3-triazol, 1 ,2,3,4-tetrazol, benzo[b]thiophen, benzo[b]furan, indol, benzo[c]thiophen, benzo[c]furan, isoindol, benzoxazol, benzothiazol, benzimidazol, benzisoxazol, benzisothiazol, benzopyrazol, benzothiadiazol, benzotriazol, dibenzofuran, dibenzothiophen, carbazol, pyridin, pyrazin, pyrimidin, pyridazin, 1 ,3,5-triazin, 1 ,2,4-triazin, 1 ,2,4,5-tetrazin, chinolin, isochinolin, chinoxalin, chinazolin, cinnolin, 1 ,8-naphthyridin, 1 ,5-naphthyridin, 1 ,6-naphthyridin, 1 ,7- naphthyridin, phthalazin, pyridopyrimidin, purin, pteridin, 4H-chinolizin, piperidin, pyrrolidin, oxazolin, tetrahydrofuran, tetrahydropyran, isoxazolidin or thiazolidin.
A saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur also is e.g. a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 to 4 heteroatoms selected from oxygen, nitrogen and sulfur, such as pyridine, pyrimidine, (1 ,2,4)-oxadiazole, (1 ,3,4)-oxadiazole, pyrrole, furan, thiophene, oxazole, thiazole, imidazole, pyrazole, isoxazole, 1 ,2,4-triazole, tetrazole, pyrazine, pyridazine, oxazoline, thiazoline, tetrahydrofuran, tetrahydropyran, morpholine, piperidine, piperazine, pyrroline, pyrrolidine, oxazolidine, thiazolidine, oxirane or oxetane ; or
a saturated, partially unsaturated or unsaturated 5-or 6-membered heterocycle which contains 1 nitrogen atom and 0 to 2 further heteroatoms selected from oxygen, nitrogen and sulfur, preferably from oxygen and nitrogen, such as piperidine, piperazin and morpholine.
Preferably, this ring system is a saturated, partially unsaturated or unsaturated 3- to 6- membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein two oxygen atoms must not be in adjacent positions and wherein at least 1 carbon atom must be in the ring system.
Most preferably, this ring system is a radical of pyridine, pyrimidine, (1 ,2,4)-oxadiazol, 1 ,3,4- oxadiazol, pyrrol, furan, thiophen, oxazol, thiazol, imidazol, pyrazol, isoxazol, 1 ,2,4-triazol, tetrazol, pyrazin, pyridazin, oxazolin, thiazolin, tetrahydrofuran, tetrahydropyran, morpholin, piperidin, piperazin, pyrrolin, pyrrolidin, oxazolidin, thiazolidin, oxiran or oxetan.
The compounds according to the invention can be prepared analogously as described in WO 2007/006670, PCT/EP2012/065650 and PCT/EP2012/065651.
The preparation of the compounds of formula I above may lead to them being obtained as isomer mixtures. If desired, these can be resolved by the methods customary for this purpose, such as crystallization or chromatography, also on optically active adsorbate, to give the pure isomers.
Agronomically acceptable salts of the compounds I can be formed in a customary manner, e.g. by reaction with an acid of the anion in question.
Preferences
The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formulae (I), (I-0), (IA), (IB), (IC), (ID), (IA-1 ) are valid on their own as well as preferably in combination with each other, as well as in combination with the stereoisomers, tautomers, N-oxides or salts thereof, and, where applicable, as well as concerning the uses and methods according to the invention and the compositions according to the invention.
Preferred compounds according to the invention are compounds of formulae (I) or (1-1 ) or a stereoisomer, N-oxide or salt thereof, wherein the salt is an agriculturally or veterinarily acceptable salt.
Preferred is a compound of formula I wherein R1 is hydrogen, Ci-C6-alkyl, cyano, C1-C6- alkylsulfonyl, or C2-C6-alkoxycarbonyl, preferably hydrogen or Ci-C4-alkyl, most preferably hydrogen.
Preferred is a compound of formula I wherein R2 and R3 each independently are R6, or R2 and R3 together with the sulfur atom to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, which ring can be fused with one or two saturated, partially unsaturated or unsaturated 5- to 6-membered rings which may contain 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of the above rings are unsubstituted or substituted by any combination of 1 to 6 groups R8.
Even more preferred are compounds of formula I wherein R2 and R3 each independently are R6, preferably hydrogen, Ci-C2o-alkyl, C2-C2o-alkenyl, C2-C2o-alkynyl, Ca-Cs-cycloalkyl, C3-C8- cycloalkenyl, C3-Cs-cycloalkynyl, phenyl, naphthyl, biphenyl, or a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of these groups are unsubstituted or substituted by any combination of 1 to 6 groups R9.
Especially preferred are compounds of formula I wherein R2 and R3 each independently are Ci- Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, C3-Cs-cycloalkyl, or phenyl, wherein these groups are unsubstituted or substituted by any combination of 1 to 6 groups selected from R10 or R11, and R10 is Ci-Cio-alkyl, C3-C8-cycloalkyl, Ci-Cio-alkyl-C3-C8-cycloalkyl or
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein these groups are unsubstituted or substituted with any combination of from 1 to 6 groups R11, and
R11 is halogen, cyano, nitro, hydroxy, mercapto, amino, formyl, Ci-Cio-alkylcarbonyl, C1-C10- alkoxy, C2-Cio-alkenyloxy, C2-Cio-alkynyloxy, Ci-Cio-haloalkoxy, Cs-Ce-cycloalkoxy, C3-C8- halocycloalkoxy, Ci-Cio-alkoxycarbonyl, C3-C8-cycloalkoxycarbonyl, Ci-Cio-alkylcarbonyloxy, C3-Ce-cyclo alkylcarbonyloxy, Ci-Cio-haloalkoxycarbonyl, Ci-Cio-haloalkylcarbonyloxy, C1-C10- alkanamido, Cs-Cs-cycloalkanamido, Ci-Cio-alkylthio, C2-Cio-alkenylthio, C2-Cio-alkynylthio, Ci- Cio-haloalkylthio, C3-C8-cycloalkylthio, Cs-Cs-halocycloalkylthio, C3-C8-cycloalkyl-Ci-C4-alkylthio, CrCio-alkylsulfinyl, C2-Cio-alkenylsulfinyl, C2-Cio-alkynylsulfinyl, Ci-Cio-haloalkylsulfinyl, C3-Ce- cycloalkylsulfinyl, Cs-Cs-halocycloalkenylsulfinyl, C3-C8-cycloalkyl-Ci-C4-alkylsulfinyl, C1-C10- alkylsulfonyl, C2-Cio-alkenylsulfonyl, C2-Cio-alkynylsulfonyl, Ci-Cio-haloalkylsulfonyl, C3-C8- cycloalkylsulfonyl, Cs-Cs-halocycloalkylsulfonyl, C3-C8-cycloalkyl-Ci-C4-alkylsulfonyl, di(Ci-Cio- alkyl)amino, Ci-Cio-alkylamino, C2-Cio-alkenylamino, C2-Cio-alkynylamino, Ci-Cio-alkyl-C2-Cio- alkenylamino, Ci-Cio-alkyl-C2-Cio-alkynylamino, Ci-Cio-haloalkylamino, C2-C10- haloalkenylamino, C3-C8-cycloalkylamino, tri(Ci-Cio-alkyl)silyl, aryl, aryloxy, arylthio, arylamino, wherein aryl is phenyl, naphthyl or biphenyl, or
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur,
wherein these aryl and these heterocyclic ringsystems are unsubstituted or substituted with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, C1-C4- haloalkylthio, di(Ci-C4-alkyl) amino and Ci-C4-alkylamino.
More preferred are compounds of formula I wherein R2 and R3 each independently are C1-C10- alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, Cs-Cs-cycloalkyl, or phenyl, wherein these groups are unsubstituted or substituted by any combination of 1 to 6 groups selected from R11, and R11 is halogen, cyano, nitro, hydroxy, mercapto, amino, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, C3-C8- cycloalkoxy, Ci-Cio-alkoxycarbonyl, Ci-Cio-alkylcarbonyloxy, Ci-Cio-alkanamido, C1-C10- alkylthio, Ci-Cio-alkylsulfinyl, Ci-Cio-alkylsulfonyl, di(Ci-Cio-alkyl)amino or Ci-Oo-alkylamino. Preferred are also compounds of formula I wherein R2 and R3 together with the sulfur atom to which they are attached form a 5- or 6-membered heterocycle which besides the sulfur atom contains 1 nitrogen or 1 oxygen atom, wherein these groups are unsubstituted or substituted by any combination of 1 to 6 groups selected from with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, di(Ci-C4-alkyl) amino and Ci- C4-alkylamino.
Preferred are also compounds of formula I wherein R2 and R3 together with the sulfur atom to which they are attached form a unit SR2R3 of the following formula:
Figure imgf000020_0001
wherein
r is 0 or 1 ;
D is a direct bond, branched or straight Ci-C4-alkylene, O, S(0)o,i,2 or NR, preferably CH2, O, or N R;
R9 is as defined above for compounds of formula I;
Rj is hydrogen, CrC4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-alkoxycarbonyl, C1-C4- alkylaminocarbonyl, di(Ci-C4-alkyl)aminocarbonyl, or Ci-C4-alkylsulfonyl;
a,b are the same or different 0, 1 , 2, 3 or 4, preferably 0, 1 , or 2.
When r = 0 then the both arylgroups are unbridged.
Preferred are compounds of formula I wherein R9 is R10, R11, or -C(=0)R1°, -C(=NOR10)R10, - C(=NNR1°2)R10 , -C(=0)OR10, -C(=O)NR10 2, -C(=O)NR10-NR10 2, -C(=O)NR10-NR 0[C(=O)R10], - SO2NR 02, -OR10, -NR1°2, or -SR10. Preferred are compounds of formula I wherein Q1 is hydrogen, halogen, cyano, SCN, nitro, hydroxy, CrCio-alkyl, Ci-Cio-haloalkyl, Cs-Cs-cycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci- Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfonyl, Ci-Cio-alkylsulfonyloxy, C1-C10- alkylamino or di(Ci-Cio-alkyl)amino, most preferably hydrogen, halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl.
Preferred are compounds of formula I wherein Q2 is halogen, cyano, SCN , nitro, hydroxy, Cr Cio-alkyl, Ci-Cio-haloalkyl, Ca-Cs-cycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, Ci-Cio-alkylsulfonyl, Ci-Cio-alkylsulfonyloxy, Ci-Cio-alkylamino or di(Ci- Cio-alkyl)amino, most preferably halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl.
Preferred are compounds of formula I wherein Q3 is halogen, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2- Cio-alkynyl, Cs-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, each unsubstituted or independently substituted with 1 to 2 groups selected from cyano, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy or C1-C10- alkylthio, or
Q3 is OR14, S(0)qR14, NR15R16, OS(0)2R17, C(S)NH2, C(R18)=NOR18; and
R14 is Ci-Cio-alkyl or Ca-Ce-cycloalkyl unsubstituted or substituted with 1 R19; and
R15 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, each unsubstituted or substituted with 1 R19; and
R16 is hydrogen, CrCio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, each
unsubstituted or substituted with 1 R19; and
R17 is Ci-Cio-alkyl, Ci-Cio-haloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, Ca-Ce-cycloalkyl, each unsubstituted or substituted with 1 R19; and
R18 is hydrogen, Ci-Cio-alkyl, or Ci-Cio-haloalkyl; and
R19 is cyano, nitro, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, or Ci-Cio-haloalkylthio.
Most preferred are compounds of formula I wherein Q3 is halogen, Ci-C4-haloalkyl or C1-C4- haloalkoxy.
Preferred are compounds of formula I wherein Q4 is halogen, cyano, nitro, Ci-Cio-alkyl, C1-C10- haloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, Ci-Cio-alkylthio, Ci-Cio-haloalkylthio, C1-C10- alkylsulfinyl, CrCio-haloalkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Cio-haloalkylsulfonyl, or Ci-Cio- alkoxycarbonyl, preferably halogen or Ci-C4-haloalkyl.
Preferred are compounds of formula I wherein X and Y are oxygen.
Preferred are compounds of formula I wherein W is N or CQ4, preferably N.
Preferred are compounds of formula I wherein n is 0.
Preferred are compounds of formula I wherein V and V each independently are N or CH.
Preferably, both V and V are CH.
Especially preferred are N-thio-anthranilamid compounds of formula I wherein
W is N;
R1 is hydrogen;
Q1 is hydrogen, halogen, cyano, Ci-C4-alkyl or Ci-C4-haloalkyl;
Q2 is halogen, cyano, CrC4-alkyl or Ci-C4-haloalkyl;
Q3 is halogen, Ci-C4-haloalkyl or Ci-C4-haloalkoxy;
Q4 is halogen or Ci-C4-haloalkyl and is in the ortho-position; and
p is 1 . Also, especially preferred are N-thio-anthranilamid compounds of formula I wherein
R2 and R3 each independently are phenyl, Ci-C6-alkyl, C2-C6-alkenyl, or C2-C6-alkynyl, which are unsubstituted or substituted with any combination of 1 to 6 groups selected from halogen and cyano. Most preferred are compounds of formula I wherein R2 and R3 each independently are C1-C4- alkyl, phenylmethyl, allylmethyl, propargylmethyl, or together with the sulfur atom to which they are attached form a 3- to 6-membered saturated ring which contains 1 to 3 heteroatoms selected from sulfur and oxygen.
In a particular embodiment, the compound I of formula (I) is a compound of formula (I-0)
Figure imgf000022_0001
wherein
Q2 is selected from the group consisting of halogen, methyl and halomethyl;
Q1 is selected from the group consisting of hydrogen, halogen, halomethyl and cyano;
R1 is selected from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkinyl, C2-C6-haloalkinyl, C3-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl,
C(=0)Ra, C(=0)ORb and C(=0)NRcRd;
Q4 is hydrogen or halogen;
R2, R3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, Ca-Ce-cycloalkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents Re, and phenyl, which is unsubstituted or carries 1 to 5 substituents Rf; or
R2 and R3 together represent a C2-C7-alkylene, C2-C7-alkenylene or
C6-Cg-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C7-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-Cg-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH, and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C7-alkenylene or C6-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, Ca-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present; is selected from the group consisting of bromo, chloro, difluoromethyl,
trifluoromethyl, nitro, cyano, OCH3, OCHF2, OCH2F, OCH2CF3, S(=0)mCH3, and S(=0)mCF3; is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3- Ce-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from C1-C4 alkoxy;
phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, (C1-C6- alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino, is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3- Ce-cycloalkyl, Ci-C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from Ci-C4-alkoxy;
phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy and (O- C6-alkoxy)carbonyl; d are, independently from one another and independently of each occurrence, selected from the group consisting of hydrogen, cyano, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Ca-Cs-cycloalkyl, wherein one or more CH2 groups of the
aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4- alkoxy; Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy, C1-C6 haloalkoxy and (Ci-C6-alkoxy)carbonyl; or
Rc and Rd, together with the nitrogen atom to which they are bound, may form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring which may additionally contain 1 or 2 further heteroatoms or heteroatom groups selected from N , O, S, NO, SO and SO2, as ring members, where the heterocyclic ring may optionally be substituted with halogen, C1-C4- haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy; is independently selected from the group consisting of halogen, cyano, nitro, -OH , - SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-Cs-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, -ORa, -N RcRd, -S(0)mRa, -S(0)mN RcRd,
-C(=0)Ra, -C(=0)NRcRd, -C(=0)ORb, -C(=S)Ra, -C(=S)NRcRd, -C(=S)ORb,
-C(=S)SRb, -C(=NRc)Rb, -C(=NRc)N RcRd, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C1-C6- alkoxy and Ci-C6-haloalkoxy; or
two vicinal radicals Re together form a group =0, =CH(Ci-C4-alkyl), =C(Ci-C4- alkyl)Ci-C4-alkyl,
Figure imgf000024_0001
or =NO(Ci-C6-alkyl); is independently selected from the group consisting of halogen, cyano, nitro, -OH , - SH , -SCN , Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, Cs-Ce-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, C1-C6- alkylsulfonyl, Ci-C6-haloalkylthio, -ORa, -N RcR , -S(0)mRa, -S(0)mN RcRd,
-C(=0)Ra, -C(=0)NRcRd, -C(=0)OR , -C(=S)Ra, -C(=S)NRcRd, -C(=S)OR ,
-C(=S)SRb, -C(=NRc)Rb, and -C(=N Rc)NRcRd; is 0 or 1 ; is 0, 1 or 2. Preferred are compounds of formula (I), wherein the compound of formula I is a compound of formula IA:
Figure imgf000025_0001
wherein
Q4 is halogen, and
wherein the variables Q2, Q1, Q3, R2, R3 and n are as defined herein.
Preferred are compounds of formula (I), in which the compound of formula I is a compound of formula IB:
Figure imgf000025_0002
wherein
Q1 is selected from the group consisting of bromo, chloro, cyano;
Q3 is selected from the group consisting of bromo, chloro, trifluoromethyl. OCHF2, and wherein the variables Q1, Q3, R2, R3 and n are as defined herein. Preferred are compounds of formula (I), in which the compound of formula I is a compound of formula IC:
Figure imgf000026_0001
wherein
Q2 is selected from the group consisting of halogen and halomethyl;
Q1 is selected from the group consisting of bromo, chloro and cyano, and
wherein the variables R2, R3 and n are as defined herein. Preferred are compounds of formula (I), in which the compound of formula I is a compound of formula I D:
Figure imgf000026_0002
wherein
Q2 is selected from the group consisting of halogen, methyl and halomethyl;
Q1 is selected from the group consisting of bromo, chloro and cyano, and
wherein the variables R2, R3 and n are as defined herein.
Preferred are compounds of formula (I), in which R2, R3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, C3-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents
Re; or
R2 and R3 together represent a C2-C7-alkylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7- or 8- membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the Chb groups in the C2-C7-alkylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, SO2 and NH, and wherein the carbon and/or nitrogen atoms in the C2-C7-alkylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cyano, Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci- C6-alkylthio, Ci-C6-haloalkylthio, Cs-Cs-cycloalkyl, C3-Cs-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present.
Preferred are compounds of formula (I), in which R2, R3 are selected independently of one another from the group consisting of hydrogen, Ci-Cio-alkyl, C3-Cs-cycloalkyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents Re.
Preferred are compounds of formula (I), in which Q3 is selected from the group consisting of bromo, difluoromethyl, trifluoromethyl, cyano, OCH F2, OCH2F and OCH2CF3,
Preferred are compounds of formula (I), in which Q3 is selected from the group consisting of bromo, difluoromethyl, trifluoromethyl and OCH F2. Preferred are compounds of formula (I), in which Re is independently selected from the group consisting of halogen, cyano, -OH, -SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8- cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from Ci-C6-alkoxy, Ci-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6-alkylsulfonyl, Ci- Ce-haloalkylthio, -ORa, -NRcRd, -S(0)mRa, -S(0)mNRcRd,
-C(=0)Ra, -C(=0)NRcRd, -C(=0)ORb, -C(=S)Ra, -C(=S)NRcRd, -C(=S)ORb,
-C(=S)SRb, -C(=NRc)Rb, -C(=NRc)NRcRd, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from Ci-C6-alkyl, 0-C6-haloalkyl, Ci-C6-alkoxy and Ci-C6-haloalkoxy.
Preferred are compounds of formula (I), in which Re is independently selected from the group consisting of halogen, cyano, -OH, -SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8- cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated.
Preferred are compounds of formula (I) as described herein, in which in the compound of formula I R2 and R3 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl.
Preferred are compounds of formula (I) as described herein, in which in the compound of formula I
R2 and R3 are identical.
In a particularly preferred embodiment, the compounds according to the invention comprise least one compound of form
Figure imgf000028_0001
wherein
Q4 is CI,
Q2 is selected from the group consisting of CI, Br, and methyl;
Q1 is selected from the group consisting of bromo and chloro;
R2, R3 are selected independently of one another from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl.
Q3 is selected from the group consisting of difluoromethyl, trifluoromethyl.
Examples of especially preferred anthranilamide compounds I of the present invention are of formula (IA-1 )
(IA-1 )
Figure imgf000028_0002
wherein Q2, Q1, Q3, 2, R3 are as defined herein.
Examples of preferred compounds of formula I as compounds I or in mixtures according to the invention are compiled in tables 1 to 60 below. Moreover, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodiment of the substituents in question.
Table 1 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is CI, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 2 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is CI, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 3 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is CI, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 4 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is CI, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 5 Compounds of the formula (IA-1 ) in which Q2 is F, Q is Br, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 6 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is Br, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 7 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is Br, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 8 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is Br, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 9 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is cyano, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 10 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is cyano, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 1 1 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is cyano, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 12 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is cyano, Q3 is CF3 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 13 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is CI, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 14 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is CI, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 15 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is CI, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 16 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is CI, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 17 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is Br, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 18 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is Br, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 19 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is Br, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 20 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is Br, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 21 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is cyano, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 22 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is cyano, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 23 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is cyano, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 24 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is cyano, Q3 is CHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 25 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is CI, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 26 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is CI, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 27 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is CI, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 28 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is CI, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 29 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is Br, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 30 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is Br, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 31 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is Br, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 32 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is Br, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 33 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is cyano, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 34 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is cyano, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 35 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is cyano, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 36 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is cyano, Q3 is Br and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 37 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is CI, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 38 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is CI, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 39 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is CI, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 40 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is CI, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 41 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is Br, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 42 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is Br, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 43 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is Br, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 44 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is Br, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 45 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is cyano, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 46 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is cyano, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 47 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is cyano, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 48 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is cyano, Q3 is CI and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 49 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is CI, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 50 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is CI, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 51 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is CI, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A;
Table 52 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is CI, Q3 is OCH F2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 53 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is Br, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 54 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is Br, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 55 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is Br, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 56 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is Br, Q3 is OCH F2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A;
Table 57 Compounds of the formula (IA-1 ) in which Q2 is F, Q1 is cyano, Q3 is OCHF2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 58 Compounds of the formula (IA-1 ) in which Q2 is Br, Q1 is cyano, Q3 is OCH F2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 59 Compounds of the formula (IA-1 ) in which Q2 is CI, Q1 is cyano, Q3 is OCH F2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A; Table 60 Compounds of the formula (IA-1 ) in which Q2 is methyl, Q1 is cyano, Q3 is OCH F2 and the combination of R2 and R3 for a compound corresponds in each case to one row of Table A.
