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WO2016034352A1 - Use of n-thio-anthranilamide compounds on cultivated plants - Google Patents

Use of n-thio-anthranilamide compounds on cultivated plants Download PDF

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Publication number
WO2016034352A1
WO2016034352A1 PCT/EP2015/068006 EP2015068006W WO2016034352A1 WO 2016034352 A1 WO2016034352 A1 WO 2016034352A1 EP 2015068006 W EP2015068006 W EP 2015068006W WO 2016034352 A1 WO2016034352 A1 WO 2016034352A1
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plant
compound
formula
plants
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William Baxter
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BASF SE
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BASF SE
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/561,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the present invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification (hereinafter abbreviated as "cultivated plant”) as compared to the respective non-modified control plant, comprising the application of a pesti- cidally active compound of formula I
  • R 1 is selected from the group consisting of H, F, CI, Br and CN;
  • R 2 is selected from the group consisting of F, CI, Br, I, CH3;
  • R 3 is selected from the group consisting of Br, CI, CHF2, CF3 and OCH2F;
  • R 4 is CI or CF 3 ;
  • R 5 , R 6 are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or
  • R 5 and R 6 together represent a C2-C7-alkylene, C2-C7-alkenylene or
  • k O or l ;
  • compound of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof is un- derstood to include a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide, even if not mentioned explicitly.
  • plant health comprises various sorts of improvements of plants that are not connected to the control of pests and which do not embrace the reduction of negative conse- quences of harmful insects.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g.
  • plant vigor e.g. improved plant growth and/or greener leaves ("greening effect")
  • quality e.g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e.g. improved biomass and/or increased content of valuable ingredients
  • plant vigor e.g. improved plant growth and/or greener leaves ("greening effect")
  • quality e.g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e.g. improved content or composition of certain ingredients
  • cultivated plants are plants that have at least one insecticidal trait. It is a wide-spread problem that insects, that are combatted with insectides, develop resistance, i.e. they become less or not all anymore susceptible to the insecticidal effect.
  • compounds of formula (I) are useful in methods of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth, wherein the plant has at least one insecticidal trait, and wherein the harmful insects are resistant to an insecticidal trait of the plant.
  • cultivated plants are specific plants that have at least one herbicidal and at least one insecticidal trait, preferably soybeans, more preferably the soybeans known as"lntacta RR2 PRO" soybean (Monsanto).
  • soybeans more preferably the soybeans known as"lntacta RR2 PRO" soybean (Monsanto).
  • compounds of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
  • cultivated plants are plants that have at least one trait or trait
  • WO2007/006670, WO2013/024009, WO2013/024010 and WO2013/174645 describe N-thio- anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides.
  • WO2014/053395 describes the use of N-thio-anthranilamide compounds on certain cultivated plants.
  • the compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein.
  • 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.
  • anthranilamide compounds of formula (I) themselves have been described in methods and uses for controlling harmful pests on certain cultivated plants, there are further cultivated plants on which the compounds of formula (I) are surprisingly effective.
  • the compounds of formula (I) as well as the terms "compounds for methods according to the (present) invention”, “compounds according to the (present) invention” or “compounds of formula (I)” or “compound(s) II", which all compound(s) are applied in methods and uses according to the present invention comprise the compound(s) as defined herein as well as a known stereoisomer, salt, tautomer or N-oxide thereof (including a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof).
  • composition(s) according to the invention or “composition(s) of the present invention” encompasses composition(s) comprising at least one compound of formula (I) or mixtures of the compounds of formula (I) with other pesticidally active compound(s) II for being used and/or applied in methods according to the invention as defined above.
  • 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).
  • 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 useful salts” or “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 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 Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci- C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substituted ammonium ions comprise me- thylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • 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 ste- reoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules (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.
  • 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 -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in 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 alkoxyalkyi) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 or 1 to 4 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-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1 -ethyl-1 -methyl
  • 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.