Table A
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
R2 R3 R2 R3
A- 175 C&H5 C(CH3)3 A-217 C-C3H5 CH(CH3)CH2CH3
A- 176 CH3 CH2CH(CH3)2 A-218 C-C4H7 CH(CH3)CH2CH3
A- 177 C2H5 CH2CH(CH3)2 A-219 C-C5H9 CH(CH3)CH2CH3
A- 178 CH=CH2 CH2CH(CH3)2 A-220 c-C6Hii CH(CH3)CH2CH3
A- 179 CH2CH2CH3 CH2CH(CH3)2 A-221 CH2-C-C3H5 CH(CH3)CH2CH3
A- 180 CH(CH3)2 CH2CH(CH3)2 A-222 CH(CH3)-c-C3H5 CH(CH3)CH2CH3
A-181 CH2CH2CH2CH3 CH2CH(CH3)2 A-223 CH2-C-C5H9 CH(CH3)CH2CH3
A- 182 C(CH3)3 CH2CH(CH3)2 A-224 CH2-C-C6H1 1 CH(CH3)CH2CH3
A- 183 CH2CH(CH3)2 CH2CH(CH3)2 A-225 C6H5 CH(CH3)CH2CH3
A- 184 CH(CH3)CH2CH3 CH2CH(CH3)2 A-226 CH3 CH2CH=CH2
A- 185 CH2CH=CH2 CH2CH(CH3)2 A-227 C2H5 CH2CH=CH2
A- 186 CH2C≡CH CH2CH(CH3)2 A-228 CH=CH2 CH2CH=CH2
A- 187 CH(CH3)CH=CH2 CH2CH(CH3)2 A-229 CH2CH2CH3 CH2CH=CH2
A- 188 CHF2 CH2CH(CH3)2 A-230 CH(CH3)2 CH2CH=CH2
A- 189 CH2CI CH2CH(CH3)2 A-231 CH2CH2CH2CH3 CH2CH=CH2
A-190 CH2CH2CN CH2CH(CH3)2 A-232 C(CH3)3 CH2CH=CH2
A-191 CH2CH2CI CH2CH(CH3)2 A-233 CH2CH(CH3)2 CH2CH=CH2
A- 192 c-C3H5 CH2CH(CH3)2 A-234 CH(CH3)CH2CH3 CH2CH=CH2
A-193 C-C4H7 CH2CH(CH3)2 A-235 CH2CH=CH2 CH2CH=CH2
A- 194 C-C5H9 CH2CH(CH3)2 A-236 CH2C≡CH CH2CH=CH2
A-195 c-C6Hii CH2CH(CH3)2 A-237 CH(CH3)CH=CH2 CH2CH=CH2
A-196 CH2-c-C3H5 CH2CH(CH3)2 A-238 CHF2 CH2CH=CH2
A-197 CH(CH3)-c-C3H5 CH2CH(CH3)2 A-239 CH2CI CH2CH=CH2
A-198 CH2-C-C5H9 CH2CH(CH3)2 A-240 CH2CH2CN CH2CH=CH2
A-199 CH2-C-C6H11 CH2CH(CH3)2 A-241 CH2CH2CI CH2CH=CH2
A-200 C6H5 CH2CH(CH3)2 A-242 c-C3H5 CH2CH=CH2
A-201 CH3 CH(CH3)CH2CH3 A-243 C-C4H7 CH2CH=CH2
A-202 C2H5 CH(CH3)CH2CH3 A-244 C-C5H9 CH2CH=CH2
A-203 CH=CH2 CH(CH3)CH2CH3 A-245 c-CeHu CH2CH=CH2
A-204 CH2CH2CH3 CH(CH3)CH2CH3 A-246 CH2-c-C3H5 CH2CH=CH2
A-205 CH(CH3)2 CH(CH3)CH2CH3 A-247 CH(CH3)-c-C3H5 CH2CH=CH2
A-206 CH2CH2CH2CH3 CH(CH3)CH2CH3 A-248 CH2-C-C5Hg CH2CH=CH2
A-207 C(CH3)3 CH(CH3)CH2CH3 A-249 CH2-c-C6Hi 1 CH2CH=CH2
A-208 CH2CH(CH3)2 CH(CH3)CH2CH3 A-250 C6H5 CH2CH=CH2
A-209 CH(CH3)CH2CH3 CH(CH3)CH2CH3 A-251 CH3 CH2C≡CH
A-210 CH2CH=CH2 CH(CH3)CH2CH3 A-252 C2H5 CH2C≡CH
A-21 1 CH2C≡CH CH(CH3)CH2CH3 A-253 CH=CH2 CH2C≡CH
A-212 CH(CH3)CH=CH2 CH(CH3)CH2CH3 A-254 CH2CH2CH3 CH2C≡CH
A-213 CHF2 CH(CH3)CH2CH3 A-255 CH(CH3)2 CH2C≡CH
A-214 CH2CI CH(CH3)CH2CH3 A-256 CH2CH2CH2CH3 CH2C≡CH
A-215 CH2CH2CN CH(CH3)CH2CH3 A-257 C(CH3)3 CH2C≡CH
A-216 CH2CH2CI CH(CH3)CH2CH3 A-258 CH2CH(CH3)2 CH2C≡CH R2 R3 R2 R3
A-259 CH(CH3)CH2CH3 CH2C≡CH A-301 CH3 CHF2
A-260 CH2CH=CH2 CH2C≡CH A-302 C2H5 CHF2
A-261 CH2C≡CH CH2C≡CH A-303 CH=CH2 CHF2
A-262 CH(CH3)CH=CH2 CH2C≡CH A-304 CH2CH2CH3 CHF2
A-263 CHF2 CH2C≡CH A-305 CH(CH3)2 CHF2
A-264 CH2CI CH2C≡CH A-306 CH2CH2CH2CH3 CHF2
A-265 CH2CH2CN CH2C≡CH A-307 C(CH3)3 CHF2
A-266 CH2CH2CI CH2C≡CH A-308 CH2CH(CH3)2 CHF2
A-267 C-C3H5 CH2C≡CH A-309 CH(CH3)CH2CH3 CHF2
A-268 C-C4H7 CH2C≡CH A-310 CH2CH=CH2 CHF2
A-269 C-C5H9 CH2C≡CH A-31 1 CH2C≡CH CHF2
A-270 c-C6Hii CH2C≡CH A-312 CH(CH3)CH=CH2 CHF2
A-271 CH2-c-C3H5 CH2C≡CH A-313 CHF2 CHF2
A-272 CH(CH3)-c-C3H5 CH2C≡CH A-314 CH2CI CHF2
A-273 CH2-C-C5Hg CH2C≡CH A-315 CH2CH2CN CHF2
A-274 CH2-c-C6Hii CH2C≡CH A-316 CH2CH2CI CHF2
A-275 C6H5 CH2C≡CH A-317 c-C3H5 CHF2
A-276 CH3 CH(CH3)CH=CH2 A-318 C-C4H7 CHF2
A-277 C2H5 CH(CH3)CH=CH2 A-319 C-C5H9 CHF2
A-278 CH=CH2 CH(CH3)CH=CH2 A-320 c-CeHu CHF2
A-279 CH2CH2CH3 CH(CH3)CH=CH2 A-321 CH2-c-C3H5 CHF2
A-280 CH(CH3)2 CH(CH3)CH=CH2 A-322 CH(CH3)-c-C3H5 CHF2
A-281 CH2CH2CH2CH3 CH(CH3)CH=CH2 A-323 CH2-c-C5H9 CHF2
A-282 C(CH3)3 CH(CH3)CH=CH2 A-324 CH2-c-C6Hi 1 CHF2
A-283 CH2CH(CH3)2 CH(CH3)CH=CH2 A-325 C6H5 CHF2
A-284 CH(CH3)CH2CH3 CH(CH3)CH=CH2 A-326 CH3 CH2CI
A-285 CH2CH=CH2 CH(CH3)CH=CH2 A-327 C2H5 CH2CI
A-286 CH2C≡CH CH(CH3)CH=CH2 A-328 CH=CH2 CH2CI
A-287 CH(CH3)CH=CH2 CH(CH3)CH=CH2 A-329 CH2CH2CH3 CH2CI
A-288 CHF2 CH(CH3)CH=CH2 A-330 CH(CH3)2 CH2CI
A-289 CH2CI CH(CH3)CH=CH2 A-331 CH2CH2CH2CH3 CH2CI
A-290 CH2CH2CN CH(CH3)CH=CH2 A-332 C(CH3)3 CH2CI
A-291 CH2CH2CI CH(CH3)CH=CH2 A-333 CH2CH(CH3)2 CH2CI
A-292 C-C3H5 CH(CH3)CH=CH2 A-334 CH(CH3)CH2CH3 CH2CI
A-293 C-C4H7 CH(CH3)CH=CH2 A-335 CH2CH=CH2 CH2CI
A-294 C-C5H9 CH(CH3)CH=CH2 A-336 CH2C≡CH CH2CI
A-295 c-CeHu CH(CH3)CH=CH2 A-337 CH(CH3)CH=CH2 CH2CI
A-296 CH2-c-C3H5 CH(CH3)CH=CH2 A-338 CHF2 CH2CI
A-297 CH(CH3)-c-C3H5 CH(CH3)CH=CH2 A-339 CH2CI CH2CI
A-298 Chb-C-CsHg CH(CH3)CH=CH2 A-340 CH2CH2CN CH2CI
A-299 Chb-C-CsHg CH(CH3)CH=CH2 A-341 CH2CH2CI CH2CI
A-300 C6H5 CH(CH3)CH=CH2 A-342 C-C3H5 CH2CI R2 R3 R2 R3
A-343 C-C4H7 CH2CI A-385 CH2CH=CH2 CH2CH2CI
A-344 C-C5H9 CH2CI A-386 CH2C≡CH CH2CH2CI
A-345 c-CeHu CH2CI A-387 CH(CH3)CH=CH2 CH2CH2CI
A-346 CH2-c-C3H5 CH2CI A-388 CHF2 CH2CH2CI
A-347 CH(CH3)-c-C3H5 CH2CI A-389 CH2CI CH2CH2CI
A-348 CH2-C-C5H9 CH2CI A-390 CH2CH2CN CH2CH2CI
A-349 CH2-C-C6H11 CH2CI A-391 CH2CH2CI CH2CH2CI
A-350 C6H5 CH2CI A-392 C-C3H5 CH2CH2CI
A-351 CH3 CH2CH2CN A-393 C-C4H7 CH2CH2CI
A-352 C2H5 CH2CH2CN A-394 C-C5H9 CH2CH2CI
A-353 CH=CH2 CH2CH2CN A-395 c-CeHu CH2CH2CI
A-354 CH2CH2CH3 CH2CH2CN A-396 CH2-C-C3H5 CH2CH2CI
A-355 CH(CH3)2 CH2CH2CN A-397 CH(CH3)-c-C3H5 CH2CH2CI
A-356 CH2CH2CH2CH3 CH2CH2CN A-398 CH2-C-C5H9 CH2CH2CI
A-357 C(CH3)3 CH2CH2CN A-399 CH2-C-C6H11 CH2CH2CI
A-358 CH2CH(CH3)2 CH2CH2CN A-400 C6H5 CH2CH2CI
A-359 CH(CH3)CH2CH3 CH2CH2CN A-401 CH3 C-C3H5
A-360 CH2CH=CH2 CH2CH2CN A-402 C2H5 C-C3H5
A-361 CH2OCH CH2CH2CN A-403 CH=CH2 C-C3H5
A-362 CH(CH3)CH=CH2 CH2CH2CN A-404 CH2CH2CH3 C-C3H5
A-363 CHF2 CH2CH2CN A-405 CH(CH3)2 C-C3H5
A-364 CH2CI CH2CH2CN A-406 CH2CH2CH2CH3 C-C3H5
A-365 CH2CH2CN CH2CH2CN A-407 C(CH3)3 C-C3H5
A-366 CH2CH2CI CH2CH2CN A-408 CH2CH(CH3)2 C-C3H5
A-367 C-C3H5 CH2CH2CN A-409 CH(CH3)CH2CH3 C-C3H5
A-368 C-C4H7 CH2CH2CN A-410 CH2CH=CH2 C-C3H5
A-369 C-C5H9 CH2CH2CN A-41 1 CH2C≡CH C-C3H5
A-370 c-CeHu CH2CH2CN A-412 CH(CH3)CH=CH2 C-C3H5
A-371 CH2-C-C3H5 CH2CH2CN A-413 CHF2 C-C3H5
A-372 CH(CH3)-c-C3H5 CH2CH2CN A-414 CH2CI C-C3H5
A-373 CH2-C-C5H9 CH2CH2CN A-415 CH2CH2CN C-C3H5
A-374 CH2-C-C5H9 CH2CH2CN A-416 CH2CH2CI C-C3H5
A-375 CsH5 CH2CH2CN A-417 C-C3H5 C-C3H5
A-376 CH3 CH2CH2CI A-418 C-C4H7 C-C3H5
A-377 C2H5 CH2CH2CI A-419 C-C5H9 C-C3H5
A-378 CH=CH2 CH2CH2CI A-420 C-CeHu C-C3H5
A-379 CH2CH2CH3 CH2CH2CI A-421 CH2-C-C3H5 C-C3H5
A-380 CH(CH3)2 CH2CH2CI A-422 CH(CH3)-c-C3H5 C-C3H5
A-381 CH2CH2CH2CH3 CH2CH2CI A-423 CH2-C-C5H9 C-C3H5
A-382 C(CH3)3 CH2CH2CI A-424 CH2-C-C6H11 C-C3H5
A-383 CH2CH(CH3)2 CH2CH2CI A-425 C6H5 C-C3H5
A-384 CH(CH3)CH2CH3 CH2CH2CI A-426 CH3 C-C4H7 R2 R3 R2 R3
A-427 C2H5 C-C4H7 A-469 C-C5H9 C-C5H9
A-428 CH=CH2 C-C4H7 A-470 c-C6Hii C-C5H9
A-429 CH2CH2CH3 C-C4H7 A-471 CH2-C-C3H5 C-C5H9
A-430 CH(CH3)2 C-C4H7 A-472 CH(CH3)-C-C3H5 C-C5H9
A-431 CH2CH2CH2CH3 C-C4H7 A-473 CH2-C-C5H9 C-C5H9
A-432 C(CH3)3 C-C4H7 A-474 CH2-C-C6H1 1 C-C5H9
A-433 CH2CH(CH3)2 C-C4H7 A-475 C6H5 C-C5H9
A-434 CH(CH3)CH2CH3 C-C4H7 A-476 CH3 c-C6Hii
A-435 CH2CH=CH2 C-C4H7 A-477 C2H5 c-C6Hii
A-436 CH2C≡CH C-C4H7 A-478 CH=CH2 c-C6Hii
A-437 CH(CH3)CH=CH2 C-C4H7 A-479 CH2CH2CH3 c-C6Hii
A-438 CHF2 C-C4H7 A-480 CH(CH3)2 c-C6Hii
A-439 CH2CI C-C4H7 A-481 CH2CH2CH2CH3 c-C6Hii
A-440 CH2CH2CN C-C4H7 A-482 C(CH3)3 c-C6Hii
A-441 CH2CH2CI C-C4H7 A-483 CH2CH(CH3)2 c-C6Hii
A-442 C-C3H5 C-C4H7 A-484 CH(CH3)CH2CH3 c-C6Hii
A-443 C-C4H7 C-C4H7 A-485 CH2CH=CH2 c-C6Hii
A-444 c-C5H9 C-C4H7 A-486 CH2C≡CH c-C6Hii
A-445 c-C6Hii C-C4H7 A-487 CH(CH3)CH=CH2 c-C6Hii
A-446 CH2-c-C3H5 C-C4H7 A-488 CHF2 c-C6Hii
A-447 CH(CH3)-c-C3H5 C-C4H7 A-489 CH2CI c-C6Hii
A-448 CH2-C-C5H9 C-C4H7 A-490 CH2CH2CN c-C6Hii
A-449 CH2-C-C6H11 C-C4H7 A-491 CH2CH2CI c-C6Hii
A-450 C6H5 C-C4H7 A-492 C-C3H5 c-C6Hii
A-451 CH3 C-C5H9 A-493 C-C4H7 c-C6Hii
A-452 C2H5 C-C5H9 A-494 C-C5H9 c-C6Hii
A-453 CH=CH2 C-C5H9 A-495 c-C6Hii c-C6Hii
A-454 CH2CH2CH3 C-C5H9 A-496 CH2-c-C3H5 c-C6Hii
A-455 CH(CH3)2 C-C5H9 A-497 CH(CH3)-c-C3H5 c-CeHu
A-456 CH2CH2CH2CH3 C-C5H9 A-498 CH2-C-C5H9 c-C6Hii
A-457 C(CH3)3 C-C5H9 A-499 CH2-C-C6H1 1 C-CeHu
A-458 CH2CH(CH3)2 C-C5H9 A-500 C6H5 C-CeHu
A-459 CH(CH3)CH2CH3 C-C5H9 A-501 CH3 CH2-C-C3H5
A-460 CH2CH=CH2 C-C5H9 A-502 C2H5 CH2-c-C3H5
A-461 CH2C≡CH C-C5H9 A-503 CH=CH2 CH2-c-C3H5
A-462 CH(CH3)CH=CH2 C-C5H9 A-504 CH2CH2CH3 CH2-c-C3H5
A-463 CHF2 C-C5H9 A-505 CH(CH3)2 CH2-c-C3H5
A-464 CH2CI C-C5H9 A-506 CH2CH2CH2CH3 CH2-C-C3H5
A-465 CH2CH2CN C-C5H9 A-507 C(CH3)3 CH2-c-C3H5
A-466 CH2CH2CI C-C5H9 A-508 CH2CH(CH3)2 CH2-C-C3H5
A-467 C-C3H5 C-C5H9 A-509 CH(CH3)CH2CH3 CH2-c-C3H5
A-468 C-C4H7 C-C5H9 A-510 CH2CH=CH2 CH2-c-C3H5 R2 R3 R2 R3
A-51 1 CH2C≡CH CH2-c-C3H5 A-553 CH=CH2 CH2-C-C5Hg
A-512 CH(CH3)CH=CH2 CH2-c-C3H5 A-554 CH2CH2CH3 CH2-C-C5H9
A-513 CHF2 CH2-c-C3H5 A-555 CH(CH3)2 CH2-C-C5H9
A-514 CH2CI CH2-c-C3H5 A-556 CH2CH2CH2CH3 CH2-C-C5H9
A-515 CH2CH2CN CH2-c-C3H5 A-557 C(CH3)3 CH2-C-C5H9
A-516 CH2CH2CI CH2-c-C3H5 A-558 CH2CH(CH3)2 CH2-C-C5H9
A-517 C-C3H5 CH2-c-C3H5 A-559 CH(CH3)CH2CH3 CH2-C-C5H9
A-518 C-C4H7 CH2-c-C3H5 A-560 CH2CH=CH2 CH2-C-C5H9
A-519 C-C5H9 CH2-c-C3H5 A-561 CH2C≡CH CH2-C-C5H9
A-520 c-C6Hii CH2-c-C3H5 A-562 CH(CH3)CH=CH2 CH2-C-C5H9
A-521 CH2-C-C3H5 CH2-c-C3H5 A-563 CHF2 CH2-C-C5H9
A-522 CH(CH3)-c-C3H5 CH2-c-C3H5 A-564 CH2CI CH2-C-C5H9
A-523 CH2-C-C5H9 CH2-c-C3H5 A-565 CH2CH2CN CH2-C-C5H9
A-524 CH2-0C6H11 CH2-c-C3H5 A-566 CH2CH2CI CH2-C-C5H9
A-525 C6H5 CH2-c-C3H5 A-567 c-C3H5 CH2-C-C5H9
A-526 CH3 CH(CH3)-c-C3H5 A-568 C-C4H7 CH2-C-C5H9
A-527 C2H5 CH(CH3)-c-C3H5 A-569 C-C5H9 CH2-C-C5H9
A-528 CH=CH2 CH(CH3)-c-C3H5 A-570 c-CeHu Ch -c-CsHg
A-529 CH2CH2CH3 CH(CH3)-c-C3H5 A-571 CH2-c-C3H5 CH2-C-C5H9
A-530 CH(CH3)2 CH(CH3)-c-C3H5 A-572 CH(CH3)-c-C3H5 CH2-C-C5H9
A-531 CH2CH2CH2CH3 CH(CH3)-c-C3H5 A-573 CH2-c-C5H9 CH2-C-C5H9
A-532 C(CH3)3 CH(CH3)-c-C3H5 A-574 CH2-c-C6Hi 1 CH2-C-C5Hg
A-533 CH2CH(CH3)2 CH(CH3)-c-C3H5 A-575 C6H5 CH2-C-C5H9
A-534 CH(CH3)CH2CH3 CH(CH3)-c-C3H5 A-576 CH3 CH2-C-C6H11
A-535 CH2CH=CH2 CH(CH3)-c-C3H5 A-577 C2H5 CH2-C-C6H11
A-536 CH2C≡CH CH(CH3)-c-C3H5 A-578 CH=CH2 CH2-C-C6H11
A-537 CH(CH3)CH=CH2 CH(CH3)-c-C3H5 A-579 CH2CH2CH3 CH2-C-C6H11
A-538 CHF2 CH(CH3)-c-C3H5 A-580 CH(CH3)2 CH2-C-C6H11
A-539 CH2CI CH(CH3)-c-C3H5 A-581 CH2CH2CH2CH3 CH2-C-C6H11
A-540 CH2CH2CN CH(CH3)-c-C3H5 A-582 C(CH3)3 CH2-C-C6H11
A-541 CH2CH2CI CH(CH3)-c-C3H5 A-583 CH2CH(CH3)2 CH2-C-C6H11
A-542 c-C3H5 CH(CH3)-c-C3H5 A-584 CH(CH3)CH2CH3 CH2-C-C6H11
A-543 C-C4H7 CH(CH3)-c-C3H5 A-585 CH2CH=CH2 CH2-C-C6H11
A-544 C-C5H9 CH(CH3)-c-C3H5 A-586 CH2C≡CH CH2-C-C6H11
A-545 c-CeHu CH(CH3)-c-C3H5 A-587 CH(CH3)CH=CH2 CH2-C-C6H11
A-546 CH2-C-C3H5 CH(CH3)-c-C3H5 A-588 CHF2 CH2-C-C6H11
A-547 CH(CH3)-c-C3H5 CH(CH3)-c-C3H5 A-589 CH2CI CH2-C-C6H11
A-548 CH2-C-C5H9 CH(CH3)-c-C3H5 A-590 CH2CH2CN CH2-C-C6H11
A-549 CH2-C-C6H11 CH(CH3)-c-C3H5 A-591 CH2CH2CI CH2-C-C6H11
A-550 C6H5 CH(CH3)-c-C3H5 A-592 C-C3H5 CH2-C-C6H11
A-551 CH3 CH2-c-C5H9 A-593 C-C4H7 CH2-C-C6H11
A-552 C2H5 CH2-c-C5H9 A-594 C-C5H9 CH2-C-C6H11 R2 R3 R2 R3
A-595 c-CeHu CH2-C-C6H11 A-637 CH(CH3)CH=CH2 CH2-C-C4H7
A-596 CH2-C-C3H5 CH2-C-C6H11 A-638 CHF2 CH2-C-C4H7
A-597 CH(CH3)-c-C3H5 CH2-C-C6H11 A-639 CH2CI CH2-C-C4H7
A-598 CH2-C-C5H9 CH2-C-C6H11 A-640 CH2CH2CN CH2-C-C4H7
A-599 CH2-C-C6H11 CH2-C-C6H11 A-641 CH2CH2CI CH2-C-C4H7
A-600 C6H5 CH2-C-C6H11 A-642 C-C3H5 CH2-C-C4H7
A-601 CH3 C6H5 A-643 C-C4H7 CH2-C-C4H7
A-602 C2H5 C6H5 A-644 C-C5H9 CH2-C-C4H7
A-603 CH=CH2 C6H5 A-645 c-CeHu CH2-C-C4H7
A-604 CH2CH2CH3 C6H5 A-646 CH2-C-C3H5 CH2-C-C4H7
A-605 CH(CH3)2 C6H5 A-647 CH(CH3)-c-C3H5 CH2-C-C4H7
A-606 CH2CH2CH2CH3 C6H5 A-648 CH2-C-C5H9 CH2-C-C4H7
A-607 C(CH3)3 C6H5 A-649 CH2-C-C6H11 CH2-C-C4H7
A-608 CH2CH(CH3)2 C6H5 A-650 CH2-C-C4H7
A-609 CH(CH3)CH2CH3 C6H5 A-651 CH3 CH2CH2-c-C3H5
A-610 CH2CH=CH2 C6H5 A-652 C2H5 CH2CH2-c-C3H5
A-61 1 CH2C≡CH C6H5 A-653 CH=CH2 CH2CH2-c-C3H5
A-612 CH(CH3)CH=CH2 C6H5 A-654 CH2CH2CH3 CH2CH2-c-C3H5
A-613 CHF2 C6H5 A-655 CH(CH3)2 CH2CH2-c-C3H5
A-614 CH2CI C6H5 A-656 CH2CH2CH2CH3 CH2CH2-c-C3H5
A-615 CH2CH2CN C6H5 A-657 C(CH3)3 CH2CH2-c-C3H5
A-616 CH2CH2CI C6H5 A-658 CH2CH(CH3)2 CH2CH2-c-C3H5
A-617 c-C3H5 C6H5 A-659 CH(CH3)CH2CH3 CH2CH2-c-C3H5
A-618 C-C4H7 C6H5 A-660 CH2CH=CH2 CH2CH2-c-C3H5
A-619 C-C5H9 C6H5 A-661 CH2C≡CH CH2CH2-c-C3H5
A-620 c-CeHu C6H5 A-662 CH(CH3)CH=CH2 CH2CH2-c-C3H5
A-621 CH2-c-C3H5 C6H5 A-663 CHF2 CH2CH2-c-C3H5
A-622 CH(CH3)-c-C3H5 C6H5 A-664 CH2CI CH2CH2-c-C3H5
A-623 CH2-C-C5H9 C6H5 A-665 CH2CH2CN CH2CH2-c-C3H5
A-624 CH2-C-C5Hg C6H5 A-666 CH2CH2CI CH2CH2-c-C3H5
A-625 C6H5 C6H5 A-667 c-C3H5 CH2CH2-c-C3H5
A-626 CH3 CH2-C-C4H7 A-668 C-C4H7 CH2CH2-c-C3H5
A-627 C2H5 CH2-C-C4H7 A-669 C-C5H9 CH2CH2-c-C3H5
A-628 CH=CH2 CH2-C-C4H7 A-670 C-CeHu CH2CH2-c-C3H5
A-629 CH2CH2CH3 CH2-C-C4H7 A-671 CH2-C-C3H5 CH2CH2-c-C3H5
A-630 CH(CH3)2 CH2-C-C4H7 A-672 CH(CH3)-c-C3H5 CH2CH2-c-C3H5
A-631 CH2CH2CH2CH3 CH2-C-C4H7 A-673 CH2-C-C5H9 CH2CH2-c-C3H5
A-632 C(CH3)3 CH2-C-C4H7 A-674 CH2-C-C6H11 CH2CH2-c-C3H5
A-633 CH2CH(CH3)2 CH2-C-C4H7 A-675 C6H5 CH2CH2-c-C3H5
A-634 CH(CH3)CH2CH3 CH2-C-C4H7 A-676 CH3 CH2(CH2)3CH3
A-635 CH2CH=CH2 CH2-C-C4H7 A-677 C2H5 CH2(CH2)3CH3
A-636 CH2C≡CH CH2-C-C4H7 A-678 CH=CH2 CH2(CH2)3CH3 R2 R3 R2 R3
A-679 CH2CH2CH3 CH2(CH2)3CH3 A-714 CH2CI CH(CH3)CH(CH3)2
A-680 CH(CH3)2 CH2(CH2)3CH3 A-715 CH2CH2CN CH(CH3)CH(CH3)2
A-681 CH2CH2CH2CH3 CH2(CH2)3CH3 A-716 CH2CH2CI CH(CH3)CH(CH3)2
A-682 C(CH3)3 CH2(CH2)3CH3 A-717 c-C3H5 CH(CH3)CH(CH3)2
A-683 CH2CH(CH3)2 CH2(CH2)3CH3 A-718 C-C4H7 CH(CH3)CH(CH3)2
A-684 CH(CH3)CH2CH3 CH2(CH2)3CH3 A-719 C-C5H9 CH(CH3)CH(CH3)2
A-685 CH2CH=CH2 CH2(CH2)3CH3 A-720 c-C6Hii CH(CH3)CH(CH3)2
A-686 CH2C≡CH CH2(CH2)3CH3 A-721 CH2-c-C3H5 CH(CH3)CH(CH3)2
A-687 CH(CH3)CH=CH2 CH2(CH2)3CH3 A-722 CH(CH3)-c-C3H5 CH(CH3)CH(CH3)2
A-688 CHF2 CH2(CH2)3CH3 A-723 CH2-C-C5H9 CH(CH3)CH(CH3)2
A-689 CH2CI CH2(CH2)3CH3 A-724 CH2-C-C6H11 CH(CH3)CH(CH3)2
A-690 CH2CH2CN CH2(CH2)3CH3 A-725 C6H5 CH(CH3)CH(CH3)2
A-691 CH2CH2CI CH2(CH2)3CH3 A-726 CH3 CH2(CH2)4CH3
A-692 c-C3H5 CH2(CH2)3CH3 A-727 C2H5 CH2(CH2)4CH3
A-693 C-C4H7 CH2(CH2)3CH3 A-728 C(CH3)3 CH2(CH2)4CH3
A-694 C-C5H9 CH2(CH2)3CH3 A-729 CH2(CH2)4CH3 CH2(CH2)4CH3
A-695 c-C6Hii CH2(CH2)3CH3 A-730 CH3 2-EtHex
A-696 CH2-c-C3H5 CH2(CH2)3CH3 A-731 C2H5 2-EtHex
A-697 CH(CH3)-c-C3H5 CH2(CH2)3CH3 A-732 C(CH3)3 2-EtHex
A-698 CH2-C-C5H9 CH2(CH2)3CH3 A-733 2-EtHex 2-EtHex
A-699 CH2-C-C6H11 CH2(CH2)3CH3 A-734 CH3 CH2CH2OH
A-700 C6H5 CH2(CH2)3CH3 A-735 C2H5 CH2CH2OH
A-701 CH3 CH(CH3)CH(CH3)2 A-736 C(CH3)3 CH2CH2OH
A-702 C2H5 CH(CH3)CH(CH3)2 A-737 CH2CH2CH2CH3 CH2CH2OH
A-703 CH=CH2 CH(CH3)CH(CH3)2 A-738 CH2(CH2)3CH3 CH2CH2OH
A-704 CH2CH2CH3 CH(CH3)CH(CH3)2 A-739 CH2CH2OH CH2CH2OH
A-705 CH(CH3)2 CH(CH3)CH(CH3)2 A-740 CH2-c-C4H7 CH2-C-C4H7
A-706 CH2CH2CH2CH3 CH(CH3)CH(CH3)2 A-741 CH2CH2-c-C3H5 CH2CH2-c-C3H5
A-707 C(CH3)3 CH(CH3)CH(CH3)2 A-742 CH(CH3)CH(CH3)2 CH(CH3)CH(CH3)2
A-708 CH2CH(CH3)2 CH(CH3)CH(CH3)2 A-743 CH2(CH2)3CH3 CH2(CH2)3CH3
A-709 CH(CH3)CH2CH3 CH(CH3)CH(CH3)2 A-744 (CH2)4
A-710 CH2CH=CH2 CH(CH3)CH(CH3)2 A-745 CH2CH2SCH2
A-71 1 CH2C≡CH CH(CH3)CH(CH3)2
A-712 CH(CH3)CH=CH2 CH(CH3)CH(CH3)2
A-713 CHF2 CH(CH3)CH(CH3)2
c-C3H5: cyclopropyl; C-C4H7: cyclobutyl; 0C5H9: cyclopentyl; c-CeHu: cyclohexyl;
CH2-c-C3H5: cyclopropylmethyl; CH(CH3)-c-C3H5: 1-cyclopropylethyl;
CH2-c-C5H9: cyclopentylmethyl; CH2-C-C5H9: cyclopentylmethyl; CeH5: phenyl;
CH2CH2-C-C3H5: 2-cyclopropylethyl; CH2-c-C4H7: 2-cyclobutylmethyl; 2-EtHex:
CH2CH(C2H5)(CH2)3CH3 A group of especially preferred compounds of formula I are compounds 1-1 to I-40 of formula IA-1 which are listed in the table C in the example section.
In one embodiment, a compound selected from the compounds 1-1 to I-40 as defined in Table C in the Example Section at the end of the description, is preferred as compound according to the invention, and is also preferred in the methods and uses according to the invention.
In one embodiment, a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 is the compound I according to the invention, and as compound I in the methods and uses according to the invention, wherein said compounds are defined in accordance with Table C of the example section:
Table C
Figure imgf000041_0001
Figure imgf000041_0002
In one embodiment, 1-1 1 is a preferred compound I, and is preferred in the methods and uses according to the invention.
In one embodiment, 1-16 is a preferred compound I, and is preferred in the methods and uses according to the invention.
In one embodiment, 1-21 is a preferred compound I, and is preferred in the methods and uses according to the invention.
In one embodiment, I-26 is a preferred compound I, and is preferred in the methods and uses according to the invention.
In one embodiment, 1-31 is a preferred compound I, and is preferred in the methods and uses according to the invention.
As pointed out above, one embodiment of the invention relates to co-crystals and solvates of the compounds of the formula I, and more preferably a compound selected from compounds I- 1 1 , 1-16, 1-21 , I-26, 1-31 according to Table C/C. The solvates are preferably with water, or also preferably with organic solvents, preferably with aromatic hydrocarbons. It was surprisingly found that the compound of formula 1-21 forms stable crystals with toluene in a stoichiometric ratio, i.e. a solvate. Especially, two forms (form A and form B) are obtained. Form B can be identified as a monosolvate.
This is described in more detail in the example section.
Pests
The compounds and mixtures according to the invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes. The compounds and mixtures according to the invention are especially suitable for efficiently combating the following pests: insects from the order of the lepidopterans (Lepidoptera), for example Acronicta major, Adoxophyes orana, Aedia leucomelas, Agrotis spp. such as Agrotis fucosa, Agrotis segetum, Agrotis ypsilon; Alabama argillacea, Anticarsia gemmatalis, Anticarsia spp., Argyresthia conjugella, Autographa gamma, Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia murinana, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp. such as Feltia subterranean; Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp. such as Heliothis armigera, Heliothis virescens, Heliothis zea; Hellula undalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homona magnanima, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma spp. such as Laphygma exigua; Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lithophane antennata, Lobesia botrana, Loxagrotis albicosta, Loxostege sticticalis, Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkella, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mocis repanda, Mythimna separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp. such as Ostrinia nubilalis; Oulema oryzae, Panolis flammea, Pectinophora spp. such as Pectinophora gossypiella; Peridroma saucia, Phalera bucephala, Phthorimaea spp. such as Phthorimaea operculella; Phyllocnistis citrella, Pieris spp. such as Pieris brassicae, Pieris rapae; Plathypena scabra, Plutella maculipennis, Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, hyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp. such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura; Thaumatopoea pityocampa, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp. such as Trichoplusia ni; Tuta absoluta, and Zeiraphera canadensis, beetles (Coleoptera), for example Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus sinuatus, Agriotes spp. such as Agriotes fuscicollis, Agriotes lineatus, Agriotes obscurus; Amphimallus solstitialis, Anisandrus dispar, Anobium punctatum, Anomala rufocuprea, Anoplophora spp. such as Anoplophora glabripennis; Anthonomus spp. such as Anthonomus grandis, Anthonomus pomorum; Anthrenus spp., Aphthona euphoridae, Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as Bruchus lentis, Bruchus pisorum, Bruchus rufimanus; Byctiscus betulae, Callosobruchus chinensis, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as Ceuthorrhynchus assimilis, Ceuthorrhynchus napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as Conoderus vespertinus; Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptorhynchus lapathi, Ctenicera ssp. such as Ctenicera destructor; Curculio spp., Dectes texanus, Dermestes spp., Diabrotica spp. such as Diabrotica 12-punctata Diabrotica speciosa, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica virgifera; Epilachna spp. such as Epilachna varivestis, Epilachna vigintioctomaculata; Epitrix spp. such as Epitrix hirtipennis; Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera brunneipennis, Hypera postica, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lema bilineata, Lema melanopus, Leptinotarsa spp. such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolontha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp. such as Monochamus alternatus; Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema oryzae, Oxycetonia jucunda, Phaedon cochleariae, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp., Phyllotreta spp. such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., hizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais; Sphenophorus spp. such as Sphenophorus levis; Sternechus spp. such as Sternechus subsignatus; Symphyletes spp., Tenebrio molitor, Tribolium spp. such as Tribolium castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., and Zabrus spp. such as Zabrus tenebrioides, flies, mosquitoes (Diptera), e.g. Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp. such as Anopheles albimanus, Anopheles crucians, Anopheles freeborni, Anopheles gambiae, Anopheles leucosphyrus, Anopheles maculipennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp. such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochliomyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp. such as Culex nigripalpus, Culex pipiens, Culex quinquefasciatus, Culex tarsalis, Culex tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia spp. such as Delia antique, Delia coarctata, Delia platura, Delia radicum; Dermatobia hominis, Drosophila spp., Fannia spp. such as Fannia canicularis; Gastraphilus spp. such as Gasterophilus intestinalis; Geomyza Tripunctata, Glossina fuscipes, Glossina morsitans, Glossina palpalis, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as Hylemyia platura; Hypoderma spp. such as Hypoderma lineata; Hyppobosca spp., Leptoconops torrens, Liriomyza spp. such as Liriomyza sativae, Liriomyza trifolii; Lucilia spp. such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetiola destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabulans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as Phorbia antiqua, Phorbia brassicae, Phorbia coarctata; Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga spp. such as Sarcophaga haemorrhoidalis; Simulium vittatum, Stomoxys spp. such as Stomoxys calcitrans; Tabanus spp. such as Tabanus atratus, Tabanus bovinus, Tabanus lineola, Tabanus similis; Tannia spp., Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp., thrips (Thysanoptera), e.g. Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp. such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp. such as Scirtothrips citri; Taeniothrips cardamoni, Thrips spp. such as Thrips oryzae, Thrips palmi, Thrips tabaci; termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis, cockroaches (Blattaria - Blattodea), e.g. Acheta domesticus, Blatta orientalis, Blattella asahinae, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta japonica, bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acrosternum spp. such as Acrosternum hilare; Acyrthosipon spp. such as Acyrthosiphon onobrychis, Acyrthosiphon pisum; Adelges laricis, Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp. such as Blissus leucopterus; Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Cercopidae, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as Cimex hemipterus, Cimex lectularius; Coccomytilus halli, Coccus spp., Creontiades dilutus, Cryptomyzus ribis, Cryptomyzus ribis, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurades spp., Diaphorina spp., Diaspis spp., Dichelops furcatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cingulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster integriceps; Euscelis bilobatus, Euschistus spp. such as Euschistuos heros, Euschistus impictiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as Lygus hesperus, Lygus lineolaris, Lygus pratensis; Macropes excavatus, Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbiae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia costalis, Monelliopsis pecanis, Myzus spp. such as Myzus ascalonicus, Myzus cerasi, Myzus persicae, Myzus varians; Nasonovia ribis-nigri, Nephotettix spp. such as Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephotettix virescens; Nezara spp. such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp. such as Pemphigus bursarius; Pentomidae, Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Piesma quadrata, Piezodorus spp. such as Piezodorus guildinii, Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as Pseudococcus comstocki; Psylla spp. such as Psylla mali, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp. such as Thyanta perditor; Tibraca spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii, ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta capiguara, Atta cephalotes, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Bombus spp., Camponotus floridanus, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Hoplocampa spp. such as Hoplocampa minuta, Hoplocampa testudinea; Lasius spp. such as Lasius niger, Linepithema humile, Monomorium pharaonis, Paravespula germanica, Paravespula pennsylvanica, Paravespula vulgaris, Pheidole megacephala, Pogonomyrmex barbatus, Pogonomyrmex californicus, Polistes rubiginosa, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Vespa spp. such as Vespa crabro, and Vespula squamosa, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Calliptamus italicus, Chortoicetes terminifera, Dociostaurus maroccanus, Gryllotalpa africana, Gryllotalpa gryllotalpa, Hieroglyphus daganensis, Kraussaria angulifera, Locusta migratoria, Locustana pardalina, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Oedaleus senegalensis, Schistocerca americana, Schistocerca gregaria, Tachycines asynamorus, and Zonozerus variegatus, arachnids (Arachnida), such as acari.e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. Amblyomma americanum, Amblyomma variegatum, Amblyomma maculatum), Argas spp. (e.g. Argas persicus), Boophilus spp. (e.g. Boophilus annulatus, Boophilus decoloratus, Boophilus microplus), Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma spp. (e.g. Hyalomma truncatum), Ixodes spp. (e.g. Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus), Ornithodorus spp. (e.g. Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata), Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. (e.g. Psoroptes ovis), Rhipicephalus spp. (e.g. Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi), Rhizoglyphus spp., Sarcoptes spp. (e.g. Sarcoptes scabiei), and Eriophyidae spp. such as Acaria sheldoni, Aculops spp. (e.g. Aculops pelekassi) Aculus spp. (e.g. Aculus schlechtendali), Epitrimerus pyri, Phyllocoptruta oleivora and Eriophyes spp. (e.g. Eriophyes sheldoni); Tarsonemidae spp. such as Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp.; Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp. such as Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae; Bryobia praetiosa, Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligonychus pratensis), Vasates lycopersici; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa. And Acarus siro, Chorioptes spp., Scorpio maurus fleas (Siphonaptera), e.g. Ceratophyllus spp., 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. Geophilus spp., Scutigera spp. such as Scutigera coleoptrata; millipedes (Diplopoda), e.g. Blaniulus guttulatus, Narceus spp., Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp., springtails (Collembola ), e.g. Onychiurus ssp. such as Onychiurus armatus,
They are also suitable for controlling nematodes: plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiyohara, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; 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 Longidorus species; Lesion nematodes, Pratylenchus brachyurus, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species such as Tylenchulus semipenetrans; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; from the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of the Symphyla, for example, Scutigerella immaculata.
Further examples of pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caenorhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalocrosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cyclocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furcatus, Dicladispa armigera , Diloboderus spp. such as Diloboderus abderus; Edessa spp., Epinotia spp.,
Formicidae, Geocoris spp., Globitermes sulfureus, Gryllotalpidae, Halotydeus destructor, Hipnodes bicolor, Hydrellia philippina, Julus spp., Laodelphax spp., Leptocorsia acuta ,
Leptocorsia oratorius , Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Maladera matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipterus, Microtheca spp., Mocis latipes, Murgantia spp., Mythemina separata ,
Neocapritermes opacus, Neocapritermes parvus, Neomegalotomus spp., Neotermes spp., Nymphula depunctalis, Oebalus pugnax, Orseolia spp. such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Rachiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp. such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinophara coarctata; Sesamia spp. such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis,
Steneotarsonemus spinki, Sylepta derogata, Telehin licus, Trichostrongylus spp..
The compounds and mixtures 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, and chewing-biting pests such as insects from the genera of
Lepidoptera and Coleoptera, in particular the following spec\es: Thysanoptera : Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips 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 gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus,
Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops siiacea, Chrysops atianticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripaipus, Culex quinquefasciatus, Culex tarsaiis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina 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, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, 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, Macrosiphum 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, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii. Lepidoptera, in particular: Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea
grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis.
The compounds and mixtures of the present invention are particularly useful for controlling insects from the order of Coleoptera, in particular Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus 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, Epilachna 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 Sitophilus granaria. The compounds and mixtures of the present invention are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Hemiptera and Thysanoptera. The compounds and mixtures of the present invention are especially suitable for efficiently combating pests like insects from the order of the lepidopterans (Lepidoptera), beetles (Coleoptera), flies and mosquitoes (Diptera), thrips (Thysanoptera), termites (Isoptera), bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), ants, bees, wasps, sawflies (Hymenoptera), crickets, grasshoppers, locusts (Orthoptera), and also Arachnoidea, such as arachnids
(Acarina).
The compounds and mixtures of the present invention are particularly useful for controlling insects of the order Lepidoptera, especially Lepidoptera selected from Agrotis, Chilo,
Cnaphalocerus, Crocidolomia, Cydia, Heliothis, Manduca, Pieris, Plutella, Pyrausta, Sesamia , Spodoptera, Thermesia, Trichloplusia, Tuta.
The compounds and mixtures of the present invention are particularly useful for controlling Thysanoptera, especially Thysanoptera selected from Franklinella.
The compounds and mixtures of the present invention are particularly useful for controlling True Bugs, especially True Bugs selected from Lygus, Murgantia.
The compounds and mixtures of the present invention are particularly useful for controlling Diptera, especially Diptera selected from Delia, Liriomyza.
The compounds and mixtures of the present invention are particularly useful for controlling Beetles, especially Beetles selected from Agriotes, Cyclocephala, Diabrotica, Epitrix,
Leptinotarsa, Oulema, Phyllotreta, Popillia.
Formulations
The compounds and mixtures according to the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compounds and mixtures according to the invention. Therefore the invention also relates to agrochemical compositions comprising an auxiliary and compound or a mixture according to the invention, i.e. a mixture of at least one compound I of formula I and of at least one compound II according to the present invention. An agrochemical composition comprises a pesticidally effective amount of a pesticidal compound or mixture according to the invention. The term "effective amount" denotes an amount of the composition or of the mixture, which is sufficient for controlling harmful pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the animal pests species to be con-trolled, the treated cultivated plant or material, the climatic conditions and the specific mixture used.
The compounds and mixtures according to the present invention can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, gran-ules, pressings, capsules, and mixtures thereof. Examples for composition types are suspen-sions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal arti-cles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pes-ticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and am- photeric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam- pies of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl- polyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or poly- ethyleneamines. Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I or the mixture according to the invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I or a mixture according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I or a mixture according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I or a mixture according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I or a mixture according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I or a mixture according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium
lignosulfonate and alcohol ethoxylate), 0, 1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g.
polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG) 50-80 wt% of a compound I or a mixture according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound lor a mixture according to the invention are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound lor a mixture according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. ix) Microemulsion (ME)
5-20 wt% of a compound I or a mixture according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I or a mixture according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g.
diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1 -10 wt% of a compound I or a mixture according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I or a mixture according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xiii) Ultra-low volume liquids (UL)
1 -50 wt% of a compound I or a mixture according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1-1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
In one embodiment, a suspoconcentration (SC) is preferred for the application in crop protection. In one sub-embodiment thereof, the SC agrochemical composition comprises between 50 to 500 g/L (grams per Litre), or between 100 and 250 g/L, or 100 g/L or 150g/L or 200g/L or 250 g/L.
In a further embodiment, the granules according to formulation type xii are especially preferred for the application in rice.
Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water- soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compound I or a mixture according to the invention and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.001 to 1 kg per ha, more preferably from 0.005 to 0.9 kg per ha, in particular from 0.005 to 0.5 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 0.1 to 300 g, more preferably from 0.1 to 100 g and most preferably from 0.25 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1. The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
Applications
Due to their excellent activity, the compounds and mixtures according to the invention may be used for controlling invertebrate pests.
The compounds I and their mixtures can be applied simultaneously, that is jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in-situ" on the desired location, as e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
The compounds I and their mixtures are usually applied in a weight ratio of from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, preferably from 625:1 to 1 :625, preferably 500:1 to 1 :100, preferably from 100:1 to 1 :100 preferably from 20:1 to 1 :50, preferably from 20:1 to 1 :20, preferab,y from 10:1 to 1 :10, in particular from 5:1 to 1 :20, in particular from 5:1 to 1 :10, in particular from 5:1 to 1 :5.
Depending on the desired effect, the application rates of the mixtures according to the invention are from 5 g/ha to 2000 g/ha, preferably from 0.5 g/ha to 1000 g/ha, preferably from 1 to 750 g/ha, in particular from 5 to 500 g/ha. The compounds and mixtures according to the invention are effective through both contact and ingestion.
The compounds and mixtures according to the invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult. The pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of the inventive compounds and mixtures or of compositions comprising them.
According to a preferred embodiment, the mixtures according to the invention are used in crop protection, especially for the protection of living plants. According to another specific embodiment of the invention, the mixtures according to the present invention are employed via soil application. Soil application is especially favorable for use against ants, termites, crickets, or cockroaches.
According to another embodiment of the invention, for use against non crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or cockroaches the mixtures according to the present invention are prepared into a bait preparation.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
The animal pest (also referred to as "invertebrate 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 and mixtures according to the invention or composition(s) comprising them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/mixtures/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the
compounds/mixtures/compositions to the locus of the animal pest or plant).
The compounds and mixtures according to the 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 the compounds and mixtures according to the invention. The term "crop" refers both to growing and harvested crops.
The compounds and mixtures according to the 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 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.
Particularly preferred is the application of the compounds and mixtures according to the invention and the compositions comprising them on rice. Particularly preferred is the application of the mixtures according to the invention and the compositions comprising them on soybeans. Particularly preferred is the application of the mixtures according to the invention and the compositions comprising them on corn (maize).
Also preferred is the application of the compounds and mixtures according to the invention, especially the compounds as individualized herein, e.g. in Table AP-T, on specialty crops like fruits and vegetables. In one embodiment thereof, the application is on fruiting vegetables, and especially on tomato, on pepper or on eggplant.
In another embodiment thereof, the application is on leafy vegetables, and especially on cabbage or on lettuce.
In still another embodiment thereof, the application is on tubers (tuber vegetables), and especially on potato or on onion. Also preferred is the application of the compounds and mixtures according to the invention and the compositions comprising them on fruit and vegetables, especially fruit and vegetables selected from apple, tomato, broccoli, pepper, cucumber, eggplant, potato, cabbage, onion, leek, radish, squash, lettuce, bean, spinach.
Also preferred is the application of the compounds and mixtures according to the invention and the compositions comprising them on a crop selected from chickpea, sunflower, alfalfa, canola (oil seed rape), cotton, peanut.
The compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show good efficacy on lepidoptera, coleoptera, diptera and true bugs. The compounds and mixtures according to the invention and the compositions comprising them especially the compounds shown in Table C, show high efficacy on lepidoptera: Chilo suppressalis, Cnaphalocerus medinalis, Spodoptera sp. Plutella xylostella, Tuta absoluta and others.
The compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show high efficacy on coleoptera: Leptinotarsa decemlineata and others.
Especially, the compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show excellent efficacy in control of the following pests: Cnaphalocerus medinalis, Chilo suppressalis, Spodoptera frugiperda, Spodoptera exigua, Spodoptera sp., Plutella xylostella, Plutella xylostella , Tuta absoluta , Leptinotarsa decemlineata, Lygus hesperus. Especially, the compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show excellent efficacy in control of the following pests in the following crops:
Rice, Corn, Chickpea, Cabbage, Broccoli, Tomato, Potato, Alfalfa, Soy. In some embodiments, the invention relates to methods and uses, wherein a compound of fomula IA as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of fomula IA-1 as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of fomula IB as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of fomula IC as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of fomula ID as defined herein, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound selected from the compounds 1-1 to I-40 as defined in Table C in the Example Section, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of formula 1-1 1 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C. In some embodiments, the invention relates to methods and uses, wherein a compound of formula 1-16, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of formula 1-21 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of formula I-26, is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In some embodiments, the invention relates to methods and uses, wherein a compound of formula 1-31 , is applied in an application type which corresponds in each case to one row of Table AP-T or Table P-C.
In one embodiment, in the methods and uses according to the invention, the following application types are used:
Table AP-T:
(Abbreviations: SPC = specialty crops; SPC-FV = fruiting vegetable; SPC-LV = leafy vegetable; SPC-T: tubers; ST = seed treatment)
Appl. Crop Pest AP-T-14 Cotton Spodoptera type littoralis
AP-T-1 Soybeans Spodoptera AP-T-15 Cotton Thrips spp.
littoralis AP-T-16 Cotton Spodoptera
AP-T-2 Soybeans Anticarsia eridania
gemmatalis AP-T-17 Cotton Helicoverpa sp.