  • 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 bicy-hack cycloaliphatic radical having usually from 3 to 10 carbon atoms (“C3-Cio-cycloalkyl”), preferably 3 to 8 carbon atoms (“Cs-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.
  • bicyclic radicals having 7 or 8 carbon atoms comprise bicyclo[2.1.1]hexyl, bicy- clo[2.2.1]heptyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and bicy- clo[3.2.1 ]octyl.
  • alkenyl denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 7 carbon atoms (“C2-C7-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
  • 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.
  • 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 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
  • 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.
  • alkoxy denotes in each case a straight-chain or branched alkyl group usually having usually froml 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.
  • Ci-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,
  • alkoxyalkyl denotes in each case alkyl usually comprising 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4 carbon atoms as defined above.
  • Ci-C4-Alkoxy-Ci-C6-alkyl is a Ci-C4-alkyl group, as defined above, in which one hydrogen atom is replaced by a Ci-C4-alkoxy group, as defined above.
  • Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH 2 -OCH(CH 3 )2, n-butoxymethyl, (1 -methylpropoxy)- methyl, (2-methylpropoxy)methyl, CH 2 -OC(CH 3 )3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n- propoxy)-ethyl, 2-(1 -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)-prop
  • 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.
  • 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.
  • Si-C2-a I kylsu If i nyl 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, at- tached via a sulfinyl [S(O)] group.
  • Ci-C6-alkylsulfinyl refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group.
  • Ci-C2-alkylsulfinyl is methylsulfinyl or ethyl- sulfinyl.
  • Ci-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl) or 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl).
  • Ci-C6-alkylsulfinyl is additionally, for example, pentylsulfinyl, 1 -methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl,
  • 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 ethyl- sulfonyl.
  • 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).
  • C1-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-dimethylbutylsul
  • 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,
  • 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, sul- fur, 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)-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.
  • the compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein.
  • 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.
  • R 1 is selected from the group consisting of CI, Br and CN.
  • R 1 is CI.
  • R 1 is CN
  • R 2 is selected from the group consisting of CI, Br and CH3 (Me).
  • R 2 is CI
  • R 2 is CH3.
  • the invention relates to methods and uses, in which in the compound of formula I
  • R 1 is selected from the group consisting of Br, CI, CN, preferably CI;
  • R 2 is selected from the group consisting of CI, CH3; preferably CH3.
  • R 1 is CI
  • R 2 is CH3.
  • R 1 is CI
  • R 2 is CI
  • R 1 is CN
  • R 2 is CH3.
  • k is 0 in the compounds of formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are as defined herein.
  • k is 1 in the compounds of formula (I):
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 are as defined herein.
  • the invention relates to methods and uses, in which in the compound of formula I
  • R 3 is CF3 or Br, preferably CF3.
  • R 4 is CI.
  • the invention relates to methods and uses, in which in the compound of formula I
  • R 1 is selected from the group consisting of Br, CI, CN, preferably CI;
  • R 2 is selected from the group consisting of CI, CH3; preferably CH3;
  • R 3 is CF3 or Br, preferably CF3;
  • R 4 is CI.
  • the invention relates to methods and uses of compounds of formula (I), in which R 5 and R 6 are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl and Cs-Cs-cycloalkyl.
  • the invention relates to methods and uses of compounds of formula (I), in which R 5 and R 6 are selected from Ci-C4-alkyl, preferably selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, more preferably methyl, ethyl, isopropyl, most preferably ethyl.
  • R 5 and R 6 are selected from Ci-C4-alkyl, preferably selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably selected from methyl, ethyl, n-prop
  • the invention relates to methods and uses of compounds of formula (IB), in which R 5 and R 6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
  • the invention relates to methods and uses of compounds of formula (IC), in which R 5 and R 6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
  • R 5 and R 6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
  • the invention relates to methods and uses of compounds of formula (ID), in which R 5 and R 6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
  • R 5 and R 6 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.
  • R 5 and R 6 are identical, and preferably selected from methyl, ethyl, and isopropyl.
  • a group of especially preferred compounds of formula I in the methods and uses according to the invention are compounds 1-1 to I-82 of formula IA which are listed in the table A.
  • a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as in Ta ble A' is the compound I in the methods and uses according to the invention.
  • a compound selected from compounds I-52, I-57, I-62, I-67, I-72 as i Table A" is the compound I in the methods and uses according to the invention.
  • 1-1 1 is the compound I in the methods and uses according to the invention
  • 1-16 is the compound I in the methods and uses according to the invention
  • 1-21 is the compound I in the methods and uses according to the invention
  • I-26 is the compound I in the methods and uses according to the invention
  • 1-31 is the compound I in the methods and uses according to the invention.
  • R 1 , R 2 , R 3 , R 4 are as defined herein and are preferably ⁇ -1 or ⁇ -2.
  • the compounds of formula I are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
  • insects from the order of Lepidoptera for example Achroia grisella, Acleris spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A.
  • Argyresthia conjugel- la Argyroploce spp., Argyrotaenia spp.
  • A. velutinana Athetis mindara, Austroasca vi- ridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bon- agota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C.
  • Cactoblastis cactorum Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indi- cus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G.
  • H. armigera Heliothis armigera
  • H. zea Heliothis zea
  • Heliothis spp. such as H. assulta, H. subflexa, H. virescens
  • Hellula spp. such as H. undalis, H.
  • Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quin- quemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M.
  • operculella Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathy- pena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P.
  • insects from the order of Coleoptera for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala diveren- ta, Anomala rufocuprea, Anoplophora spp. such as A.
  • Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aula- cophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B.
  • vespertinus Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryp- torhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D.
  • Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E.
  • hypomeces squamosus Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lath- ridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decem- lineata; Leptispa pygmaea, Limonius califomicus, Lissorhoptrus oryzophilus, Lixus spp., Lu- perodes spp., Lyctus spp. such as L.
  • Saperda Candida Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Stemechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T.
  • Trogoderma spp. Tychius spp.
  • Xylotrechus spp. such as X. pyrrhoderus
  • Za- brus spp. such as Z. tenebrioides
  • insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C.
  • Aedes spp. such as A. aegypti, A. albopictus, A. vexans
  • Anastrepha ludens Anopheles spp.
  • A. albimanus such as A.
  • insects from the order of Thysanoptera for example, Basothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S.
  • insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A.
  • Diaspis spp. such as D. bromeliae; Dichelops eatus, Diconoco- ris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. such as E.
  • Idiocerus spp. Idioscopus spp., Laodelphax striatellus, Lecani- um spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lep- toglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L.
  • Nasonovia ribis-nigri Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O.
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastro- coccus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R.
  • T. accerra, T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
  • Paravespula spp. such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S.invicta, S.
  • Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M.
  • Boophilus spp. such as B. annulatus, B. decoloratus, B. mi- croplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O.
  • Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp. such asS. Scabiei; and Family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassi; Aculus spp.
  • Tetranychidae including Eotetranychus spp., Eute- tranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as T. cinnabarinus, T. evansi, T. kanzawai, ⁇ , pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O.
  • Pests from the Phylum Nematoda for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A.
  • plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. ros
  • Awl nematodes Dolichodorus spp.
  • Spiral nematodes Heliocotylenchus multicinctus
  • Sheath and sheathoid nematodes Hem- icycliophora spp. and Hemicriconemoides spp.
  • Hirshmanniella spp. Lance nematodes, Hop- loaimus spp.
  • False rootknot nematodes Nacobbus spp.
  • Needle nematodes Longidorus spp. such as L. elongatus
  • Lesion nematodes Pratylenchus spp. such as P.
  • brachyurus P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P.
  • Stunt nematodes Tylencho- rhynchus spp. such as T. claytoni, T. dubius
  • Citrus nematodes Tylenchulus spp. such as T. semipenetrans
  • Dagger nematodes Xiphinema spp.