AP-T-3 Soybeans Spodoptera AP-T-18 Canola Pollen beetle exigua AP-T-19 SPC Tuta Absoluta
AP-T-4 Soybeans Stinkbug AP-T-20 SPC Fruit Borer
AP-T-5 Soybeans Helicoverpa sp. AP-T-21 SPC Spodoptera
AP-T-6 Soybeans Spodoptera littoralis
eridania AP-T-22 SPC Plusia gamma
AP-T-7 Corn Spodoptera AP-T-23 SPC Plutella xylostella
Frugiperta AP-T-24 SPC Frankliniella
AP-T-8 Corn Spodoptera occidentalis exigua AP-T-25 SPC Trichoplusia ni
AP-T-9 Rice Sesamia inferens AP-T-26 SPC Pieris rapae
AP-T-10 Rice Cnaphalocerus AP-T-27 SPC Spodoptera sp.
medinalis AP-T-28 SPC Crocidolomia
AP-T-1 1 Rice Chilo pavonana
suppressalis AP-T-29 SPC Pyrausta
AP-T-12 Rice Leptocorisa furnacalis
oratorius AP-T-30 SPC Liromyza trifolii
AP-T-13 Rice Brown plant AP-T-31 SPC Cydia pomonella hopper AP-T-32 SPC Epitrix sp. AP-T-33 SPC Leptinotarsa AP-T-65 Tomato Plutella xylostella decern lineata AP-T-66 Tomato Frankliniella
AP-T-34 SPC Bemisia tabaci occidentalis
AP-T-35 SPC Thrips tabaci AP-T-67 Tomato Trichoplusia ni
AP-T-36 SPC Spodoptera AP-T-68 Tomato Pieris rapae eridania AP-T-69 Tomato Spodoptera sp.
AP-T-37 SPC Lobesia botrana AP-T-70 Tomato Crocidolomia
AP-T-38 SPC Altica chapybea pavonana
AP-T-39 SPC Phyllocnistis AP-T-71 Tomato Pyrausta
citrella furnacalis
AP-T-40 SPC-FV Tuta Absoluta AP-T-72 Tomato Liromyza trifolii
AP-T-41 SPC-FV Fruit Borer AP-T-73 Tomato Cydia pomonella
AP-T-42 SPC-FV Spodoptera AP-T-74 Tomato Epitrix sp.
littoralis AP-T-75 Tomato Leptinotarsa
AP-T-43 SPC-FV Plusia gamma decemlineata
AP-T-44 SPC-FV Plutella xylostella AP-T-76 Tomato Bemisia tabaci
AP-T-45 SPC-FV Frankliniella AP-T-77 Tomato Thrips tabaci occidentalis AP-T-78 Tomato Spodoptera
AP-T-46 SPC-FV Trichoplusia ni eridania
AP-T-47 SPC-FV Pieris rapae AP-T-79 Tomato Lobesia botrana
AP-T-48 SPC-FV Spodoptera sp. AP-T-80 Tomato Altica chapybea
AP-T-49 SPC-FV Crocidolomia AP-T-81 Tomato Phyllocnistis pavonana citrella
AP-T-50 SPC-FV Pyrausta AP-T-82 Pepper Tuta Absoluta furnacalis AP-T-83 Pepper Fruit Borer
AP-T-51 SPC-FV Liromyza trifolii AP-T-84 Pepper Spodoptera
AP-T-52 SPC-FV Cydia pomonella littoralis
AP-T-53 SPC-FV Epitrix sp. AP-T-85 Pepper Plusia gamma
AP-T-54 SPC-FV Leptinotarsa AP-T-86 Pepper Plutella xylostella decemlineata AP-T-87 Pepper Frankliniella
AP-T-55 SPC-FV Bemisia tabaci occidentalis
AP-T-56 SPC-FV Thrips tabaci AP-T-88 Pepper Trichoplusia ni
AP-T-57 SPC-FV Spodoptera AP-T-89 Pepper Pieris rapae eridania AP-T-90 Pepper Spodoptera sp.
AP-T-58 SPC-FV Lobesia botrana AP-T-91 Pepper Crocidolomia
AP-T-59 SPC-FV Altica chapybea pavonana
AP-T-60 SPC-FV Phyllocnistis AP-T-92 Pepper Pyrausta
citrella furnacalis
AP-T-61 Tomato Tuta Absoluta AP-T-93 Pepper Liromyza trifolii
AP-T-62 Tomato Fruit Borer AP-T-94 Pepper Cydia pomonella
AP-T-63 Tomato Spodoptera AP-T-95 Pepper Epitrix sp.
littoralis AP-T-96 Pepper Leptinotarsa
AP-T-64 Tomato Plusia gamma decemlineata AP-T-97 Pepper Bemisia tabaci AP-T-129 SPC-LV Frankliniella
AP-T-98 Pepper Thrips tabaci occidentalis
AP-T-99 Pepper Spodoptera AP-T-130 SPC-LV Trichoplusia ni eridania AP-T-131 SPC-LV Pieris rapae
AP-T-100 Pepper Lobesia botrana AP-T-132 SPC-LV Spodoptera sp.
AP-T-101 Pepper Altica chapybea AP-T-133 SPC-LV Crocidolomia
AP-T-102 Pepper Phyllocnistis pavonana
citrella AP-T-134 SPC-LV Pyrausta
AP-T-103 Eggplant Tuta Absoluta furnacalis
AP-T-104 Eggplant Fruit Borer AP-T-135 SPC-LV Liromyza trifolii
AP-T-105 Eggplant Spodoptera AP-T-136 SPC-LV Cydia pomonella littoralis AP-T-137 SPC-LV Epitrix sp.
AP-T-106 Eggplant Plusia gamma AP-T-138 SPC-LV Leptinotarsa
AP-T-107 Eggplant Plutella xylostella decemlineata
AP-T-108 Eggplant Frankliniella AP-T-139 SPC-LV Bemisia tabaci occidentalis AP-T-140 SPC-LV Thrips tabaci
AP-T-109 Eggplant Trichoplusia ni AP-T-141 SPC-LV Spodoptera
AP-T-110 Eggplant Pieris rapae eridania
AP-T-11 1 Eggplant Spodoptera sp. AP-T-142 SPC-LV Lobesia botrana
AP-T-112 Eggplant Crocidolomia AP-T-143 SPC-LV Altica chapybea pavonana AP-T-144 SPC-LV Phyllocnistis
AP-T-113 Eggplant Pyrausta citrella
furnacalis AP-T-145 Cabbage Tuta Absoluta
AP-T-114 Eggplant Liromyza trifolii AP-T-146 Cabbage Fruit Borer
AP-T-115 Eggplant Cydia pomonella AP-T-147 Cabbage Spodoptera
AP-T-116 Eggplant Epitrix sp. littoralis
AP-T-117 Eggplant Leptinotarsa AP-T-148 Cabbage Plusia gamma decemlineata AP-T-149 Cabbage Plutella xylostella
AP-T-118 Eggplant Bemisia tabaci AP-T-150 Cabbage Frankliniella
AP-T-119 Eggplant Thrips tabaci occidentalis
AP-T-120 Eggplant Spodoptera AP-T-151 Cabbage Trichoplusia ni eridania AP-T-152 Cabbage Pieris rapae
AP-T-121 Eggplant Lobesia botrana AP-T-153 Cabbage Spodoptera sp.
AP-T-122 Eggplant Altica chapybea AP-T-154 Cabbage Crocidolomia
AP-T-123 Eggplant Phyllocnistis pavonana
citrella AP-T-155 Cabbage Pyrausta
AP-T-124 SPC-LV Tuta Absoluta furnacalis
AP-T-125 SPC-LV Fruit Borer AP-T-156 Cabbage Liromyza trifolii
AP-T-126 SPC-LV Spodoptera AP-T-157 Cabbage Cydia pomonella littoralis AP-T-158 Cabbage Epitrix sp.
AP-T-127 SPC-LV Plusia gamma AP-T-159 Cabbage Leptinotarsa
AP-T-128 SPC-LV Plutella xylostella decemlineata
AP-T-160 Cabbage Bemisia tabaci AP-T-161 Cabbage Thrips tabaci AP-T-193 SPC-T Trichoplusia ni
AP-T-162 Cabbage Spodoptera AP-T-194 SPC-T Pieris rapae eridania AP-T-195 SPC-T Spodoptera sp.
AP-T-163 Cabbage Lobesia botrana AP-T-196 SPC-T Crocidolomia
AP-T-164 Cabbage Altica chapybea pavonana
AP-T-165 Cabbage Phyllocnistis AP-T-197 SPC-T Pyrausta
citrella furnacalis
AP-T-166 Lettuce Tuta Absoluta AP-T-198 SPC-T Liromyza trifolii
AP-T-167 Lettuce Fruit Borer AP-T-199 SPC-T Cydia pomonella
AP-T-168 Lettuce Spodoptera AP-T-200 SPC-T Epitrix sp.
littoralis AP-T-201 SPC-T Leptinotarsa
AP-T-169 Lettuce Plusia gamma decemlineata
AP-T-170 Lettuce Plutella xylostella AP-T-202 SPC-T Bemisia tabaci
AP-T-171 Lettuce Frankliniella AP-T-203 SPC-T Thrips tabaci occidentalis AP-T-204 SPC-T Spodoptera
AP-T-172 Lettuce Trichoplusia ni eridania
AP-T-173 Lettuce Pieris rapae AP-T-205 SPC-T Lobesia botrana
AP-T-174 Lettuce Spodoptera sp. AP-T-206 SPC-T Altica chapybea
AP-T-175 Lettuce Crocidolomia AP-T-207 SPC-T Phyllocnistis pavonana citrella
AP-T-176 Lettuce Pyrausta AP-T-208 Potatoes Tuta Absoluta furnacalis AP-T-209 Potatoes Fruit Borer
AP-T-177 Lettuce Liromyza trifolii AP-T-210 Potatoes Spodoptera
AP-T-178 Lettuce Cydia pomonella littoralis
AP-T-179 Lettuce Epitrix sp. AP-T-21 1 Potatoes Plusia gamma
AP-T-180 Lettuce Leptinotarsa AP-T-212 Potatoes Plutella xylostella decemlineata AP-T-213 Potatoes Frankliniella
AP-T-181 Lettuce Bemisia tabaci occidentalis
AP-T-182 Lettuce Thrips tabaci AP-T-214 Potatoes Trichoplusia ni
AP-T-183 Lettuce Spodoptera AP-T-215 Potatoes Pieris rapae eridania AP-T-216 Potatoes Spodoptera sp.
AP-T-184 Lettuce Lobesia botrana AP-T-217 Potatoes Crocidolomia
AP-T-185 Lettuce Altica chapybea pavonana
AP-T-186 Lettuce Phyllocnistis AP-T-218 Potatoes Pyrausta
citrella furnacalis
AP-T-187 SPC-T Tuta Absoluta AP-T-219 Potatoes Liromyza trifolii
AP-T-188 SPC-T Fruit Borer AP-T-220 Potatoes Cydia pomonella
AP-T-189 SPC-T Spodoptera AP-T-221 Potatoes Epitrix sp.
littoralis AP-T-222 Potatoes Leptinotarsa
AP-T-190 SPC-T Plusia gamma decemlineata
AP-T-191 SPC-T Plutella xylostella AP-T-223 Potatoes Bemisia tabaci
AP-T-192 SPC-T Frankliniella AP-T-224 Potatoes Thrips tabaci occidentalis AP-T-225 Potatoes Spodoptera AP-T-241 Onions Liromyza trifolii eridania AP-T-242 Onions Cydia pomonella
AP-T-226 Potatoes Lobesia botrana AP-T-243 Onions Epitrix sp.
AP-T-227 Potatoes Altica chapybea AP-T-244 Onions Leptinotarsa
AP-T-228 Potatoes Phyllocnistis decemlineata citrella AP-T-245 Onions Bemisia tabaci
AP-T-229 Potatoes wireworm AP-T-246 Onions Thrips tabaci
AP-T-230 Onions Tuta Absoluta AP-T-247 Onions Spodoptera
AP-T-231 Onions Fruit Borer eridania
AP-T-232 Onions Spodoptera AP-T-248 Onions Lobesia botrana littoralis AP-T-249 Onions Altica chapybea
AP-T-233 Onions Plusia gamma AP-T-250 Onions Phyllocnistis
AP-T-234 Onions Plutella xylostella citrella
AP-T-235 Onions Frankliniella AP-T-251 ST Agrotis ipsilon occidentalis AP-T-252 ST Spodoptera
AP-T-236 Onions Trichoplusia ni frugiperta
AP-T-237 Onions Pieris rapae AP-T-253 ST Phyllotreta sp.
AP-T-238 Onions Spodoptera sp. AP-T-254 ST Stem Girdler
AP-T-239 Onions Crocidolomia AP-T-255 ST Agriotes sp.
pavonana AP-T-256 ST Delia platura
AP-T-240 Onions Pyrausta
furnacalis
Especially, the compounds and mixtures according to the invention and the compositions comprising them, especially the compounds shown in Table C, show excellent efficacy in control of the following pests in the following crops:
Table P-C:
Pest Crop
P-C-1 Cnaphalocerus medinalis Rice
P-C-2 Chilo suppressalis Rice
P-C-3 Spodoptera frugiperda Rice
P-C-4 Spodoptera exigua Rice
P-C-5 Spodoptera sp. Rice
P-C-6 Plutella xylostella Rice
P-C-7 Tuta absoluta Rice
P-C-8 Lygus hesperus Rice
P-C-9 Spodoptera frugiperda Corn
P-C-10 Spodoptera exigua Corn
P-C-1 1 Spodoptera sp. Corn
P-C-12 Plutella xylostella Corn
P-C-13 Tuta absoluta Corn
P-C-14 Leptinotarsa decemlineata Corn Pest Crop
P-C-15 Lygus hesperus Corn
P-C-16 Spodoptera frugiperda Chickpea
P-C-17 Spodoptera exigua Chickpea
P-C-18 Spodoptera sp. Chickpea
P-C-19 Plutella xylostella Chickpea
P-C-20 Tuta absoluta Chickpea
P-C-21 Leptinotarsa decemlineata Chickpea
P-C-22 Lygus hesperus Chickpea
P-C-23 Spodoptera frugiperda Cabbage
P-C-24 Spodoptera exigua Cabbage
P-C-25 Spodoptera sp. Cabbage
P-C-26 Plutella xylostella Cabbage
P-C-27 Tuta absoluta Cabbage
P-C-28 Leptinotarsa decemlineata Cabbage
P-C-29 Lygus hesperus Cabbage
P-C-30 Spodoptera frugiperda Broccoli
P-C-31 Spodoptera exigua Broccoli
P-C-32 Spodoptera sp. Broccoli
P-C-33 Plutella xylostella Broccoli
P-C-34 Tuta absoluta Broccoli
P-C-35 Leptinotarsa decemlineata Broccoli
P-C-36 Lygus hesperus Broccoli
P-C-37 Spodoptera frugiperda Tomato
P-C-38 Spodoptera exigua Tomato
P-C-39 Spodoptera sp. Tomato
P-C-40 Plutella xylostella Tomato
P-C-41 Tuta absoluta Tomato
P-C-42 Leptinotarsa decemlineata Tomato
P-C-43 Lygus hesperus Tomato
P-C-44 Spodoptera frugiperda Potato
P-C-45 Spodoptera exigua Potato
P-C-46 Spodoptera sp. Potato
P-C-47 Plutella xylostella Potato
P-C-48 Tuta absoluta Potato
P-C-49 Leptinotarsa decemlineata Potato
P-C-50 Lygus hesperus Potato
P-C-51 Spodoptera frugiperda Alfalfa
P-C-52 Spodoptera exigua Alfalfa
P-C-53 Spodoptera sp. Alfalfa
P-C-54 Plutella xylostella Alfalfa Pest Crop
P-C-55 Tuta absoluta Alfalfa
P-C-56 Leptinotarsa decemlineata Alfalfa
P-C-57 Lygus hesperus Alfalfa
P-C-58 Spodoptera frugiperda Soy
P-C-59 Spodoptera exigua Soy
P-C-60 Spodoptera sp. Soy
P-C-61 Plutella xylostella Soy
P-C-62 Tuta absoluta Soy
P-C-63 Leptinotarsa decemlineata Soy
P-C-64 Lygus hesperus Soy
P-C-65 tortricides tree fruits
P-C-66 tortricides grapes
P-C-67 Tuta absoluta fruiting vegetables
P-C-68 Lepidoptera field brassica
P-C-69 coleoptera potatoe
P-C-70 Coleoptera oil-seed rape
P-C-71 Lepidoptera corn
P-C-72 Lepidoptera cotton
P-C-73 thrips flowers
P-C-74 Eupoecilia ambiguella grape
P-C-75 Lobesia botrana grape
P-C-76 Haltica ampelophaga grape
P-C-77 Cydia pomonella apple
P-C-78 Grapholita molesta Peach
P-C-79 Phyllocnistis citrella Citrus
P-C-80 Tuta absoluta Tomato
P-C-81 Tuta absoluta Tomato (greenhouse)
P-C-82 Scrobipalpula absoluta Tomato
P-C-83 Scrobipalpula absoluta Tomato (greenhouse)
P-C-84 Thrips sp. flower
P-C-85 Thrips sp Tagetes
Leptinotarsa decemlineata
P-C-86
(Colorado potato beetle ) potatoe
P-C-87 Pieris brassicae Cabbage
P-C-88 Anticarsia (Thermesia) gemmatalis Soybean
P-C-89 Spodoptera littoralis Soybean
P-C-90 Plutella xylostella Collard
P-C-91 Plutella xylostella Cabbage
P-C-92 Pieris rapae Cabbage
P-C-93 Sesamia nonagriodes Corn Pest Crop
P-C-94 Helicoverpa armigera Corn
P-C-95 Ostrinia nubilalis Corn
P-C-96 Spodoptera sp. Soybean
P-C-97 Earias sp. Cotton
P-C-98 Spodoptera sp. Cabbage
P-C-99 Pyrausta furnacalis Corn
P-C-100 Spodoptera sp. Corn
P-C-101 Spodoptera frugiperda Corn
P-C-102 Chilo suppressalis Rice
P-C-103 Cnaphalocrocis medinalis Rice
P-C-104 Sesamia inferens Rice
P-C-105 Phyllotreta sp Cabbage
P-C-106 Epitrix fuscula Eggplant
P-C-107 Diabrotica virgifera virgifera Corn (Seed Treatment)
P-C-108 Pollen beetle oilseed rape
P-C-109 Meligethes aeneus Oilseed rape
P-C-1 10 Pollen beetle flowers
P-C-1 1 1 Meligethes aeneus flowers
P-C-1 12 Pollen beetle vegetables
P-C-1 13 Meligethes aeneus vegetables
P-C-1 14 Pollen beetle Brassica
P-C-1 15 Meligethes aeneus Brassica
The application types are understood to include several applications per crop season, so as to control first and second and higher generations of pests. The compounds and mixtures according to the 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 an insecticidally 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 habitat, breeding ground, food supply, cultivated 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 I and at least one active compound II.
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 a mixture according to the 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 and mixtures according to the invention can also be applied preventively to places at which occurrence of the pests is expected.
The compounds and mixtures according to the 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 and mixtures according to the 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 and mixtures according to the invention /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, the genetic material of which has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) for example by glycosylation or polymer additions such as prenylated, acetylated or 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- phenyl pyruvate 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 6222100, 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, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are 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 content or protein content), tolerance to drought, salinity or other growth-limiting environ-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 ingredients or mixture according to the invention 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 mixtures/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 foliar treatment ,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, or from 1 to 100 g per hectare, preferably from 10 to 50 g per hectare, or from 12 to 50 g per hectare, or from 10 to 30 g per hectare, or from 20 to 40 g per hectare, or from 10 to 20 g per hectare, or from 20 to 30 g per hectare, or from 30 to 40 g per hectare, or from 40 to 50 g per hectare.
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 compounds 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.
The compounds and mixtures according to the invention are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part). The mixtures according to 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, the compounds and mixtures according to the invention are preferably used in a bait composition. The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredients is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compounds.
Formulations of compounds of formula I or mixtures according to the invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound(s), 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 %.
The compounds and mixtures according to the invention respective their 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 and mixtures according to the invention and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are N,N-Diethyl- meta-toluamide (DEET), 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 extracts like limonene, eugenol, (+)-Eucamalol (1), (-)-1 -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 and mixtures according to the 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 and mixtures according to the invention 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. Seed treatment
The compounds and mixtures according to the 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 and mixtures according to the 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 compounds and mixtures according to the invention. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected from piercing and sucking insects, most preferably a method, wherein the plants shoots are protected from aphids. Also preferred ist a method, wherein the plant's roots and shoots are protected from chewing and biting insects, most preferably a method, wherein the plants shoots and roots are protected from Lepidoptera and/or Coleoptera, most preferably wherein the plant shoots and roots are protected from rice leaf beetle .
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 compounds and mixtures according to the invention.
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 product 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.
Particularly preferred is the application of the mixtures according to the invention and the compositions comprising them on rice.
In addition, the active compounds and mixtures according to the invention may also be used for the treatment of seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
For example, the active compounds and mixtures according to the invention 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 242 236, EP-A 242 246) (WO
92/00377) (EP-A 257 993, U.S. 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 142 924, EP-A 193 259),
Furthermore, the active compounds and mixtures according to the invention 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 generation 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 compounds 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. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter
In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of compounds of formula I, compounds II or the compounds and mixtures according to the invention, 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, polysaccharides 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. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108. Examples of a gelling agent is carrageen (Satiagel®)
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.
Animal health
The compounds and mixtures according to the invention 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. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions comprising a parasiticidally effective amount of the compounds and mixtures according to the invention 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 mixture according to the invention or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a mixture according to the invention or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, 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 the compounds and mixtures according to the invention are suitable for combating endo- and ectoparasites in and on animals.
Compounds and mixtures according to the invention and compositions comprising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds and mixtures according to the invention 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 and mixtures according to the invention and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds and mixtures according to the invention are especially useful for combating ectoparasites.
The compounds and mixtures according to the invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus 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, Phlebotomus 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, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Omithodorus turicata and parasitic mites (Mesostigmata), e.g. Omithonyssus bacoti and Dermanyssus gallinae,
Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp.,
Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., 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., Ostertagia 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., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp., Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
The compounds and mixtures according to the invention and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida. Moreover, the use of the compounds and mixtures according to the invention and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds and mixtures according to the invention and compositions containing them for combating flies is a further preferred embodiment of the present invention.
Furthermore, the use of the compounds of formula I and compositions containing them for combating fleas is especially preferred.
The use of the compounds and mixtures according to the invention and compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds and mixtures according to the invention also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians). Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds or mixtures is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the compounds of formula I, compounds II or the mixtures accordingto the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of formula I, compounds II or the mixtures accordingto the invention may be administered to the animals in their drinking water.
For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula I, compounds II or the mixtures accordingto the invention, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of formula I, compounds II or the mixtures accordingto the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula I, compounds II or the mixtures accordingto the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula I, compounds II or the mixtures accordingto the invention may be formulated into an implant for subcutaneous administration. In addition the compounds of formula I, compounds II or the mixtures accordingto the 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 compounds of formula I, compounds II or the mixture accordingto the invention.
The compounds of formula I, compounds II or the mixtures accordingto the 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 compounds of formula I, compounds II or the mixtures accordingto the invention. In addition, the compounds of formula I, compounds II or the mixtures accordingto the 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, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and
methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-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, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n- octylpyrrolidone, N-methylpyrrolidone, 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, polyacrylates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are:
liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Ce-Cio fatty acids,
fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof. Suitable emulsifiers are:
non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether;
ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin;
anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt;
cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked
polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various
compounds/mixtures/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like. The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the the mixture according to the invention.
Generally it is favorable to apply the mixture according to the invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds and mixtures according to the 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.
In a preferred embodiment of the present invention, the compositions comprising the compounds and mixtures according to the inventionare applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound- containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release the active compounds 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 active compounds. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
Mixtures
Mixtures according to the invention are mixtures of at least one compound of formula I with at least one further pesticidal compound II.
The pesticidally active compounds II with which the compounds of formula I are combined with for the methods according to present invention are the following:
In one embodiment of the invention, the compounds of formula I can be combined and used in mixture with another pesticidally active compound (II) and applied in agriculture. A skilled person is familiar with such compounds and knows which compounds are active against a specific target organism.