  • other plant parasitic nematode species such as T. claytoni, T. dubius
  • Neotermes spp. Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis; Blat- tella spp. such as B. asahinae, B.
  • Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica
  • Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;
  • Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp.
  • Pests from the class Symphyla for example Scutigerella immaculata
  • Insects from the order Collembola for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
  • Insects from the order Phthiraptera for example Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; 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.,
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, 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
  • Haemonchus contortus such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum 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, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • 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 species: Thysanoptera : Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips pa Imi and Thrips tabaci.
  • Mixtures of the present invention are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Hemiptera and Thysanoptera.
  • the 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, white- flies, scale insects, cicadas (Hemiptera), ants, bees, wasps, sawflies (Hymenoptera), crickets, grasshoppers, locusts (Orthoptera), and also Arachnoidea, such as arachnids (Acarina).
  • the compounds of formula I are employed as a solo prod- uct.
  • the present invention also relates to methods for controlling pests and/or increasing the plant health of a cultivated plant, comprising in the application of a mixture of a compound of formula I and a pesticide II to a cultivated plant, parts of such plant, plant propagation material, or at its locus of growth.
  • the compounds of formula I are employed in combination (e.g. a mixture) with one or more compounds II which is a preferably a further in- secticide or a fungicide.
  • 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:
  • 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
  • M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofu- ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfen
  • GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
  • M.3 Sodium channel modulators from the class of M.3A pyrethroids for example 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, fen
  • M.4 Nicotinic acetylcholine receptor agonists from the class of M.4A neonicotinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thia- cloprid and thiamethoxam; or the compounds M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]-N'- nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
  • M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin; M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydroprene, ki- noprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
  • M.8 miscellaneous non-specific (multi-site) inhibitors for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
  • M.9 Selective homopteran feeding blockers for example M.9B pymetrozine, or M.9C floni- camid;
  • M.10 Mite growth inhibitors for example M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
  • M.1 1 Microbial disruptors of insect midgut membranes, for example 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: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase for example M.12A diafenthiuron, or M.12B or- ganotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • benzoylureas as for example bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novalu- ron, noviflumuron, teflubenzuron or triflumuron;
  • M.16 Inhibitors of the chitin biosynthesis type 1 as for example buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors for example M.20A hydramethyl- non, or M.20B acequinocyl, or M.20C fluacrypyrim;
  • M.21 Mitochondrial complex I electron transport inhibitors for example M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22 Voltage-dependent sodium channel blockers for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4- (difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid deriva- tives, for example spirodiclofen, spiromesifen or spirotetramat;
  • M.24 Mitochondrial complex IV electron transport inhibitors for example 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, for example cyenopyrafen or cyflumetofen;
  • M.28 Ryanodine receptor-modulators from the class of diamides as for example flubendia- mide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chlor-N1 - ⁇ 2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -
  • insecticidal active compounds of unknown or uncertain mode of action as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, flu- ensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butox- ide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the com- pounds
  • M.29.5 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, 1-1582); or
  • M.29.6a (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide
  • M.29.6b (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide
  • M.29.6c (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide
  • M.29.6d (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2
  • M.29.9.a 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or M.29.9.b): fluxametamide; or
  • M.29.10 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 , 2,2,3,3,3- hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]-benzamide; M.29.
  • M.29.14a 1 -[(6-Chloro-3-pyridinyl)methyl]-1 , 2,3,5, 6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; or M.29.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compounds
  • M.29.16a 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1 - (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1 - [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
  • M.29.16e N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide
  • M.29.16f 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide
  • M.29.16h N-methyl-1 -(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide
  • M.29.16i 1 -(4,4-difluorocyclohexyl)-N-ethyl-5
  • M.29.17 a compound selected from the compounds M.29.17a) to M.29.17j): M.29.17a) N-(1 - methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17b) N-cyclopropyl-2-(3- pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4- carboxamide; M.29.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; M.29.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide;
  • M.29.171) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; M.29.17g) N- [(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17h) N-(2,2- difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17i) 2-(3-pyridinyl )-N-(2- pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.29.17j) N-[(5-methyl-2-pyrazinyl)methyl]-2- (3-pyridinyl)-2H-indazole-5-carboxamide, or
  • M.29.18 a compound selected from the compounds M.29.18a) to M.29.18d): M.29.18a) N-[3- chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfanyl)propanamide; M.29.18b) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfinyl)propanamide;
  • M.29.18c N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N- ethyl-propanamide; M.29.18d) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2- difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide; or the compound
  • the M.4 neonicotinoid cycloxaprid is known from WO2010/069266 and WO201 1/069456, the neonicotinoid M.4A.2, sometimes also to be named as guadipyr, is known from
  • WO2013/003977 and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from WO2007/101369.
  • the metaflumizone analogue M.22B.1 is described in CN10171577 and the analogue M.22B.2 in CN102126994.
  • the phthalamides M.28.1 and M.28.2 are both known from WO2007/101540.
  • the anthranilamide M.28.3 is described in WO2005/077934.
  • the hydra- zide compound M.28.4 is described in WO2007/043677.
  • the anthranilamide M.28.5i) is de- scribed in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and
  • the diamide compound M.28.6 can be found in WO2012/034472.
  • the spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.29.4 from WO2008/06791 1.
  • the tri- azoylphenylsulfide M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707.
  • the compounds M.29.6a) to M.29.6i) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in
  • the nematicide M.29.8 is known from WO2013/055584.
  • the isoxazoline M.29.9.a) is described in WO2013/050317.
  • the isoxazoline M.29.9.b) is described in
  • the pyridalyl-type analogue M.29.10 is known from WO2010/060379.
  • the carboxamides broflanilide and M.29.1 1.b) to M.29.1 1.h) are described in WO2010/018714, and the carboxamides M.29.1 1 i) to M.29.1 1.p) in WO2010/127926.
  • the pyridylthiazoles M.29.12.a) to M.29.12.C) are known from WO2010/006713, M.29.12.d) and M.29.12.e) are known from WO2012/000896, and M.29.12.f) to M.29.12.m) from WO2010/129497.
  • the compounds M.29.14a) and M.29.14b) are known from WO2007/101369.
  • the pyrazoles M.29.16.a) to M.29.16h) are described in WO2010/034737, WO2012/084670, and WO2012/143317, respectively, and the pyrazoles M.29.16i) and M.29.16j) are described in US 61/891437.
  • the pyridinyl- indazoles M.29.17a) to M.29.17.j) are described in WO2015/038503.
  • the pyridylpyrazoles M.29.18a) to M.29.18d) are described in US2014/0213448.
  • the isoxazoline M.29.19 is described in WO2014/036056.
  • the isoxazoline M.29.20 is known from WO2014/090918.
  • a compound of formula (I) in mixture with fipronil is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'
  • a compound of formula (I) in mixture with ethiprole is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with chlorfenapyr is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with teflubenzuron is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with chlorfenapyr and teflubenzuron is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with dinotefuran is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with chlorantraniliprole is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with cyantraniliprole is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with pyrethroids, preferably alpha-cypermethrin, is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • the pesticide II is selected from the group of fipronil, alpha-cypermethrin, dinotefuran, chlorfenapyr, teflubenzuron and sulfoxaflor.
  • a compound II selected from group M.2 GABA-gated chloride channel antagonists as defined above is preferred, in particular group M.2B (fiproles), especially preferred ethiprole and fipronil.
  • a compound II selected from group M.3 (Sodium channel modulators) as defined above is preferred, in particular group M.3A (pyrethroids), especially preferred alpha-cypermethrin and cyhalothrin.
  • group M.3A pyrethroids
  • alpha-cypermethrin cyhalothrin.