The compound (II) pesticides, together with which the compounds of formula I may be used according to the purpose of the present invention, and with which potential synergistic effects with regard to the method of uses might be produced, are selected and grouped according to the Mode of Action Classification from the Insecticde Resistance Action Committee (IRAC) and are selected from group M consisting of
Acetylcholine esterase (AChE) inhibitors from the class of
carbamates, including aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
organophosphates, including acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion;
GABA-gated chloride channel antagonists such as:
cydodiene organochlorine compounds, including endosulfan or chlordane; or fiproles (phenylpyrazoles), including ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
Sodium channel modulators from the class of
pyrethroids, including acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin and transfluthrin; or
sodium channel modulators such as DDT or methoxychlor;
II-M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of II-M.4A neonicotinoids, including acetamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds
II-M.4A.1 : 1 -[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-(5S,8 )-5,8- Epoxy-1 H-imidazo[1 ,2-a]azepine; or
II-M.4A.2: 1 -[(6-chloro-3-pyridyl)methyl]-2-nitro-1-[(E)-pentylideneamino]guanidine; or
II-M.4A.3: 1 -[(6-chloro-3-pyridyl)methyl]-7-methyl-8-nitro-5-propoxy-3,5,6J-tetrahydro- 2H-imidazo[1 ,2-a]pyridine; or
II-M.4B nicotine.
II-M.5 Nicotinic acetylcholine receptor allosteric activators from the class of
spinosyns, including spinosad or spinetoram;
II-M.6 Chloride channel activators from the class of avermectins and milbemycins, including abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
II-M.7 Juvenile hormone mimics, such as
II-M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as
I I-M.7B fenoxycarb, or
II-M.7C pyriproxyfen;
II-M.8 miscellaneous non-specific (multi-site) inhibitors, including
II-M.8A alkyl halides as methyl bromide and other alkyl halides, or
II-M.8B chloropicrin, or
II-M.8C sulfuryl fluoride, or
II-M.8D borax, or
II-M.8E tartar emetic;
II-M.9 Selective homopteran feeding blockers, including
II-M.9B pymetrozine, or
II-M.9C flonicamid;
II-M.10 Mite growth inhibitors, including
II-M.10A clofentezine, hexythiazox and diflovidazin, or
II-M.10B etoxazole;
II-M.1 1 Microbial disruptors of insect midgut membranes, including bacillus
thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
II-M.12 Inhibitors of mitochondrial ATP synthase, including
II-M.12A diafenthiuron, or
II-M.12B organotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or II-M.12C propargite, or
II-M.12D tetradifon; II-M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, including chlorfenapyr, DNOC or sulfluramid;
II-M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, including
nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
II-M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylure including bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
II-M.16 Inhibitors of the chitin biosynthesis type 1 , including buprofezin;
II-M.17 Moulting disruptors, Dipteran, including cyromazine; II-M.18 Ecdyson receptor agonists such as diacylhydrazines, including
methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
II-M.19 Octopamin receptor agonists, including amitraz; II-M.20 Mitochondrial complex III electron transport inhibitors, including
II-M.20A hydramethylnon, or
II-M.20B acequinocyl, or
II-M.20C fluacrypyrim; II-M.21 Mitochondrial complex I electron transport inhibitors, including
II-M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate,
pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or
II-M.21 B rotenone; II-M.22 Voltage-dependent sodium channel blockers, including
II-M.22A indoxacarb, or
II-M.22B metaflumizone; or -M.22C 1 -[(E)-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]ami (difluoromethoxy)phenyl]urea;
-M.23 Inhibitors of the acetyl CoA carboxylase, including Tetronic and Tetramic acid derivatives, including spirodiclofen, spiromesifen or spirotetramat;
-M.24 Mitochondrial complex IV electron transport inhibitors, including
-M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or
-M.24B cyanide.
-M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, including cyenopyrafen or cyflumetofen;
-M.26 Ryanodine receptor-modulators from the class of diamides, including
flubendiamide, chloranthraniliprole (rynaxypyr®), cyanthraniliprole
(cyazypyr®), or
the phthalamide compounds
-M.26.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1-(trifluormethyl)ethyl]phenyl}-
N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and
-M.26.2: (S)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1-(trifluormethyl)ethyl]phenyl}-
N2-(1-methyl-2-methylsulfonylethyl)phthalamid, or the compound -M.26.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1 -(3- chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or the compound
-M.26.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; or a compound selected from ll-M.26.5a) to ll-M.26.5d):
-M.26.5a: N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methyl-phenyl]-5-bromo-2-(3- chloro-2-pyridyl)pyrazole-3-carboxamide;
-M.26.5b: 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(1-cyano-1-methyl- ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide;
-M.26.5c: 5-bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2- pyridyl)pyrazole-3-carboxamide;
-M.26.5d: N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-
(fluoromethoxy)pyrazole-3-carboxamide; or
-M.26.6: N2-(1-cyano-1-methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthalamide; or -M.26.7: 3-chloro-N2-(1-cyano-1-methyl-ethyl)-N1 -(2,4-dimethylphenyl)phthalamide; ll-M.X insecticidal active compounds of unknown or uncertain mode of action, including afidopyropen, azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, pyflubumide or the compound
II-M.X.1 : 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2- methyl-N-[(2,2,2 rifluoro-ethylcarbamoyl)-methyl]-benzamide, or the compound
II-M.X.2: cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2- cyclopropylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12- hydroxy-4,6a, 12b-trimethyl-1 1 -oxo-9-(3-pyridinyl)-2H, 11 H-naphtho[2, 1 - b]pyrano[3,4-e]pyran-3,6-diyl] ester, or the compound
II-M.X.3: 1 1-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]- tetradec-1 1-en-10-one, or the compound
II-M.X.4 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3- en-2-one, or the compound
II-M.X.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)- 1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, I-
1582), or
II-M.X.6: a compound selected from the group of
ll-M.X.6a: (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; ll-M.X.6b: (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide;
ll-M.X.6c: (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; ll-M.X.6d: (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; ll-M.X.6e: (E/Z)-N-[1 -[1-(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; ll-M.X.6f: (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; ll-M.X.6g: (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide;
ll-M.X.6h: (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide andll-M.X.6i: (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,3,3,3-pentafluoro-propanamide); or
II-M.X.7: triflumezopyrim; or
II-M.X.8: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-
[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1-carboxamide, or II-M.X.9: 3-[3-chloro-5-(trifluoromethyl)phenyl]-4-oxo-1-(pyrimidin-5-ylmethyl)pyrido[1 ,2- a]pyrimidin-1 -ium-2-olate; or
II-M.X.10: 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2- a]pyridine-2-carboxamide; or
II-M.X.1 1 : 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or
II-M.X.12: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or ll-M.Y Biopesticides, e.g. ΙΙ-Μ.Υ-1 : Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Bacillus firmus, B. thuringiensis ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, Beauveria bassiana, Burkholderia sp., Chromobacterium subtsugae, Cydia pomonella granulosis virus, Isaria fumosorosea,
Lecanicillium longisporum, L. muscarium (formerly Verticillium lecanii),
Metarhizium anisopliae, M. anisopliae var. acridum, Paecilomyces
fumosoroseus, P. lilacinus, Paenibacillus poppiliae, Pasteuria spp., P.
nishizawae, P. reneformis, P. usagae, Pseudomonas fluorescens,
Steinernema feltiae, Streptomces galbus;
ll-M.Y-2) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Ζ,Ζ,Ε)- 7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, 2-methyl 1 -butanol, methyl eugenol, methyl jasmonate, (E,Z)- 2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13- octadecadien-1-ol, R-1 -octen-3-ol, pentatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12- tetradecadien-1-yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1-yl acetate, Z-1 1-tetradecenal, Z-11 -tetradecen-1-ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil,
Neem oil, Quillay extract, Tagetes oil.
The commercially available compounds II of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.
The quinoline derivative flometoquin is shown in WO2006/013896. The aminofuranone compounds flupyradifurone is known from WO 2007/1 15644. The sulfoximine compound sulfoxaflor is known from WO2007/149134. The pyrethroid momfluorothrin is known from US6908945. The pyrazole acaricide pyflubumide is known from WO2007/020986. The isoxazoline compound II-M.X.1 has been described in WO2005/085216, II-M.X.8 in
WO2009/002809 and in WO201 1/149749 and the isoxazoline II-M.X.11 in WO2013/050317. The pyripyropene derivative II-M.X.2 has been described in WO 2006/129714. The spiroketal- substituted cyclic ketoenol derivative II-M.X.3 is known from WO2006/089633 and the biphenyl- substituted spirocyclic ketoenol derivative II-M.X.4 from WO2008/06791 1. Triazoylphenylsulfide like II-M.X.5 have been described in WO2006/043635 and biological control agents on basis of bacillus firmus in WO2009/124707. The neonicotionids II-M4A.1 is known from
WO20120/069266 and WO201 1/06946, the II-M.4A.2 from WO2013/003977, the ll-M4A.3.from WO2010/069266. The metaflumizone analogue II-M.22C is described in CN 10171577.
Cyantraniliprole (Cyazypyr) is known from e.g. WO 2004/067528. The phthalamides ll-M.26.1 and ll-M.26.2 are both known from WO 2007/101540. The anthranilamide ll-M.26.3 has been described in WO 2005/077934. The hydrazide compound ll-M.26.4 has been described in WO 2007/043677. The anthranilamide ll-M.26.5a) is described in WO201 1/085575, the ll-M.26.5b) in WO2008/134969, the ll-M.26.5c) in US201 1/046186 and the ll-M.26.5d in WO2012/034403. The diamide compounds ll-M.26.6 and ll-M.26.7 can be found in CN102613183.
The compounds ll-M.X.6a) to I Ι-Μ.Χ.6Ϊ) listed in II-M.X.6 have been described in
WO2012/029672.
The mesoionic antagonist compound II-M.X.9 was described in WO2012/092115, the nematicide II-M.X.10 in WO2013/055584 and the Pyridalyl-type analogue II-M.X.12 in
WO2010/060379.
Biopesticides
The biopesticides from group ll-M.Y, and from group F.XIII) as described below, their preparation and their biological activity e.g. against harmful fungi, pests is known (e-Pesticide Manual V 5.2 (ISBN 978 1 901396 85 0) (2008-201 1);
http://www.epa.gov/opp00001/biopesticides/, see product lists therein; http://www.omri.org/omri- lists, see lists therein; Bio-Pesticides Database BPDB http://sitem.herts.ac.uk/aeru/bpdb/, see A to Z link therein). Many of these biopesticides are registered and/or are commercially available: aluminium silicate (SCREEN™ DUO from Certis LLC, USA), Ampelomyces quisqualis M-10 (e.g. AQ 10® from Intrachem Bio GmbH & Co. KG, Germany), Ascophyllum nodosum
(Norwegian kelp, Brown kelp) extract (e.g. ORKA GOLD from Becker Underwood, South Africa), Aspergillus flavus NRRL 21882 (e.g. AFLA-GUARD® from Syngenta, CH), Aureobasidium pullulans (e.g. BOTECTOR® from bio-ferm GmbH, Germany), Azospirillum brasilense XOH
(e.g. AZOS from Xtreme Gardening, USA USA or RTI Reforestation Technologies International; USA), Bacillus amyloliquefaciens IT-45 (CNCM I 3800, NCBI 1091041) (e.g. RHIZOCELL C from ITHEC, France), B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595, deposited at United States Department of Agriculture) (e.g. INTEGRAL®, CLARITY, SUBTILEX NG from Becker Underwood, USA), B. pumilus QST 2808 (NRRL Accession No. B 30087) (e.g. SONATA® and BALLAD® Plus from AgraQuest Inc., USA), B. subtilis GB03 (e.g. KODIAK from Gustafson, Inc., USA), B. subtilis GB07 (EPIC from Gustafson, Inc., USA), B. subtilis QST-713 (NRRL-Nr. B 21661 in RHAPSODY®, SERENADE® MAX and SERENADE® ASO from Agra- Quest Inc., USA), B. subtilis var. amylolique-'faciens FZB24 (e.g. TAEGRO® from Novozyme Biologicals, Inc., USA), B. subtilis var. amyloliquefaciens D747 (e.g. Double Nickel 55 from Certis LLC, USA), Bacillus thuringiensis ssp. kurstaki SB4 (e.g. BETA PRO® from Becker Underwood, South Africa), Beauveria bassiana GHA (BOTANIGARD® 22WGP from Laverlam Int. Corp., USA), B. bassiana 12256 (e.g. BIOEXPERT® SC from Live Sytems Technology S.A., Colombia), B. bassiana PRPI 5339 (ARSEF number 5339 in the US DA ARS collection of entomopathogenic fungal cultures) (e.g. BROADBAND® from Becker Underwood, South Africa), Bradyrhizobium sp. (e.g. VAULT® from Becker Underwood, USA), B. japonicum (e.g. VAULT® from Becker Underwood, USA), Candida oleophila I-82 (e.g. ASPIRE® from Ecogen Inc., USA), Candida saitoana (e.g. BIOCURE® (in mixture with lysozyme) and BIOCOAT® from Micro Flo Company, USA (BASF SE) and Arysta), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., NZ), Clonostachys rosea f. catenulata, also named Gliocladium catenulatum (e.g. isolate J1446: PRESTOP® from Verdera, Finland), Coniothyrium minitans CON/M/91-08 (e.g.
Contans® WG from Prophyta, Germany), Cryphonectria parasitica (e.g. Endothia parasitica from CNICM, France), Cryptococcus albidus (e.g. YIELD PLUS® from Anchor Bio- Technologies, South Africa), Ecklonia maxima (kelp) extract (e.g. KELPAK SL from Kelp Products Ltd, South Africa), Fusarium oxysporum (e.g. BIOFOX® from S.I.A.P.A., Italy, FUSAC LEAN® from Natural Plant Protection, France), Glomus intraradices (e.g. MYC 4000 from ITHEC, France), Glomus intraradices RTI-801 (e.g. MYKOS from Xtreme Gardening, USA or RTI Reforestation Technologies International; USA), grapefruit seeds and pulp extract (e.g. BC-1000 from Chemie S.A., Chile), Isaria fumosorosea Apopka-97 (ATCC 20874) (PFR-97™ from Certis LLC, USA), Lecanicillium muscarium (formerly Verticillium lecanii) (e.g. MYCOTAL from Koppert BV, Netherlands), Lecanicillium longisporum KV42 and KV71 (e.g. VERTALEC® from Koppert BV, Netherlands), Metarhizium anisopliae var. acridum IMI 330189 (deposited in European Culture Collections CABI) (e.g. GREEN MUSCLE® from Becker Underwood, South Africa), M. anisopliae FI-1045 (e.g. BIOCANE® from Becker Underwood Pty Ltd, Australia), M. anisopliae var. acridum FI-985 (e.g. GREEN GUARD® SC from Becker Underwood Pty Ltd, Australia), M. anisopliae F52 (e.g. MET52® Novozymes Biologicals BioAg Group, Canada), M. anisopliae ICIPE 69 (e.g. METATHR POL from ICIPE, Kenya), Metschnikowia fructicola (e.g. SHEMER® from Agrogreen, Israel), Microdochium dimerum (e.g. ANTIBOT® from Agrauxine, France), Neem oil (e.g. TRILOGY®, TRIACT® 70 EC from Certis LLC, USA), Paecilomyces fumosoroseus strain FE 9901 (e.g. NO FLY™ from Natural Industries, Inc., USA), P. lilacinus DSM 15169 (e.g. NEMATA® SC from Live Systems Technology S.A., Colombia), P. lilacinus BCP2 (e.g. PL GOLD from Becker Underwood BioAg SA Ltd, South Africa), mixture of
Paenibacillus alvei NAS6G6 and Bacillus pumilis (e.g. BAC-UP from Becker Underwood South Africa), Penicillium bilaiae (e.g. JUMP START® from Novozymes Biologicals BioAg Group, Canada), Phlebiopsis gigantea (e.g. ROTSTOP® from Verdera, Finland), potassium silicate (e.g. Sil-MATRIX™ from Certis LLC, USA), Pseudozyma flocculosa (e.g. SPORODEX® from Plant Products Co. Ltd., Canada), Pythium oligandrum DV74 (e.g. POLYVERSUM® from Remeslo SSRO, Biopreparaty, Czech Rep.), Reynoutria sachlinensis extract (e.g. REGALIA® from Marrone Biolnnovations, USA), Rhizobium leguminosarum bv. phaseolii (e.g. RHIZO-STICK from Becker Underwood, USA), R. I. trifolii (e.g. DORMAL from Becker Underwood, USA), R. I. bv. viciae (e.g. NODULATOR from Becker Underwood, USA), Sinorhizobium meliloti (e.g.
DORMAL ALFALFA from Becker Underwood, USA; NITRAGIN® Gold from Novozymes Biologicals BioAg Group, Canada), Steinernema feltiae (NEMA->SHIELD® from BioWorks, Inc., USA), Streptomyces lydicus WYEC 108 (e.g. Actinovate® from Natural Industries, Inc., USA, US 5,403,584), S. violaceusniger YCED-9 (e.g. DT-9® from Natural Industries, Inc., USA, US 5,968,503), Talaromyces flavus V117b (e.g. PROTUS® from Prophyta, Germany), Trichoderma asperellum SKT-1 (e.g. ECO-HOPE® from Kumiai Chemical Industry Co., Ltd., Japan), T.
atroviride LC52 (e.g. SENTINEL® from Agrimm Technologies Ltd, NZ), T. fertile JM41 R (e.g. RICHPLUS™ from Becker Underwood Bio Ag SA Ltd, South Africa), T. harzianum T-22 (e.g. PLANTSHIELD® der Firma BioWorks Inc., USA), T. harzianum TH 35 (e.g. ROOT PRO® from Mycontrol Ltd., Israel), T. harzianum T-39 (e.g. TRICHODEX® and TRICHODERMA 2000® from Mycontrol Ltd., Israel and Makhteshim Ltd., Israel), T. harzianum and T. viride (e.g.
TRICHOPEL from Agrimm Technologies Ltd, NZ), T. harzianum ICC012 and T. viride ICC080 (e.g. REMEDIER® WP from Isagro Ricerca, Italy), T. polysporum and T. harzianum (e.g.
BINAB® from BINAB Bio-Innovation AB, Sweden), T. stromaticum (e.g. TRICOVAB® from C.E.P.L.A.C., Brazil), T. virens GL-21 (also named Gliocladium virens) (e.g. SOILGARD® from Certis LLC, USA), T. viride (e.g. T IECOO from Ecosense Labs. (India) Pvt. Ltd., Indien, BIO- CURE® F from T. Stanes & Co. Ltd., Indien), T. viride TV1 (e.g. T. viride TV1 from Agribiotec srl, Italy), Ulocladium oudemansii HRU3 (e.g. BOTRY-ZEN® from Botry-Zen Ltd, NZ), Bacillus amyloliquefaciens AP-136 (NRRL B-50614), B. amyloliquefaciens AP-188 (NRRL B-50615), B. amyloliquefaciens AP-218 (NRRL B-50618), B. amyloliquefaciens AP-219 (NRRL B-50619), B. amyloliquefaciens AP-295 (NRRL B-50620), B. mojavensis AP-209 (No. NRRL B-50616), B. solisalsi AP-217 (NRRL B-50617), B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B-50185)), B. simplex ABU 288 (NRRL B-50340) and B. amyloliquefaciens subsp. plantarum MBI600 (NRRL B-50595) have been mentioned i.a. in US patent appl. 20120149571 , WO 2012/079073. Beauveria bassiana DSM 12256 is known from US200020031495. Bradyrhizobium japonicum USDA is known from US patent 7,262,151. Sphaerodes mycoparasitica IDAC 301008-01 (IDAC = International Depositary Authority of Canada Collection) is known from WO 201 1/022809.
Bacillus amyloliquefaciens subsp. plantarum MBI600 having the accession number NRRL B- 50595 is deposited with the United States Department of Agriculture on Nov. 10, 201 1 under the strain designation Bacillus subtilis 1430. It has also been deposited at The National Collections of Industrial and Marine Bacteria Ltd. (NCIB), Torry Research Station, P.O. Box 31 , 135 Abbey Road, Aberdeen, AB9 8DG, Scotland. under accession number 1237 on December 22, 1986. Bacillus amyloliquefaciens MBI600 is known as plant growth-promoting rice seed treatment from Int. J. Microbiol. Res. ISSN 0975-5276, 3(2) (201 1 ), 120-130 and further described e.g. in US 2012/0149571 A1 . This strain MBI600 is commercially available as liquid formulation product Integral® (Becker-Underwood Inc., USA). Recently, the strain MBI 600 has been reclassified as Bacillus amyloliquefaciens subsp. plantarum based on polyphasic testing which combines classical microbiological methods relying on a mixture of traditional tools (such as culture-based methods) and molecular tools (such as genotyping and fatty acids analysis).
Thus, Bacillus subtilis MBI600 (or MBI 600 or MBI-600) is identical to Bacillus amyloliquefaciens subsp. plantarum MBI600, formerly Bacillus subtilis MBI600.
Metarhizium anisopliae IMI33 is commercially available from Becker Underwood as product Green Guard. M. anisopliae var acridium strain IMI 330189 (NRRL-50758) is commercially available from Becker Underwood as product Green Muscle.
Bacillus subtilis strain FB17 was originally isolated from red beet roots in North America (System Appl. Microbiol 27 (2004) 372-379). This Bacillus subtilis strain promotes plant health (US 2010/0260735 A1 ; WO 201 1/109395 A2). B. subtilis FB17 has also been deposited at American Type Culture Collection (ATCC), Manassas, VA, USA, under accession number PTA- 1 1857 on April 26, 2011. Bacillus subtilis strain FB17 may also be referred to as UD1022 or UD10-22.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from the groups ll-M.Y-1 to ll-M.Y-2:
ll-M.Y-1 :Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity:
Bacillus firmus St 1582, B. thuringiensis ssp. israelensis SUM-6218, B. t. ssp. galleriae SDS-502, B. t. ssp. kurstaki, Beauveria bassiana GHA, B. bassiana H 123, B. bassiana DSM 12256, B. bassiana PRPI 5339, Burkholderia sp. A396, Chromobacterium subtsugae P AA4-1T, Cydia pomonella granulosis virus isolate V22, Isaria
fumosorosea Apopka-97, Lecanicillium longisporum KV42, L. longisporum KV71 , L. muscarium (formerly Verticillium lecanii), Metarhizium anisopliae FI-985, M. anisopliae FI-1045, M. anisopliae F52, M. anisopliae ICIPE 69, M. anisopliae var. acridum IMI 330189, Paecilomyces fumosoroseus FE 9901 , P. lilacinus DSM 15169, P. lilacinus
BCP2, Paenibacillus poppiliae Dutky-1940 (NR L B-2309 = ATCC 14706), P. poppiliae KLN 3, P. poppiliae Dutky 1 , Pasteuria spp. Ph3, P. nishizawae PN-1 , P. reneformis Pr- 3, P. usagae, Pseudomonas fluorescens CL 145A, Steinernema feltiae, Streptomces galbus;
ll-M.Y-2:Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1 -yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,1 1 ,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1 -ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1-ol, R-1 -octen-3-ol, pentatermanone, potassium silicate, sorbitol actanoate, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12-tetradecadien-1- yl acetate, Z-7-tetradecen-2-one, Z-9-tetradecen-1-yl acetate, Z-11-tetradecenal, Z-11 - tetradecen-1 -ol, Acacia negra extract, extract of grapefruit seeds and pulp, extract of Chenopodium ambrosiodae, Catnip oil, Neem oil, Quillay extract, Tagetes oil;
According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from group ll-M.Y-1.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is selected from ll-M.Y-2.
According to one embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus amyloliquefaciens subsp. plantarum MBI600. These mixtures are particularly suitable in soybean.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is B. pumilus strain INR-7 (otherwise referred to as BU-F22 (NRRL B-50153) and BU-F33 (NRRL B- 50185; see WO 2012/079073). These mixtures are particularly suitable in soybean and corn. According to another embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus pumilus, preferably B. pumilis strain INR-7 (otherwise referred to as BU-F22 (NRRL B- 50153) and BU-F33 (NRRL B-50185). These mixtures are particularly suitable in soybean and corn.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is Bacillus simplex, preferably B. simplex strain ABU 288 (NRRL B-50340). These mixtures are particularly suitable in soybean and corn.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is selected from Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum; mixture of T. harzia-mum and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens) and T. viride; preferably Trichoderma fertile, in particular T. fertile strain JM41 R. These mixtures are particularly suitable in soybean and corn. According to another embodiment of the inventive mixtures, the at least one biopesticide II is Sphaerodes mycoparasitica, preferably Sphaerodes mycoparasitica strain IDAC 301008-01 (also referred to as strain SMCD2220-01). These mixtures are particularly suitable in soybean and corn.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is Beauveria bassiana, preferably Beauveria bassiana strain PPRI5339. These mixtures are particularly suitable in soybean and corn.
According to another embodiment of the inventive mixtures, the at least one biopesticide II is Metarhizium anisopliae or M. anisopliae var. acridium, preferably selectged from M anisolpiae strain IMI33 and M. anisopliae var. acridium strain IMI 330189. These mixtures are particularly suitable in soybean and corn.
According to another embodiment of the inventive mixtures, Bradyrhizobium sp. (meaning any Bradyrhizobium species and/or strain) as biopesticide II is Bradyrhizobium japonicum (B.
japonicum). These mixtures are particularly suitable in soybean. Preferably B. japonicum is not one of the strains TA-1 1 or 532c. B. japonicum strains were cultivated using media and fermentation techniques known in the art, e.g. in yeast extract-mannitol broth (YEM) at 27°C for about 5 days.
References for various B. japonicum strains are given e.g. in US 7,262,151 (B. japonicum strains USDA 1 10 (= II TA 2121 , SEMIA 5032, RCR 3427, ARS 1-110, Nitragin 61A89; isolated from Glycine max in Florida in 1959, Serogroup 1 10; Appl Environ Microbiol 60, 940-94, 1994), USDA 31 (= Nitragin 61A164; isolated from Glycine max in Wisoconsin in 1941 , USA,
Serogroup 31 ), USDA 76 (plant passage of strain USDA 74 which has been isolated from Glycine max in California, USA, in 1956, Serogroup 76), USDA 121 (isolated from Glycine max in Ohio, USA, in 1965), USDA 3 (isolated from Glycine max in Virginia, USA, in 1914,
Serogroup 6) and USDA 136 (= CB 1809, SEMIA 586, Nitragin 61A136, RCR 3407; isolated from Glycine max in Beltsville, Maryland in 1961 ; Appl Environ Microbiol 60, 940-94, 1994). USDA refers to United States Department of Agriculture Culture Collection, Beltsville, Md., USA (see e.g. Beltsville Rhizobium Culture Collection Catalog March 1987 ARS-30). Further suitable B. japonicum strain G49 (INRA, Angers, France) is described in Fernandez-Flouret, D. & Cleyet- Marel, J. C. (1987) C R Acad Agric Fr 73, 163-171 ), especially for soybean grown in Europe, in particular in France. Further suitable B. japonicum strain TA-1 1 (TA1 1 NOD+) (NRRL B-18466) is i.a. described in US 5,021 ,076; Appl Environ Microbiol (1990) 56, 2399-2403 and
commercially available as liquid inoculant for soybean (VAULT® NP, Becker Underwood, USA). Further B. japonicum strains as example for biopesticide II are described in US2012/0252672A. Further suitable and especially in Canada commercially available strain 532c (The Nitragin Company, Milwaukee, Wisconsin, USA, field isolate from Wisconsin; Nitragin strain collection No. 61A152; Can J Plant Sci 70 (1990), 661-666).
Other suitable and commercially available B. japonicum strains (see e.g. Appl Environ Microbiol 2007, 73(8), 2635) are SEMIA 566 (isolated from North American inoculant in 1966 and used in Brazilian commercial inoculants from 1966 to 1978), SEMIA 586 (= CB 1809; originally isolated in Maryland, USA but received from Austrailia in 1966 and used in Brazilian inoculants in 1977), CPAC 15 (= SEMIA 5079; a natural varaiant of SEMIA 566 used in commercial inoculants since 1992) and CPAC 7 (= SEMIA 5080; a natural variant of SEMIA 586 used in commercial inoculants since 1992). These strains are especially suitable for soybean grown in Australia or South America, in particular in Brazil. Some of the abovementioned strains have been reclassified as a novel species Bradyrhizobium elkanii, e.g. strain USDA 76 (Can. J. Microbiol., 1992, 38, 501 -505).
Another suitable and commercially available B. japonicum strain is E-109 (variant of strain USDA 138, see e.g. Eur. J. Soil Biol. 45 (2009) 28-35; Biol Fertil Soils (2011 ) 47:81-89, deposited at Agriculture Collection Laboratory of the Instituto de Microbiologia y Zoologia Agncola (IMYZA), Instituto Nacional de Tecnologi'a Agropecuaria (INTA), Castelar, Argentina). This strain is especially suitable for soybean grown in South America, in particular in Argentina. The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Bradyrhizobium elkanii and Bradyrhizobium liaoningense (B. elkanii and B.
liaoningense), more preferably from B. elkanii. These mixtures are particularly suitable in soybean. B. elkanii and liaoningense were cultivated using media and fermentation techniques known in the art, e.g. in yeast extract-mannitol broth (YEM) at 27°C for about 5 days.
Suitable and commercially available B. elkanii strains are SEMIA 587 and SEMIA 5019 (=29W) (see e.g. Appl Environ Microbiol 2007, 73(8), 2635) and USDA 3254 and USDA 76 and USDA 94. Further commercially available B. elkanii strains are U-1301 and U-1302 (e.g. product Nitroagin® Optimize from Novozymes Bio As S.A., Brazil or NITRASEC for soybean from LAGE y Cia, Brazil). These strains are especially suitable for soybean grown in Australia or South America, in particular in Brazil.
The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Bradyrhizobium japonicum (B. japonicum) and further comprisies a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis- jasmone, preferably methyl-jasmonate or cis-jasmone.
The present invention also relates to mixtures, wherein biopesticide II is selected from
Bradyrhizobium sp. (Arachis) (B. sp. Arachis) which shall describe the cowpea miscellany cross- inoculation group which includes inter alia indigenous cowpea bradyrhizobia on cowpea (Vigna unguiculata), siratro (Macroptilium atropurpureum), lima bean (Phaseolus lunatus), and peanut (Arachis hypogaea). This mixture comprising as biopesticide II B. sp. Arachis is especially suitable for use in peanut, Cowpea, Mung bean, Moth bean, Dune bean, Rice bean, Snake bean and Creeping vigna, in particular peanut.
Suitable and commercially available B. sp. (Arachis) strain is CB1015 (= IITA 1006, USDA 3446 presumably originally collected in India; from Australian Inoculants Research Group; see e.g. http://www.qaseeds.com.au/inoculant_applic.php; Beltsville Rhizobium Culture Collection Catalog March 1987 USDA-ARS ARS-30). These strains are especially suitable for peanut grown in Australia, North America or South America, in particular in Brazil. Further suitable strain is bradyrhizobium sp. PNL01 (Becker Underwood; ISO Rep Marita McCreary, QC
Manager Padma Somasageran; IDENTIFICATION OF RHIZOBIA SPECIES THAT CAN ESTABLISH NITROGEN-FIXING NODULES IN CROTALARIA LONGIROSTRATA. April 29, 2010, University of Massachusetts Amherst: http://www.wpi.edu/Pubs/E-project/Available/E- project-042810-
163614/unrestricted/Bisson. Mason._ldentification_of_Rhizobia_Species_That_can_Establish_Nit rogen-Fixing_Nodules_in_Crotalia_Longirostrata.pdf). Suitable and commercially available Bradyrhizobium sp. (Arachis) strains especially for cowpea and peanut but also for soybean are Bradyrhizobium SEMIA 6144, SEMIA 6462 (= BR 3267) and SEMIA 6464 (= BR 3262) (deposited at FEPAGRO-MIRCEN, R. Gongalves Dias, 570 Porto Alegre - RS, 90130-060, Brazil; see e.g. FEMS Microbiology Letters (2010) 303(2), 123-131 ; Revista Brasileira de Ciencia do Solo (201 1) 35(3);739-742, ISSN 0100-0683).
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Arachis) and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis-jasmone, preferably methyl-jasmonate or cis-jasmone.
The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Lupine) (also called B. lupini, B. lupines or Rhizobium lupini). This mixture is especially suitable for use in dry beans and lupins.
Suitable and commercially available B. lupini strain is LL13 (isolated from Lupinus iuteus nodules from French soils; deposited at INRA, Dijon and Angers, France;
http://agriculture.gouv.fr/IMG/pdf/ch20060216.pdf). This strain is especially suitable for lupins grown in Australia, North America or Europe, in particular in Europe.
Further suitable and commercially available B. lupini strains WU425 (isolated in Esperance, Western Australia from a non-Australian legume Ornthopus compressus), WSM4024 (isolated from lupins in Australia by CRS during a 2005 survey) and WSM471 (isolated from Ornithopus pinnatus in Oyster Harbour, Western Australia) are described e.g. in Palta J.A. and Berger J.B. (eds), 2008, Proceedings 12th International Lupin Conference, 14-18 Sept. 2008, Fremantle, Western Australia. International Lupin Association, Canterbury, New Zealand, 47-50, ISBN 0- 86476-153-8:
http://www.lupins.org/pdf/conference/2008/Agronomy%20and%20Production/John%20Howieso n%20and%20G%20OHara.pdf; Appl Environ Microbiol (2005) 71 , 7041-7052 and Australian J. Exp. Agricult. (1996) 36(1 ), 63-70.
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Lupine) (B. lupini) and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis- jasmone, preferably methyl-jasmonate or cis-jasmone.
The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Mesorhizobium sp. (meaning any Mesorhizobium species and/or strain), more preferably Mesorhizobium ciceri. These mixtures are particularly suitable in cowpea.
Suitable and commercially available M. sp. strains are e.g. M. ciceri CC1192 (=UPM 848, CECT 5549; from Horticultural Research Station, Gosford, Australia; collected in Israel from Cicer arietinum nodules; Can J Microbial (2002) 48, 279-284) and Mesorhizobium sp. strains
WSM1271 (collected in Sardinia, Italy, from plant host Biserrula pelecinus), WSM 1497
(collected in Mykonos, Greece, from plant host Biserrula pelecinus), M. loti strains CC829 (commerical inoculant for Lotus pedunculatus and L. ulginosus in Australia, isolated from L. ulginosus nodules in USA) and SU343 (commercial inoculant for Lotus corniculatus in Australia; isolated from host nodules in USA) all of which are deposited at Western Australian Soil Microbiology (WSM) culture collection, Australia and/or CSIRO collection (CC), Canberra, Australian Capirtal Territory (see e.g. Soil Biol Biochem (2004) 36(8), 1309-1317; Plant and Soil (201 1 ) 348(1 -2), 231 -243).
Suitable and commercially available M. loti strains are e.g. M. loti CC829 for Lotus
pedunculatus.
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Bradyrhizobium sp. (Lupine) (B. lupini) and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis- jasmone, preferably methyl-jasmonate or cis-jasmone.
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Mesorhizobium huakuii, also referred to as Rhizobium huakuii (see e.g. Appl. Environ.
Microbiol. 2011 , 77(15), 5513-5516). These mixtures are particularly suitable in Astralagus, e.g. Astalagus sinicus (Chinese milkwetch), Thermopsis, e.g. Thermopsis luinoides (Goldenbanner) and alike.
Suitable and commercially available M. huakuii strain is HN3015 which was isolated from Astralagus sinicus in a rice-growing field of Southern China (see e.g. World J. Microbiol.
Biotechn. (2007) 23(6), 845-851 , ISSN 0959-3993).
The present invention also relates to mixtures wherein the at least one biopesticide II is selected from Mesorhizobium huakuii and further comprises a compound III, wherein compound III is selected from jasmonic acid or salts or derivatives thereof including cis-jasmone, preferably methyl-jasmonate or cis-jasmone.
The present invention also relates to mixtures, wherein the at least one biopesticide II is selected from Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A.
halopraeferens, more preferably from A. brasilense, in particular selected from A. brasilense strains BR 1 1005 (SP 245) and AZ39 which are both commercially used in Brazil and are obtainable from EMBRAPA, Brazil. These mixtures are particularly suitable in soybean.
Humates are humic and fulvic acids extracted from a form of lignite coal and clay, known as leonardite. Humic acids are organic acids that occur in humus and other organically derived materials such as peat and certain soft coal. They have been shown to increase fertilizer efficiency in phosphate and micro-nutrient uptake by plants as well as aiding in the development of plant root systems.
Salts of jasmonic acid (jasmonate) or derivatives include without limitation the jasmonate salts potassium jasmonate, sodium jasmonate, lithium jasmonate, ammonium jasmonate, dimethylammonium jasmonate, isopropylammonium jasmonate, diolammonium jasmonate, diethtriethanolammonium jasmonate, jasmonic acid methyl ester, jasmonic acid amide, jasmonic acid methylamide, jasmonic acid-L-amino acid (amide-linked) conjugates (e.g., conjugates with L- isoleucine, L- valine, L-leucine, or L-phenylalanine), 12-oxo-phytodienoic acid, coronatine, coronafacoyl- L-serine, coronafacoyl-L-threonine, methyl esters of 1 - oxo- indanoyl-isoleucine, methyl esters of 1 -oxo-indanoyl-leucine, coronalon (2- [ (6- ethyl-l-oxo- indane-4-carbonyl) -amino] -3- methyl -pentanoic acid methyl ester), linoleic acid or derivatives thereof and cis-jasmone, or combinations of any of the above.
According to one embodiment, the microbial pesticides embrace not only the isolated, pure cultures of the respective micro-organism as defined herein, but also its cell-free extract, its suspensions in a whole broth culture or as a metabolite-containing supernatant or a purified metabolite obtained from a whole broth culture of the microorganism or microorganism strain. According to a further embodiment, the microbial pesticides embrace not only the isolated, pure cultures of the respective micro-organism as defined herein, but also a cell-free extract thereof or at least one metabolite thereof, and/or a mutant of the respective micro-organism having all the identifying characteristics thereof and also a cell-free extract or at least one metabolite of the mutant.
"Whole broth culture" refers to a liquid culture containing both cells and media.
"Supernatant" refers to the liquid broth remaining when cells grown in broth are removed by centrifugation, filtration, sedimentation, or other means well known in the art.
The term "metabolite" refers to any compound, substance or byproduct produced by a microorganism (such as fungi and bacteria) that has improves plant growth, water use efficiency of the plant, plant health, plant appearance, or the population of beneficial microorganisms in the soil around the plant activity.
The term "mutant" refers a microorganism obtained by direct mutant selection but also includes microorganisms that have been further mutagenized or otherwise manipulated (e.g., via the introduction of a plasmid). Accordingly, embodiments include mutants, variants, and or derivatives of the respective microorganism, both naturally occurring and artificially induced mutants. For example, mutants may be induced by subjecting the microorganism to known mutagens, such as N-methyl-nitrosoguanidine, using conventional methods.
According to the invention, the solid material (dry matter) of the biopesticides (with the exception of oils such as Neem oil, Tagetes oil, etc.) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction medium or the suspension medium in case of liquid formulations of the microbial pesticides).
In accordance with the present invention, the weight ratios and percentages used herein for biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
For microbial pesticides, weight ratios and/or percentages refer to the total weight of a preparation of the respective biopesticide with at least 1 x 106 CFU/g ("colony forming units per gram total weight"), preferably with at least 1 x 108 CFU/g, even more preferably from 1 x 108 to 1 x 1012 CFU/g dry matter. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here CFU may also be understood as number of (juvenile) individual nematodes in case of (entomo-'pathogenic) nematode biopesticides, such as Steinernema feltiae.
Herein, microbial pesticides may be supplied in any physiological state such as active or dormant. Such dormant active component may be supplied for example frozen, dried, or lyophilized or partly desiccated (procedures to produce these partly desiccated organisms are given in WO2008/002371 ) or in form of spores.
Microbial pesticides used as organism in an active state can be delivered in a growth medium without any additional additives or materials or in combination with suitable nutrient mixtures. According to a further embodiment, microbial pesticides are delivered and formulated in a dormant stage, more preferably in form of spores. The total weight ratios of compositions, which comprise a microbial pesticide as component 2, can be determined based on the total weight of the solid material (dry matter) of component 1 ) and using the amount of CFU of component 2) to calclulate the total weight of component 2) with the following equation that 1 x 109 CFU equals one gram of total weight of component 2). According to one embodiment, the compositions, which comprise a microbial pesticide, comprise between 0.01 and 90% (w/w) of dry matter (solid material) of component 1 ) and from 1 x 105 CFU to 1 x 1012 CFU of component 2) per gram total weight of the composition.
According to another embodiment, the compositions, which comprise a microbial pesticide, comprise between 5 and 70% (w/w) of dry matter (solid material) of component 1 ) and from 1 x 106 CFU to 1 x 1010 CFU of component 2) per gram total weight of the composition.
According to another embodiment, the compositions, wherein one component is a microbial pesticide, comprise between 25 and 70% (w/w) of dry matter (solid material) of component 1 ) and from 1 x 107 CFU to 1 x 109 CFU of component 2) per gram total weight of the composition. In the case of mixtures comprising a microbial pesticide, the application rates preferably range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 101 1 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
In the case of mixtures comprising microbial pesticides, the application rates with respect to plant propagation material preferably range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 1011 CFU/seed. In the case of microbial pesticides, the application rates with respect to plant propagation material also preferably range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1011 CFU per 100 kg of seed.
In another embodiment of the invention, the compound (II) pesticides, together with which the compounds of formula I may be used according to the purpose of the present invention, and with which potential synergistic effects with regard to the method of uses might be produced, are selected from from group F consisting of
Respiration Inhibitors
Inhibitors of complex III at Qo site selected from the group of strobilurins including azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, mandestrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/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 selected from famoxadone, fenamidone; Inhibitors of complex II selected from the group of carboxamides,
including carboxanilides selected from benodanil, benzovindiflupyr, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isofetamid, 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 (fluxapyroxad), N-(4'- trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1-methyl-1 H pyrazole-4- carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H- pyrazole-4 carboxamide, 3 (difluoromethyl)-1-methyl-N-(1 ,1 ,3-trimethyhindan- 4-yl)pyrazole-4-carboxamide, 3 (trifluoromethyl)-1 -methyl-N-(1 ,1 ,3- trimethyhindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pynazole-4-carboxamide, S-itrifluorometh-'y^-l ,5- dimethyl-N-(1 ,1 ^-trimethylindan^-y^pyrazole^-carboxamide, 3- (difluoro^methylj-l ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4 yl)pyrazole-4- carboxamide, 3-(trifluorometl"Hyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4- y -'pyrazole^-carboxamide, 1 ,3,5-trhmethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3- dimethyl-pyrazole^-carbox-'amide, N-[2-(2,4-dichlorophenyl)-2-methoxy-1 - methyl-ethyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide;
Inhibitors of complex III at Qi site including cyazofamid, amisulbrom,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]- 6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8- benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8- benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8- benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, 3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl- 4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate;
Other respiration inhibitors (complex I uncouplers), including diflumetorim; (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)- phenyl]-ethyl}-amine; tecnazen; ametoctradin; silthiofam;
and including nitrophenyl derivates selected from binapacryl, dinobuton, dinocap, fluazinam, ferimzone; nitrthal-isopropyl,
and including organometal compounds selected from fentin salts, including fentin-acetate, fentin chloride or fentin hydroxide;
Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors,
including triazoles selected from azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, 1 -[re/- (2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3/?)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 1 -[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1 - yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 - yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 - (1 ,2,4-triazol-1-yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]- 1 -(1 ,2,4-triazol-1-yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-3- methyl-1-(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2-ol; and including imidazoles selected from imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;
and including pyrimidines, pyridines and piperazines selected from fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol;
Delta14-reductase inhitors,
including morpholines selected from aldimorph, dodemorph, dodemorph- acetate, fenpropimorph, tridemorph;
and including piperidines selected from fenpropidin, piperalin;
and including spiroketalamines selected from spiroxamine;
Inhibitors of 3-keto reductase including hydroxyanilides selected from fenhexamid;
Nucleic acid synthesis inhibitors
RNA, DNA synthesis inhibitors,
including phenylamides or acyl amino acid fungicides selected from benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
and including isoxazoles and iosothiazolones selected from hymexazole, octhilinone;
DNA topisomerase inhibitors selected from oxolinic acid;
Nucleotide metabolism inhibitors including hydroxy (2-amino)-pyrimidines selected from bupirimate;
Inhibitors of cell division and or cytoskeleton
Tubulin inhibitors:
including benzimidazoles and thiophanates selected from benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; and including triazolopyrimidines selected from 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
including benzamides and phenyl acetamides selected from diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide;
F.IV-3) Actin inhibitors including benzophenones selected from metrafenone;
pyriofenone;
F.V) Inhibitors of amino acid and protein synthesis
F.V-1 ) Methionine synthesis inhibitors including anilino-pyrimidines selected from cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
F.V-2) Protein synthesis inhibitors including antibiotics selected from blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors
F.VI-1 ) MAP / Histidine kinase inhibitors including dicarboximides selected from
fluoroimid, iprodione, procymidone, vinclozolin;
and including phenylpyrroles selected from fenpiclonil, fludioxonil; F.VI-2) G protein inhibitors including quinolines selected from quinoxyfen;
F.VII) Lipid and membrane synthesis inhibitors
F.VI 1-1 ) Phospholipid biosynthesis inhibitors including organophosphorus compounds selected from edifenphos, iprobenfos, pyrazophos;
and including dithiolanes selected from isoprothiolane;
F.VII-2) Lipid peroxidation
including aromatic hydrocarbons selected from dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;
F.VII-3) Carboxyl acid amides (CAA fungicides)
including cinnamic or mandelic acid amides selected from dimethomorph, flumorph, mandiproamid, pyrimorph;
and including valinamide carbamates selected from 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 including carbamates selected from propamocarb, propamocarb-hydrochlorid; F.VII-5) fatty acid amide hydrolase inhibitors: 1 -[4-[4-[5-(2,6-difluorophenyl)-4,5- dihydro-3 isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-
1 H-pyrazol-1 yl]ethanone;
F.VII I) Inhibitors with Multi Site Action
F.VII 1-1 ) Inorganic active substances selected from Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VII I-2) Thio- and dithiocarbamates selected from ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
F.VII I-3) Organochlorine compounds including phthalimides, sulfamides, chloronitriles selected from anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyW-methyl- benzenesulfonamide;
F.VIII-4) Guanidines selected from guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), dithianon, 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6- c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
F.VIII-5) Ahtraquinones selected from dithianon;
F.IX) Cell wall synthesis inhibitors
F.IX-1 ) Inhibitors of glucan synthesis selected from validamycin, polyoxin B;
F.IX-2) Melanin synthesis inhibitors selected from pyroquilon, tricyclazole,
carpropamide, dicyclomet, fenoxanil;
F.X) Plant defence inducers
F.X-1 ) Salicylic acid pathway selected from acibenzolar-S-methyl;
F.X-2) Others selected from probenazole, isotianil, tiadinil, prohexadione-calcium;
including phosphonates selected from fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxathiapiprolin, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1-yl]-
1 - [4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]^,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3- thiazol-2-yl)piperidin-1-yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1-yl]- 1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yl-oxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-
1 ,3-th azol-2-yl)piperidin-1-yl]ethanone, 2 [3,5-bis(difluoromethyl)-1 H-pyrazol- l -yl]-! -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yl-oxy)phenyl]-4,5-dihydro-1 ,2-oxazol- 3-yl}-1 ,3-thiazol-2 yl)piperidin-1-yl]ethanone, 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-trifluoro- methyl-1 H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4- tetrahydronaphthalen-1-yl]-4-thiazolecarboxamide, 3-[5-(4-chloro-phenyl)-2,3- dimethyl-isoxazolidin-3 yl]-pyridine, pyrisoxazole, 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, ethyl (Z)
3 amino-2-cyano-3-phenyl-prop-2-enoate , tert-butyl N-[6-[[(Z)-[(1 - methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate , pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]- 2-pyridyl]carbamate , 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro- phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol , 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihydroiso-'quinolin-l-y quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4- dihydroisoquinolin-l -yl^quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4- dihydroisoquinolin-1 -yl)quinoline;
F.XII) Growth regulators:
abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, 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.XIII) Biopesticides
F.XII 1-1 ) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus amyloliquefaciens, B. mojavensis, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavibacter michiganensis (bacteriophages), Coniothyrium minitans,
Cryphonectria parasitica, Cryptococcus albidus, Fusarium oxysporum, Clonostachys rosea f. catenulate (also named Gliocladium catenulatum), Gliocladium roseum, Metschnikowia fructicola, Microdochium dimerum, Paenibacillus polymyxa, Pantoea agglomerans, Phlebiopsis gigantea, Pseudozyma flocculosa, Pythium oligandrum, Sphaerodes mycoparasitica,
Streptomyces lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum; mixture of T. harzianum and T. viride; mixture of T. polysporum and T. harzianum; T. stromaticum, T. virens (also named Gliocladium virens), T. viride, Typhula phacorrhiza, Ulocladium oudema, U. oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
F.XIII-2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant
defense activator activity: chitosan (hydrolysate), jasmonic acid or salts or derivatives thereof, laminarin, Menhaden fish oil, natamycin, Plum pox virus coat protein, Reynoutria sachlinensis extract, salicylic acid, tea tree oil;
F.XIII-3) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity: Azospirillum amazonense A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium sp., B. japonicum, Glomus intraradices, Mesorhizobium sp., Paenibacillus alvei, Penicillium bilaiae, Rhizobium leguminosarum bv. phaseolii, R. I. trifolii, R. I. bv. viciae, Sinorhizobium meliloti;
F.XIII-4) Biochemical pesticides with plant stress reducing, plant growth regulator and/or plant yield enhancing activity: abscisic acid, aluminium silicate (kaolin),
3-decen-2-one, homobrassinlide, humates, lysophosphatidyl ethanolamine, polymeric polyhydroxy acid, Ascophyllum nodosum (Norwegian kelp, Brown kelp) extract and Ecklonia maxima (kelp) extract. The commercially available compounds II of the group F listed above may be found in The
Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (2011 ) among other publications. Their preparation and their activity against harmful fungi is known (cf.:
http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by lUPAC nomenclature, their preparation and their fungicidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP A 141 317; EP-A 152 031 ; EP-A 226 917; EP A 243 970; EP A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A 1 035 122; EP A 1 201 648; EP A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657).
The biopesticides of group F.XIII are disclosed above in the paragraphs about biopesticides from group ll-M.Y.
Examples
The present invention is now illustrated in further detail by the following examples.
The compounds I of formula I can be accomplished according to standard methods of organic chemistry, e.g. by the methods or working examples described in WO 2007/006670,
PCT/EP2012/065650, PCT/E P2012/065651.
The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
A group of especially preferred compounds of formula I are compounds of formula IA-1 as listed in table C above. Method A: Analytical HPLC column: RP-18 column Chromolith Speed ROD from Merck KgaA (Germany). Elution: acetonitrile + 0.1 % trifluoroacetic acid (TFA) / water + 0.1 % trifluoroacetic acid (TFA) in a ratio of from 5:95 to 95:5 in 5 minutes at 40 °C.
Method B: Analytical UPLC column: Phenomenex Kinetex 1 ,7 pm XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0,8-1 ,0ml_/min in 1 ,50 minutes at 60°C.
MS-method: ESI positive.
1H-NMR. The signals are characterized by chemical shift (ppm) vs. tetramethylsilane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.
Preparation Examples:
logP determinations were performed via capillary electrophorese on a cePro9600™ from CombiSep.
Starting materials
6,8-dichloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione and 6-chloro-8-methyl-1 H-3,1- benzoxazine-2,4-dione were prepared according to WO 2007/43677.
S,S-Diisopropyl-S-aminosulfonium 2,4,6-trimethylphenylsulfonat was prepared according to Y. Tamura et al, Tetrahedron 1975, 31 , 3035-3040.
2-(3-Chloropyridin-2-yl)-5-bromo-2H-pyrazole-3-carbonyl chloride was prepared according to WO 2007/24833. Preparation Examples P.1 to P.4
Example P.1 : S,S-Dimethyl sulfinium sulfate
To a solution of sodium methylate (15.76 g of a 30% solution in methanol, 87.54 mmol, 1.100 equiv.) in methanol (60 ml_) was added dimethyl sulphide (5.44 g, 6.40 ml_, 87.6 mmol, 1.10 equiv.) at -5-0°C. To this mixture was added a pre-cooled solution (-20°C) of
hydroxylamine-O-sulfonic acid (9.00 g, 79.6 mmol) in methanol (60 ml_) and the internal temperature was maintained at -5-0°C. After stirring at room temperature overnight, all solids were removed by filtration. The filtrate was concentrated in vacuo and the residue was triturated with acetonitrile (50 ml_) to yield the title compound (7.88 g, 39%).
The following compounds were prepared by analogy to example P.1 :
S,S-diethyl sulfinium sulfate
S-ethyl-S-isopropyl sulfinium sulfate
S,S-diisopropyl sulfinium sulfate
S,S-bis(2-cyclopropylmethyl) sulfinium sulfate
S,S-bis(2-cyclopropylethyl) sulfinium sulfate
S,S-bis(cyclobutylmethyl) sulfinium sulfate
S,S-bis(cyclopentylmethyl) sulfinium sulfate S-cyclopropylmethyl-S-ethyl sulfinium sulfate
S-(2-cyclopropylethyl)-S-ethyl sulfinium sulfate
S-(2-cyclopropylethyl)-S-isopropyl sulfinium sulfate
S-(1-cyclopropylethyl)-S-isopropyl sulfinium sulfate
S-cyclobutylmethyl-S-ethyl sulfinium sulfate
S-cyclopentylmethyl-S-ethyl sulfinium sulfate
S-cyclopropylmethyl-S-isopropyl sulfinium sulfate
S-cyclobutylmethyl-S-isopropyl sulfinium sulfate
S-cyclopentylmethyl-S-isopropyl sulfinium sulfate
S,S-di-n-propyl sulfinium sulfate
5- vinyl-S-ethyl sulfinium sulfate
Example P.2: 8-Bromo-6-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione
To a solution of 2-amino-3-bromo-5-chlorobenzoic acid (10.0 g, 39.9 mmol) in dioxane (170 mL) was added phosgene (20% in toluene, 42.0 mL, 79.9 mmol) over a period of 15 mins. The reaction was stirred at ambient temperature for 48 h and then concentrated in vacuo. The resulting solid was crushed and further dried in vacuo to yield the desired product (12.6 g, 1 14%) which was used in the subsequent step without further purification. The following compounds were prepared by analogy to example P.2:
6,8-dichloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6,8-dibromo-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6- Bromo-8-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
8-Bromo-6-chloro-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-chloro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-bromo-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-cyano-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-chloro-8-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
8-chloro-6-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-bromo-8-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
8-bromo-6-trifluoromethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
8-chloro-6-cyano-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-chloro-8-methoxy-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-chloro-8-cyclopropyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-chloro-8-ethyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-difluoromethoxy-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-cyano-8-methoxy-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-fluoro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-iodo-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-nitro-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-(5-chloro-2-thienyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-(3-pyrazol-1 H-yl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-(3-isoxazolyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione, 6-(hydroxyiminomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-(methoxyiminomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione,
6-(dimethylhydrazonomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione and
6-(2,2,2-trifluoroethylhydrazonomethyl)-8-methyl-1 H-benzo[d][1 ,3]oxazine-2,4-dione.
Example P.3: 1-(3-chloro-2-pyridyl)-3-trifluoromethyl-1 H-pyrazol
a) 2.71 kg of 1 ,1 ,1-trifluoro-4-methoxy-but-3-en-2-one, 2,44 kg of ethanol and 3.10 kg of water were charged into a reaction vessel. 20 ml of concentrated hydrochloric acid and 0,80 kg of hydrazine hydrate were successively added and the mixture was heated to reflux for 4 h. The mixtures was allowed to cool and neutralized by addition of 10 % aqueous NaOH to about pH 4- 5. Then the mixture was evaporated. Toluene was added and the mixture was again evaporated to yield 2 kg of raw 3-trifluoromethylpyrazole with a purity of > 85 %.
b) 1 .72 kg (10.75 mol) of the raw 3-trifluoromethylpyrazole obtained in step a), 1.75 kg (1 1.83 mol) of 2,3-dichloropyridine and 4.73 kg of dimethyl formamide were charged to a reaction vessel. 2.97 kg (21.50 mol) of potassium carbonate were added, the mixture was heated to 120°C with stirring and kept at 120-125°C for further 3 h. The reaction mixtures was cooled to 25°C and poured into 20 I of water. The thus obtained mixture was extracted twice with 5 L of tert.-butylmethyl ether. The combined organic phases were washed with 4 I of water and then evaporated to dryness. Toluene was added and the mixture was again evaporated to dryness. Thereby, the 2.7 kg of the title compound was obtained (purity > 75% as determined by GC; yield 81.5%). The product can be purified by distillation.
1H-NMR (400 MHz, CDCb): δ [delta] = 6.73 (d, 1 H), 7.38 (d, 1 H), 7.95 (m, 1 H), 8.14 (m, 1 H), 8.46 (m, 1 H). Example P.4: 2-(3-Chloropyridin-2-yl)-5-trifluoromethyl-2H-pyrazole-3-carbonyl chloride
In a reaction vessel equipped with a thermometer, septum, nitrogen inlet and stirring bar, 10.0 g (40.4 mmol) of 1 -(3-chloro-2-pyridyl)-3-trifloromethyl-1 H-pyrazole were dissolved in 50 ml of dry dimethoxyethane. By means of a syringe, 40.4 ml of a 2 M solution (80.8 mmol, 2.0 equiv.) of isopropyl magnesium chloride in tetrahydrofuran were added dropwise with stirring, while cooling the vessel with an ice bath and keeping the internal temperature at about 5°C. The mixture was stirred for further 2 hours at 5°C. Then the ice-bath was removed and carbon dioxide was bubbled through mixture causing an increase of the temperature up to 28°C. After 10 minutes, the exothermic reaction has ceased, and, the mixture was cooled and all volatiles were removed by evaporation. The residue containing the carboxylate compound l-A was taken up in 50 ml_ of dichloromethane and one drop of dry DMF was added. To this mixture, 14.41 g (121.2 mmol, 3.0 equiv.) of thionyl chloride were added and heated to reflux for 3 hours. After cooling, the resulting precipitate was removed by filtration and the mother liquid was concentrated in vacuum to obtain 13.0 g of the title compound (purity >85%, yield 100%) which was used in the next step without further purification.
H-NMR (400 MHz, CDCI3): 5[delta] = 7.43-7.54 (m, 2H), 7.93 (d, 1 H), 8.52 (m, 1 H).
Example P.5: 2-amino-5-chloro-N-(dimethyl- 4-sulfanylidene)-3-methyl-benzamide
To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (3.00 g, 12.8 mmol) in dichloromethane (40 ml_) was added dimethyl sulfinium sulfate (2.25 g, 8.93 mmol, 0.70 equiv.) and potassium tert-butylate (1.58 g, 14.0 mmol, 1.10 equiv.) at room temperature. The mixture was stirred for 1.5 h, upon which water was added and the layers were separated. The aqueous layer was extracted with dichloromethane, combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was purified by flash-chromatography on silica gel to yield the title compound (2.63 g, 84%).
Characterization by HPLC-MS: 1.855 min, M = 245.00.
Example P.6: 2-amino-5-chloro-N-(bis-2-methylpropyl^4-sulfanylidene)-3-methyl-benzamide To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (3.00 g, 12.8 mmol) in dichloromethane (40 ml_) was added bis-2-methylpropyl sulfinium sulfate (3.76 g, 8.93 mmol, 0.70 equiv.) and potassium tert-butylate (1 .58 g, 14.0 mmol, 1.10 equiv.) at room temperature. The mixture was stirred for 1.5 h, upon which water was added and the layers were separated. The aqueous layer was extracted with dichloromethane, combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was purified by flash- chromatography on silica gel to yield the title compound (2.89 g, 69%).
Characterization by 1H-NMR (400 MHz, DMSO-afe): 5[delta] = 1.04 (m, 12 H), 2.06 (s, 3H), 2.96
(m, 2H), 3.01 (m, 2H), 6.62 (br. s, 2H), 7.03 (s, 1 H), 7.72 (s, 1 H).
Example P.7: 2-amino-5-chloro-N-(diethyl^4-sulfanylidene)-3-methyl-benzamide
To a solution of 6-chloro-8-methyl-1 H-3,1 -benzoxazine-2,4-dione (2 g, 0.01 mol) in anhydrous propylene carbonate (30 ml_) was added bis-2-ethyl sulfinium sulfate (2.04 g, 0.01 mol, 0.70 equiv.) and triethyl amine (1.38 ml_, 1.0 g g, 0.01 mol, 1.05 equiv.) at room temperature. The mixture was stirred for 4.5 h, and then added dropwise to ice-water. The mixture was extracted with dichloromethane and the combined organic layers were dried over sodium sulphate and concentrated in vacuo. The residue was triturated with ether to yield the title compound (1.43 g, 55%).
Characterization by 1H-NMR (400 MHz, CDCI3): 5[delta] = 1.39 (t, 6 H), 2.13 (s, 3H), 3.02 (q, 4H), 5.95 (br. S, 2H), 7.01 (s, 1 H), 7.98 (s, 1 H).
Example P.8: 2-amino-3,5-dichloro-N-(bis-2-methylpropyl- 4-sulfanylidene)-benzamide
The title compound was prepared by analogy to the method of example P.6
Yield: 60%
Characterization by H-NMR (400 MHz, DMSO-de): 5[delta] = 1.23 (d, 6H), 1.38 (d, 6H), 3.42 (m, 2H), 7.02 (br. s, 2H), 7.41 (s, 1 H), 7.95 (s, 1 H). Example P.9: 2-amino-3,5-dibromo-N-(bis-2-methylpropyl^4-sulfanylidene)-benzamide The title compound was prepared by analogy to the method of example P.6
Yield: 66%
Characterization by HPLC-MS: 3.409 min, m/z = 410.90 (Method A)
Preparation of the compounds of formula IA-1 (Examples 1 to 4) Example 1 : 2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(diethyl- 4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-16) To a suspension of potassium carbonate (8.08 g, 58.5 mmol, 1.50 equiv) and 2-amino-3,5- dichloro-N-(diethyl- 4-sulfanylidene)benzamide (11.43 g, 38.98 mmol) in acetonitrile (100 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (15.8 g, 43.31 mmol, 1 .10 equiv.) in acetonitrile (50 mL) at room temperature. After 6 h at this temperature, the solids were filtered off. The resulting filtrate was washed with water and dried over Na2SC>4. After filtration, the filtrate was concentrated in vacuum and the resulting solids were crystallized from diisopropyl ether to yield the title compound (19.53 g, 88%).
Characterization by H-NM (400 MHz, DMSO-cfe):
5[delta] = 1.13 (t, 6H), 2.91 (m, 2H), 3.08 (m, 2H), 7.67 (dd, 1 H), 7.77 (s, 2H), 7.89 (s, 1 H), 8.22 (d, 1 H), 8.51 (d, 1 H), 10.73 (s, 1 H).
Example 2: Synthesis of 2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(bis-2-propyl^4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound (I-26) To a suspension of potassium carbonate (0.892 g, 6.46 mmol, 1 .10 equiv) and 2-amino-3,5- dichloro-N-(bis-2-propyl- 4-sulfanylidene)benzamide (2.05 g, 5.87 mmol) in toluene (30 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (2.02 g, 5.87 mmol, 1.00 equiv.) in toluene (20 mL) at 60°C. After 45 min at this temperature, the mixture was cooled and water was added. The resulting precipitate was collected by filtration, washed with water and toluene and dried to obtain the title compound (3.07 g, 84%).
Characterization by HPLC-MS: 1.395 min, M = 602.1 (Method B)
Characterization by 1H-NMR (400 MHz, DMSO-afe):
5[delta] = 1.18 (d, 6H), 1.22 (d, 6H), 3.30 (m, 2H), 7.68 (dd, 1 H), 7.75 (m, 2H), 7.81 (s, 1 H), 8.21 (d, 1 H), 8.54 (d, 1 H), 10.76 (s, 1 H).
Example 3: Synthesis of 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(bis-2-propyl^4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-21 ) To a suspension of potassium carbonate (126.01 g, 911 .76 mmol, 1.30 equiv) and 2-amino-3- methyl-5-chloro-N-(bis-2-propyl^4-sulfanylidene)benzamide (21 1 g, 701 mmol) in
dichloromethane (300 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carbonyl chloride (256.78 g, 771.49 mmol, 1.10 equiv.) in
dichloromethane (200 mL) at room temperature. After 2 h at this temperature, the solids were filtered off. The resulting filtrate was washed with water and dried over Na2S04. After filtration, the filtrate was concentrated in vacuum and the resulting solids were crystallized from diisopropyl ether to yield the title compound (344.2 g, 85%).
Characterization by HPLC-MS: 1.303 min, M= 574.3 (Method B)
Characterization by H-NMR (400 MHz, DMSO-afe): 5[delta] = 1.20 (d, 6H), 1.30 (d, 6H), 2.15 (s, 3H), 3.30 (m, 2H), 7.41 (s, 1 H), 7.62 (m, 2H), 7.80 (s, 1 H), 8.22 (d, 1 H), 8.52(d, 1 H), 10.88 (s, 1 H).
Example 4a: 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(diethyl^4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-1 1 ) To a suspension of potassium carbonate (0.71 g, 10 mmol, 1.3 equiv) and 2-amino-3-methyl-5- chloro-N-(diethyl- 4-sulfanylidene)benzamide (1.42 g, 3.96 mmol) in propylene carbonate (20 mL) was added a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride (1 .35 g, 4.35 mmol, 1.10 equiv.) in propylene carbonate (10 mL) at room temperature. After 24 h at this temperature, the mixture was poured onto water and spiked with ethanol under vigorous stirring. The resulting solids were collected by filtration and contained pure title compound (1.57 g, 73%).
Characterization by HPLC-MS: 1.19 min, m/z 546.1 (M+H)+; (Method B)
Characterization by H-NMR (500 MHz, DMSO) [delta]: 10.87 (s, 1 H), 8.53 (d, 1 H), 8.22 (d, 1 H), 7.75 (s, 1 H), 7.65 (m, 2H), 7.40 (s, 1 H), 3.09 (m, 2H), 2.92 (m, 2H) 1.15 (m, 6H).
Example 4b: 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(diethyl^4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-1 1 ) To a solution of 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbonyl chloride
(150 g, 435 mmol) in acetonitrile (900 mL) at room temperature was added potassium carbonate (59 g, 427 mmol). A solution of 2-amino-5-chloro-N-(diethyl-sulfanylidene)-3-methyl- benzamide (1 17 g, 427 mmol) in acetonitrile (100 mL) was added dropwise within 1 hour while maintaining a reaction temperature of 25-28°C with occasional cooling (slightly exothermic reaction). The mixture was stirred for 16 hours at room temperature. The reaction mixture was then poured on ice-water mixture (5
L) and the pH was adjusted to 7-8 with concentrated HCI. The mixture stirred for an additional 2 hours. The light brown solid was filtered, washed with water and dried under air to give the crude product (229 g).
3 combined batches of crude product (789 g) were suspended in acetonitrile (2.6 L) and dissolved upon heating at 60°C. After 1 hour of stirring at 60°C the solution was cooled by means of an ice-bath and the thereby formed solid was filtered off. The mother-liquor was concentrated to 300 mL and cooled with ice-bath. Thereby additional solid formed was filtered. The combined solids were washed with cold acetonitrile and dried at 50°C in a vacuum-oven over night to give the title product (703 g, 89%) as a crystalline white solid.
By the methods described in examples 1 to 4 or analogy therof, the compounds of formula (IA- 1 ) summarized in table C were prepared:
Figure imgf000110_0001
Table C
Figure imgf000110_0002
Figure imgf000111_0001
Example for preparation of solvate/co-crystal: Toluene solvates of compound 1-21
The synthesis of 2-(3-chloro-2-pyridyl)-N-[2-methyl-4-chloro-6-[(bis-2-propyl^4- sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-21 ) is done as described above, e.g. as described in Example 3 or in similar ways.
A variety of solvates may be prepared from 1-21 , e.g. the toluene solvates form A and form B (I- 21 -Tol-A and l-21 -Tol-B) as described in the following. l-21 -Tol-A and l-21 -Tol-B are each a stable crystalline form, which forms crystals and thus allows a much easier handling than amorphous 1-21.
The inventive solvates l-21 -Tol-A and l-21 -Tol-B can be identified by means of X-ray powder diffractometry on the basis of its diffraction diagram. Thus, an X-ray powder diffractogram recorded at 25°C using Cu-Ka radiation (1.54178 A) shows at least 2, as a rule at least 4, frequently at least 5, in particular at least 7, especially at least 9 and specifically all of the 10 reflexes detailed in the tables hereinbelow as 20 values, or as interplanar spacings d.
Besides X-ray powder diffractometry, differential scanning calorimetry (DSC) may also be employed for identifying l-21 -Tol-A and 1-21 -Tol-B.
Preparation of toluene solvate form A of 1-21 (l-21 -Tol-A):
100 mg of 1-21 were dissolved in 2 ml of toluene at 60 °C. The warm solution was placed into an ice bath for 2 hours. The precipitated solid was separated by filtration, dried at 25 °C for 12 hours and analysed by XRPD and thermal analyisis. DSC and TGA traces show a desolvation process. The corresponding XRPD is shown in figure 1 and the most relevant diffraction lines are listed in table Xray-l-21 -Tol-A.
Table Xray-l-21 -Tol-A:
Relevant reflections in the XRPD pattern of l-21 -Tol-A 2Θ values d [A]
6,83±0,2° 12,94
1 1 ,44+0,2° 7,74
12,91 ±0,2° 6,86
13,31 ±0,2° 6,65
13,78±0,2° 6,43
15,00±0,2° 5,91
16,86±0,2° 5,26
19,30±0,2° 4,60
22,39±0,2° 3,97
23,35±0,2° 3,81
Preparation of toluene solvate form B of 1-21 (l-21 -Tol-B):
20 mg of 1-21 were dissolved in 1 ml of toluene at 25 °C. The solvent was evaporated at 25 °C. Good quality crystals were obtained and they were analysed by single crystal XRD. The single crystal structure shows the formation on the toluene mono-solvate. The corresponding crystallographic parameters are listed in table Xray-l-21-Tol-B.
Table Xray-l-21 -Tol-A:
Single crystal parameters of l-21 -Tol-B
Figure imgf000112_0001
a,b,c = Length of the edges of the unit cell
α,β,γ = Angles of the unit cell
Z = Number of molecules, in the unit cell
The following figures and examples further illustrate the present invention:
Figure 1 : X-ray Powder Diffractogramm (XRPD) of l-21-Tol-A (Form A)

Claims

We claim:
N-Thio-anthranilamide compounds of formula (I)
Figure imgf000113_0001
wherein
R1 is hydrogen; or Ci-Cio-alkyl, C2-Ci0-alkenyl, C2-Cio-alkynyl, or C3-C8-cycloalkyl, each of which is unsubstituted or substituted with 1 to 5 groups independently selected from halogen, cyano, nitro, hydroxy, Ci-Cio-alkoxy, Ci-Ci0-alkylthio, C1-C10- alkylsulfinyl, Ci-Ci0-alkylsulfonyl, C2-Ci0-alkoxycarbonyl, Ci-Ci0-alkylamino, di(Cr Cio-alkyl)amino and C3-C8-cycloalkylamino; or Ci-Ci0-alkylcarbonyl, C1-C10- alkoxycarbonyl, Ci-Cio-alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl;
A is
Figure imgf000113_0002
wherein # denotes the binding site;
R2 and R3 each independently are R6 or together with the sulfur atom to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, which ring can be fused with one or two saturated, partially unsaturated or unsaturated 5- to 6-membered rings which may contain 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of the above rings are unsubstituted or substituted by any combination of 1 to 6 groups R8;
G is oxygen or sulfur;
R6 is CrC2o-alkyl, C2-C20-alkenyl, C2-C20-alkynyl, C3-C8-cycloalkyl, C3-C8-cycloalkenyl, C3-C8-cycloalkynyl, phenyl, naphthyl, biphenyl, or a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein all of these groups are unsubstituted or substituted by any combination of 1 to 6 groups R8; R8 is R9; or two groups R8 together with the atoms to which they are attached form a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which may contain 1 to 4 heteroatoms /heterogroups selected from oxygen, nitrogen, sulfur, SO and S02, and which ring system is unsubstituted or substituted with any combination of 1 to 6 groups R9.
R9 is R10, R11, -C(=G)R10, -C(=NOR10)R10, -C(=NNR10 2)R10 , -C (=G)OR10, - -
Figure imgf000114_0001
C(=G)NR10 2, -NR10-NR10C(=G)R10, -NR10-N[C(=G)R10]2, -N[(C=G)R10]-NR10 2, -NR10- NR10[(C=G)GR10], -NR10[(C=G)NR10 2, -NR10[C=NR10]R10, -NR10(C=NR10)NR10 2, -O- NR102, -O-NR10(C=G)R10, -SO2NR10 2, -NR10SO2R10, -S02OR10, -OS02R10, -OR10, - NR102, -SR10, -SiR103, -PR10 2, -P(=G)R10, -SOR10, -S02R10, -PG2R10 2, -PG3R10 2, or two groups R9 together are (=G), (=N-R10), (=CR10 2), (=CHR10), or (=CH2);
R10 is CrCio-alkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, C3-C8-cycloalkyl, C4-C8- cycloalkenyl, C3-C8-cycloalkyl- CrC4-alkyl, C4-C8-cycloalkenyl-CrC4-alkyl, C3-C8- cycloalkyl-C2-C4-alkenyl, C4-C8-cycloalkenyl-C2-C4-alkenyl, Ci-Ci0-alkyl-C3-C8- cycloalkyl, C2-Ci0-alkenyl-C3-C8-cycloalkyl, C2-Ci0-alkynyl-C3-C8-cycloalkyl, C1-C10- alkyl-C4-C8-cycloalkenyl, C2-Cio-alkenyl-C4-C8-cycloalkenyl, C2-Ci0-alkynyl-C4-C8- cycloalkenyl,
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein the above groups are unsubstituted or substituted with any combination of from 1 to 6 groups R11;
R11 is halogen, cyano, nitro, hydroxy, mercapto, amino, formyl, Ci-Ci0-alkylcarbonyl, Ci-Cio-alkoxy, C2-Ci0-alkenyloxy, C2-Ci0-alkynyloxy, CrCio-haloalkoxy, C3-Ci0- haloalkenyloxy, C3-Ci0-haloalkynyloxy, C3-C8-cycloalkoxy, C4-C8-cycloalkenyloxy, C3-C8-halocycloalkoxy, C4-C8-halocycloalkenyloxy, C3-C8-cycloalkyl- Ci-C4-alkoxy,
C4-C8-cycloalkenyl-Ci-C4-alkoxy, C3-C8-cycloalkyl- C2-C4-alkenyloxy, C4-C8- cycloalkenyl-C2-C4-alkenyloxy, Ci-Ci0-alkyl-C3-C8-cycloalkoxy, CrCi0-alkenyl-C3- C8-cycloalkoxy, Ci-Ci0-alkynyl-C3-C8-cycloalkoxy, C-i-Cio-alkyl-C3-C8- cycloalkenyloxy, Ci-Ci0-alkenyl-C3-C8-cycloalkenyloxy, CrC4-alkoxy-Ci-Ci0- alkoxy, CrC4-alkoxy-C2-Ci0-alkenyloxy, mono- or di(Ci-Ci0-alkyl)carbamoyl, mono- or di(Ci-Cio-haloalkyl)carbamoyl, mono- or di(C3-C8-cycloalkyl)carbamoyl, Ci-Cio-alkoxycarbonyl, C3-C8-cycloalkoxycarbonyl, Ci-Ci0-alkylcarbonyloxy, C3-C8- cyclo alkylcarbonyloxy, Ci-Ci0-haloalkoxycarbonyl, Ci-Ci0-haloalkylcarbonyloxy, Ci-Cio-alkanamido, Ci-Ci0-haloalkanamido, C2-Ci0-alkenamido, C3-C8- cycloalkanamido, C3-C8-cycloalkyl-Ci-C -alkanamido,
C Cio-alkylthio, C2-Ci0-alkenylthio, C2-Ci0-alkynylthio, Ci-Ci0-haloalkylthio, C2-Ci0- haloalkenylthio, C2-Ci0-haloalkynylthio, C3-C8-cycloalkylthio, C3-C8- cycloalkenylthio, C3-C8-halocycloalkylthio, C3-C8-halocycloalkenylthio, C3-C8- cycloalkyl- Ci-C4-alkylthio, C4-C8-cycloalkenyl-CrC4-alkylthio, C3-C8-cycloalkyl- C2 C4-alkenylthio, C4-C8-cycloalkenyl-C2-C4-alkenylthio, Ci-Ci0-alkyl-C3-C8- cycloalkylthio, Ci-Cio-alkenyl-C3-C8-cycloalkylthio, Ci-Ci0-alkynyl-C3-C8- cycloalkylthio, Ci-Cio-alkyl-C3-C8-cycloalkenylthio, Ci-Ci0-alkenyl-C3-C8- cycloalkenylthio, CrCio-alkylsulfinyl, C2-Cio-alkenylsulfinyl, C2-Ci0-alkynylsulfinyl, Ci-Cio-haloalkylsulfinyl, C2-Ci0-haloalkenylsulfinyl, C2-Ci0-haloalkynylsulfinyl, C3- Cs-cycloalkylsulfinyl, C3-C8-cycloalkenylsulfinyl, C3-C8-halocycloalkylsulfinyl, C3-C8 halocycloalkenylsulfinyl, C3-C8-cycloalkyl- CrC4-alkylsulfinyl, C4-C8-cycloalkenyl- Ci-C4-alkylsulfinyl, C3-C8-cycloalkyl- C2-C4-alkenylsulfinyl, C -C8-cycloalkenyl-C2- C4-alkenylsulfinyl, Ci-Ci0-alkyl-C3-C8-cycloalkylsulfinyl, Ci-Ci0-alkenyl-C3-C8- cycloalkylsulfinyl, Ci-Ci0-alkynyl-C3-C8-cycloalkylsulfinyl, Ci-Ci0-alkyl-C3-C8- cycloalkenylsulfinyl, Ci-Ci0-alkenyl-C3-C8-cycloalkenylsulfinyl, Ci-Ci0-alkylsulfonyl, C2-Cio-alkenylsulfonyl, C2-Ci0-alkynylsulfonyl, C Cio-haloalkylsulfonyl, C2-Ci0- haloalkenylsulfonyl, C2-Ci0-haloalkynylsulfonyl, C3-C8-cycloalkylsulfonyl, C3-C8- cycloalkenylsulfonyl, C3-C8-halocycloalkylsulfonyl, C3-C8-halocycloalkenylsulfonyl, C3-C8-cycloalkyl- C-i-C -alkylsulfonyl, C4-C8-cycloalkenyl-Ci-C4-alkylsulfonyl, C3-C8 cycloalkyl- C2-C4-alkenylsulfonyl, C4-C8-cycloalkenyl-C2-C4-alkenylsulfonyl, C1-C10- alkyl-C3-C8-cycloalkylsulfonyl, Ci-Ci0-alkenyl-C3-C8-cycloalkylsulfonyl, C1-C10- alkynyl-C3-C8-cycloalkylsulfonyl, Ci-Cio-alkyl-C3-C8-cycloalkenylsulfonyl, C1-C10- alkenyl-C3-C8-cycloalkenylsulfonyl, di(Ci-Ci0-alkyl)amino, Ci-Ci0-alkylamino, C2- Cio-alkenylamino, C2-Ci0-alkynylamino, Ci-Ci0-alkyl-C2-Cio-alkenylamino, C1-C10- alkyl-C2-Ci0-alkynylamino, Ci-Ci0-haloalkylamino, C2-Cio-haloalkenylamino, C2- Cio-haloalkynylamino, C3-C8-cycloalkylamino, C3-C8-cycloalkenylamino, C3-C8- halocycloalkylamino, C3-C8-halocycloalkenylamino, C3-C8-cycloalkyl- C1-C4- alkylamino, C4-C8-cycloalkenyl-Ci-C4-alkylamino, C3-C8-cycloalkyl- C2-C4- alkenylamino, C4-C8-cycloalkenyl-C2-C4-alkenylamino, Ci-Ci0-alkyl-C3-C8- cycloalkylamino, Ci-Ci0-alkenyl-C3-C8-cycloalkylamino, CrCi0-alkynyl-C3-C8- cycloalkylamino, Ci-Ci0-alkyl-C3-C8-cycloalkenylamino, Ci-Ci0-alkenyl-C3-C8- cycloalkenylamino, tri(Ci-Cio-alkyl)silyl, aryl, aryloxy, arylthio, arylamino, aryl-Cr C4-alkoxy, aryl-C3-C4-alkenyloxy, aryl-Ci-C4-alkylthio, aryl-C2-C4-alkenylthio, aryl- Ci-C4-alkylamino, aryl-C3-C4-alkenylamino, aryl-di(C-i-C4-alkyl)silyl, triarylsilyl, wherein aryl is phenyl, naphthyl or biphenyl, or
a saturated, partially unsaturated or unsaturated 3- to 8-membered ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein these aryl and these heterocyclic ringsystems are unsubstituted or substituted with any combination of from 1 to 6 groups selected from halogen, cyano, nitro, amino, hydroxy, mercapto, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C8-cycloalkyl, d- C4-alkoxy, Ci-C4-haloalkoxy, CrC4-alkylthio, CrC4-haloalkylthio, di(CrC4- alkyl)amino, Ci-C4-alkylarmino, Ci-C4-haloalkylamino, formyl and Ci-C - alkylcarbonyl;
Q1 and Q2 each independently are hydrogen, halogen, cyano, SCN , nitro, hydroxy, C1-C10 alkyl, Ci-Ci0-haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-C10- haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ci0-alkoxy, C1-C10- haloalkoxy, Ci-Ci0-alkylthio, Ci-Ci0-haloalkylthio, Ci-Ci0-alkylsulfinyl, C1-C10- haloalkylsulfinyl, CrCio-alkylsulfonyl, CrCio-haloalkylsulfonyl, C1-C10- alkylsulfonyloxy, Ci-Ci0-haloalkylsulfonyloxy, Ci-Ci0-alkylamino, di(Ci-Ci0- alkyl)amino, C3-C8-cyclalkylamino, alkylcarbonyl, Ci-Ci0-alkoxycarbonyl, C1-C10- alkylaminocarbonyl, di(Ci-Cio-alkyl)aminocarbonyl, or tri(Ci-Cio)-alkylsilyl, or Q1 and Q2 are each independently phenyl, benzyl or phenoxy, wherein each ring is unsubstituted or substituted with any combination of from 1 to 3 substituents independently selected from the group halogen, cyano, nitro, Ci-Ci0-alkyl, C1-C10- haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0-haloalkynyl,
C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-Ci0-alkoxy, CrCi0-haloalkoxy, C1-C10- alkylthio, CrCio-alkylsulfinyl, CrCio-alkylsulfonyl, CrCio-alkylamino, di(Ci-Cio- alkyl)amino, C3-C8-cycloalkylamino, Ci-Ci0-alkyl-C3-C8-cycloalkylamino, C1-C10- alkylcarbonyl, CrCio-alkoxycarbonyl, Ci-Cio-alkylaminocarbonyl, di(Ci-Cio- alkyl)aminocarbonyl and tri(Ci-Cio)-alkylsilyl;
Q3 is halogen; or Ci-Ci0-alkyl, Ci-C10-haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2- Cio-alkynyl, C3-Ci0-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C1-C10- alkyl-C3-C8-cycloalkyl, Ci-Ci0-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or in- dependency substituted with 1 to 2 groups selected from cyano, Ci-Ci0-alkoxy, C
Cio-haloalkoxy, CrCio-alkylthio, Ci-Cio-haloalkylthio, CrCio-alkylsulfinyl, C1-C10- haloalkylsulfinyl, CrCio-alkylsulfonyl, CrCio-haloalkylsulfonyl, and C1-C10- alkoxycarbonyl; or
Q3 is OR14, S(0)qR14, NR15R16, OS(0)2R17, NR16S(0)2R17, C(S)NH2, C(R18)=NOR18, C3-C8-cycloalkyl-Ci-C4-alkyl, Ci-Ci0-alkylaminothiocarbonyl, or di(CrCi0- alkyl)aminothiocarbonyl;
R14 is CrCio-alkyl, Ci-Cio-haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3- Cio-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C3-C8-cycloalkyl-Ci-C4- alkyl, Ci-C4-alkyl-C3-C8-cycloalkyl, C3-C8-halocycloalkyl-Ci-C4-alkyl, C C4- haloalkyl-C3-C8-cycloalkyl, or Ci-Ci0-haloalkylcarbonyl, each unsubstituted or substituted with 1 R19;
R15 is C Cio-alkyl, Ci-Ci0-haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3- Cio-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, CrC -alkyl-C3-C8- cycloalkyl, Ci-C4-haloalkyl-C3-C8-cycloalkyl, or Ci-Ci0-haloalkylcarbonyl, each unsubstituted or substituted with 1 R19;
R16 is hydrogen; or CrCio-alkyl, Ci-Ci0-haloalkyl, C2-Ci0-alkenyl, C2-C10-haloalkenyl, C2- Cio-alkynyl, C3-Ci0-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-C -alkyl-
C3-C8-cycloalkyl, or Ci-C4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1 R19; R17 is Ci-Cio-alkyl, Ci-Ci0-haloalkyl, C2-Ci0-alkenyl, C2-Cio-haloalkenyl, C2-Ci0-alkynyl, C3- Cio-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkyl-C3-C8- cycloalkyl, or CrC4-haloalkyl-C3-C8-cycloalkyl, each unsubstituted or substituted with 1 R19;
R19 is cyano, nitro, Ci-Ci0-alkoxy, Ci-Ci0-haloalkoxy, Ci-Ci0-alkylthio, Ci-Ci0-haloalkylthio, C Cio-alkylsulfinyl, Ci-Ci0-haloalkylsulfinyl, Ci-Ci0-alkylsulfonyl, C1-C10- haloalkylsulfonyl, Ci-Ci0-alkoxycarbonyl, Ci-Ci0-alkylamino, or di(CrCi0- alkyl)amino; or
R19 is phenyl or a heteroaromatic 5- or 6-membered ring which contains 1 to 4
heteroatoms selected from oxygen, nitrogen, sulfur, the phenyl radical and the heteroaromatic ring being unsubstituted or substituted with any combination of from 1 to 3 groups selected from halogen, cyano, nitro, Ci-Ci0-alkyl, C1-C10- haloalkyl, C2-Ci0-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, CrCi0-alkoxy, CrCi0-haloalkoxy, C1-C10- alkylthio, Ci-C10-alkylsulfinyl, CrCi0-alkylsulfonyl, Ci-C10-alkylamino, di(Ci-C10- alkyl)amino, C3-C8-cycloalkylamino, Ci-Ci0-alkyl-C3-C8-cycloalkylamino, C1-C10- alkylcarbonyl, CrCio-alkoxycarbonyl, Ci-Cio-alkylaminocarbonyl, di(Ci-Cio- alkyl)aminocarbonyl and tri(Ci-Ci0)-alkylsilyl;
R18 is the same or different: hydrogen, Ci-Ci0-alkyl, or C Ci0-haloalkyl; q is 0, 1 or 2;
Q4 is halogen, cyano, nitro, hydroxy, COOH, C(0)NH2, Ci-Cio-alkyl, CrCio-haloalkyl, C2-Cio-alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0-haloalkynyl, C3-C8- cycloalkyl, C3-C8-halocycloalkyl, Ci-Cio-alkoxy, Ci-Cio-haloalkoxy, CrCio-alkylthio, CrCio-haloalkylthio, CrCio-alkylsulfinyl, Ci-Ci0-haloalkylsulfinyl, C1-C10- alkylsulfonyl, Ci-Ci0-haloalkylsulfonyl, Ci-Ci0-alkylamino, di(CrCi0-alkyl)amino, C3- Ce-cycloalkylamino, Ci-Ci0-alkylcarbonyl, CrCio-alkoxycarbonyl C1-C10- alkylaminocarbonyl, di(Ci-Ci0-alkyl)aminocarbonyl or tri(CrCi0)-alkylsilyl; or
Q4 is phenyl, benzyl, benzyloxy, phenoxy, a 5- or 6-membered heteroaromatic ring which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur or an aromatic 8-, 9- or 10-membered fused heterobicyclic ring system which contains 1 to 4 heteroatoms selected from oxygen, nitrogen, sulfur, wherein each of the above ring systems is unsubstituted or substituted with any combination of from 1 to 3 groups selected from halogen, cyano, nitro, Ci-Ci0-alkyl, d-Cio-haloalkyl, C2-C-|0- alkenyl, C2-Ci0-haloalkenyl, C2-Ci0-alkynyl, C3-Ci0-haloalkynyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C Cio-alkoxy, C Cio-haloalkoxy, CrCio-alkylthio, CrCio- alkylsulfinyl, Ci-Cio-alkylsulfonyl, Ci-Ci0-alkylamino, di(Ci-Ci0-alkyl)amino, C3-C8- cycloalkylamino, Ci-Ci0-alkyl-C3-C8-cycloalkylamino, C Ci0-alkylcarbonyl, Ci-C10- alkoxycarbonyl, Ci-Ci0-alkylaminocarbonyl, di(Ci-Ci0-alkyl)aminocarbonyl and tri(C Cio)-alkylsilyl;
X and Y are each independently oxygen or sulfur;
V and V are each independently N or CQ2;
W is N, CH or CQ4; n is 0 or 1 ; p is 0, 1 , 2, 3, or 4; or a stereoisomer, salt, tautomer, or N-oxide, or a polymorphic crystalline form, a co- crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof.
2. Compounds according to claim 1 wherein formula (I) is formula (I-0)
Figure imgf000118_0001
wherein
Q2 is selected from the group consisting of halogen, methyl and halomethyl;
Q1 is selected from the group consisting of hydrogen, halogen, halomethyl and cyano;
R1 is selected from hydrogen, Ci-C6 alkyl, Ci-C6 haloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkinyl, C2-C6-haloalkinyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl,
C(=0)Ra, C(=0)ORb and C(=0)NRcRd;
Q is hydrogen or halogen; R2, R3 are selected independently of one another from the group consisting of hydrogen, CrCio-alkyl, C3-C8-cycloalkyl, C2-Ci0-alkenyl, C2-Ci0-alkynyl, wherein the aforementioned aliphatic and cycloaliphatic radicals may be substituted with 1 to 10 substituents Re, and phenyl, which is unsubstituted or carries 1 to 5 substituents Rf; or
R2 and R3 together represent a C2-C7-alkylene, C2-C7-alkenylene or
C6-C9-alkynylene chain forming together with the sulfur atom to which they are attached a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered saturated, partially unsaturated or fully unsaturated ring, wherein 1 to 4 of the CH2 groups in the C2-C7-alkylene chain or 1 to 4 of any of the CH2 or CH groups in the C2-C7-alkenylene chain or 1 to 4 of any of the CH2 groups in the C6-C9-alkynylene chain may be replaced by 1 to 4 groups independently selected from the group consisting of C=0, C=S, O, S, N, NO, SO, S02 and NH, and wherein the carbon and/or nitrogen atoms in the C2- C7-alkylene, C2-C -alkenylene or Ce-Cg-alkynylene chain may be substituted with 1 to 5 substituents independently selected from the group consisting of halogen, cy- ano, CrC6-alkyl, C C5-haloalkyl, CrC6-alkoxy, Ci-C6-haloalkoxy, CrC6-alkylthio, CrC6-haloalkylthio, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C2-C6-alkenyl, C2-C6- haloalkenyl, C2-C6-alkynyl and C2-C6-haloalkynyl; said substituents being identical or different from one another if more than one substituent is present;
Q3 is selected from the group consisting of bromo, chloro, difluoromethyl, trifluorome- thyl, nitro, cyano, OCH3, OCHF2, OCH2F, OCH2CF3, S(=0)mCH3, and S(=0)mCF3;
Ra is selected from the group consisting of Ci-C3-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3- Ca-cycloalkyl, C C6-alkoxy, C C6-alkylthio, C C6-alkylsulfinyl, CrC6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from d-C4 alkoxy;
phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from CrC6-alkyl, C C6-haloalkyl, CrC6-alkoxy, CrC6-haloalkoxy, (C C6-alkoxy)carbonyl, Ci-C6-alkylamino and di-(Ci-C6-alkyl)amino, Rb is selected from the group consisting of Ci-C3-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-
Ce-cycloalkyl, C C6-alkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, CrC6-alkylsulfonyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 substituents selected from CrC4-alkoxy;
phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from CrC6-alkyl, CrC6-haloalkyl, CrC6-alkoxy, C-i-C6-haloalkoxy and (Ci-C3- alkoxy)carbonyl;
Rc, Rd are, independently from one another and independently of each occurrence, se- lected from the group consisting of hydrogen, cyano, CrC6-alkyl, C2-C6-alkenyl, C2-
C6-alkinyl, C3-C8-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halo- genated and/or may carry 1 or 2 radicals selected from d-C4-alkoxy;
CrC6-alkoxy, C-i-C6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6- alkylsulfonyl, CrC6-haloalkylthio, phenyl, benzyl, pyridyl and phenoxy, wherein the four last mentioned radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from CrC6-alkyl, Ci-C6-haloalkyl, Ci-C6- alkoxy, Ci-C6 haloalkoxy and (CrC6-alkoxy)carbonyl; or
Rc and Rd, together with the nitrogen atom to which they are bound, may form a 3-,
4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring which may additionally contain 1 or 2 further heteroatoms or heteroatom groups selected from N, O, S, NO, SO and S02, as ring members, where the heterocyclic ring may optionally be substituted with halogen, CrCzrhaloalkyl, C1-C4- alkoxy or CrC4-haloalkoxy;
Re is independently selected from the group consisting of halogen, cyano, nitro, -OH, - SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy;
CrC6-alkoxy, CrC6-haloalkoxy, CrC6-alkylthio, CrC6-alkylsulfinyl, Ci-C6- alkylsulfonyl, CrC6-haloalkylthio, -ORa, -NRcRd, -S(0)mRa, -S(0)mNRcRd,
-C(=0)Ra, -C(=0)NRcRd, -C(=0)OR , -C(=S)Ra, -C(=S)NRcRd, -C(=S)OR ,
-C(=S)SRb, -C(=NRc)Rb, -C(=NRc)NRcRd, phenyl, benzyl, pyridyl and phenoxy, wherein the last four radicals may be unsubstituted, partially or fully halogenated and/or carry 1 , 2 or 3 substituents selected from CrC6-alkyl, Ci-C6-haloalkyl, Ci-C6- alkoxy and CrC6-haloalkoxy; or
two vicinal radicals Re together form a group =0, =CH(CrC4-alkyl), =C(Ci-C4- alkyl)C C4-alkyl,
Figure imgf000120_0001
Rf is independently selected from the group consisting of halogen, cyano, nitro, -OH, - SH, -SCN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl, C3-C8-cycloalkyl, wherein one or more CH2 groups of the aforementioned radicals may be replaced by a C=0 group, and/or the aliphatic and cycloaliphatic moieties of the aforementioned radicals may be unsubstituted, partially or fully halogenated and/or may carry 1 or 2 radicals selected from C1-C4 alkoxy; CrC6-alkoxy, CrC6-haloalkoxy, Ci-C6-alkylthio, Ci-C6-alkylsulfinyl, Ci-C6- alkylsulfonyl, Ci-C6-haloalkylthio, -ORa, -NRcRd, -S(0)mRa, -S(0)mNRcRd, -C(=0)Ra, -C(=0)NRcRd, -C(=0)ORb, -C(=S)Ra, -C(=S)NRcRd, -C(=S)OR , -C(=S)SRb, -C(=NRc)Rb, and -C(=NRc)NR°Rd; n is 0 or 1 ; m is 0, 1 or 2.
Compounds according to claim 1 or 2, wherein the compound of formula (I) is a pound of formula I A:
Figure imgf000121_0001
wherein
Q4 is halogen.
4. Compounds according to claim 1 , 2 or 3, wherein the compound of formula (I) is a compound of formula IB:
Figure imgf000122_0001
wherein
Q1 is selected from the group consisting of bromo, chloro, cyano;
Q3 is selected from the group consisting of bromo, chloro, trifluorom ethyl. OCHF2.
5. Compounds according to any of claims 1 to 4, wherein the compound of formula (I) is a compound of formula ID:
Figure imgf000122_0002
wherein
Q2 is selected from the group consisting of halogen, methyl and halomethyl;
Q1 is selected from the group consisting of bromo, chloro and cyano.
6. A compound according to any of claims 1 to 5, wherein the compound is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 of formula IA-1
Figure imgf000123_0001
wherein the substituents are defined as follows:
Figure imgf000123_0002
Salts of N-Thio-anthranilamide compounds of formula I according to any of claims 1 to 6.
Salt according to claim 7 which is a hydrochloride.
A crystalline toluene solvate of compound 1-21 [2-(3-chloro-2-pyridyl)-N-[2-methyl-4- chloro-6-[(bis-2-propyl^4-sulfanylidene)carbamoyl]phenyl]-5-(trifluoromethyl)pyrazole-3- carboxamide) which is selected from l-21-Tol-A (form A) and l-21-Tol-B(form B);
wherein
l-21 -Tol-A, in an X-ray powder diffractogram at 25°C and Cu-Κα radiation, shows at least four of the ten following reflexes, given as 2Θ values: 6.83, 11 .44, 12.91 , 13.31 , 13.78, 15.00, 16.86, 19.30, 22.39, 23.35; and wherein
1-21 -Tol-B has the following crystal parameters:
Crystal system: Monoclinic; Space group: P2i;
a,b,c (Length of the edges of the unit cell): a 9.7390(6) A; b 25.7706(2) A; c 12.7405(8) A; α,β,γ (Angles of the unit cell): a 90°; β 93.179(3) °; γ 90°;
Volume 3192,69 A3;
Z (Number of molecules, in the unit cell): 4;
R-Factor (%): 6.88
10. Use of compounds of formula I as defined in claims 1 to 6, or salts or solvates as defined in claims 7 to 9, for combating insects, acarids, or nematodes.
1 1. A method for the control of insects, acarids or nematodes by contacting the insect, acarid or nematode or their food supply, habitat, breeding ground or their locus with a pesticidal- ly effective amount of compositions or compounds of formula I as defined in claims 1 to 6, or salts or solvates as defined in claims 7 to 9.
12. A method of protecting growing plants from attack or infestation by insects, acarids or nematodes by applying to the foliage of the plants, or to the soil or water in which they are growing, a pesticidally effective amount of compositions or compounds of formula I as defined in claims 1 to 6, or salts or solvates as defined in claims 7 to 9.
13. 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 compositions or compounds of formula I as defined in claims 1 to 6 or their enantiomers or veterinarily acceptable salts or solvates as defined in claims 7 to 9. 14. A process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of compositions or compounds of formula I as defined in claims 1 to 6 or their enantiomers or veterinarily acceptable salts or solvates as defined in 7 to 9. 15. Compositions comprising a pesticidally or parasiticidally active amount of compounds of formula I as defined in claims 1 to 6, or salts or solvates as defined in claims 7 to 9, and an agronomically or veterinarily acceptable carrier.
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