  • a compound II selected from group M.4A (Neonicotinoids) as defined above is preferred, in particular clothianidin, dinotefuran, imidacloprid, thiacloprid, or thiamethoxam.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with clothianidin as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with dinotefuran as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with imidacloprid as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with thiacloprid as compound II are also preferred. Mixtures of compounds of formula I with sulfoxaflor as compound II are also preferred.
  • the compound II is selected from group M.5 (Nicotinic acetylcholine receptor allosteric activators) and is preferably spinosad or spinetoram.
  • the compound II is selected from group M.6 (Chloride channel activators) and is preferably an avermectin.
  • the compound II is selected from group M.9 (Selective homopteran feeding blockers) and is preferably pymetrozine or flonicamid. Mixtures of compounds of formu- la I as individualized herein, e.g. in Table A, Table A' or Table A", with pymetrozine as compound II are especially preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with flonicamid as compound II are especially preferred.
  • the compound II is selected from group M.13 (Uncouplers of oxidative phosphorylation via disruption of the proton gradient) and is preferably chlorfenapyr.
  • group M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient
  • chlorfenapyr Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with chlorfenapyr as compound II are especially preferred.
  • the compound II is selected from group M.16 (Inhibitors of the chitin biosynthesis type 1 ) and is preferably buprofezin.
  • the compound II is selected from group M.22 (Voltage-dependent sodium channel blockers) and is preferably metaflumizone.
  • the compound II is selected from group M.23 (Inhibitors of the of acetyl CoA carboxylase) and is preferably a Tetronic or Tetramic acid derivative, spirodiclofen, spi- romesifen or spirotetramat.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with Tetronic Acid as compound II are preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with Tetramic Acid as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with Tetramic Acid as compound II are also preferred.
  • the compound II is selected from group M.26 (Ryanodine receptor- modulators) and is preferably chlorantraniliprole or cyantraniliprole.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with chlorantraniliprole as compound II are especially preferred.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with cyantraniliprole as compound II are especially preferred.
  • the compound II is sulfoxaflor.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with sulfoxaflor as compound II are especially preferred.
  • the compound (II) pesticides are selected from fungicides.
  • the following list of fungicides, in conjunction with which the com- pounds of the present invention can be used, is intended to illustrate the possible combinations but does not limit them:
  • Inhibitors of complex III at Q 0 site e. g. strobilurins: azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1 .4), enestroburin (A.1.5), fenamin- strobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxy.strobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1 .16), tri- floxystrobin (A.1 .17), 2-(2-
  • inhibitors of complex II e. g. carboxamides: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)-
  • respiration inhibitors e. g. complex I, uncouplers: diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)
  • SBI fungicides Sterol biosynthesis inhibitors
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1 .4), difenoconazole (B.1 .5), diniconazole (B.1.6), diniconazole-M (B.1 .7), epoxiconazole (B.1.8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1 .15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclo
  • Delta14-reductase inhibitors aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
  • Inhibitors of 3-keto reductase fenhexamid (B.3.1 );
  • phenylamides or acyl amino acid fungicides benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1 .6), oxadixyl (C.1.7); others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
  • diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
  • methionine synthesis inhibitors anilino-pyrimidines: cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
  • blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
  • MAP / histidine kinase inhibitors fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1 .4), fenpiclonil (F.1 .5), fludioxonil (F.1.6);
  • quinoxyfen F.2.1 ;
  • Phospholipid biosynthesis inhibitors edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);
  • lipid peroxidation dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
  • phospholipid biosynthesis and cell wall deposition dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
  • inorganic active substances Bordeaux mixture (H.1.1 ), copper acetate (H.1 .2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1.5), sulfur (H.1 .6);
  • thio- and dithiocarbamates ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
  • organochlorine compounds e. g. phthalimides, sulfamides, chloronitriles: anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
  • organochlorine compounds e. g. phthalimides, sulfamides, chloronitriles
  • guanidines and others guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
  • inhibitors of glucan synthesis validamycin (1.1 .1 ), polyoxin B (1.1 .2);
  • melanin synthesis inhibitors pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
  • acibenzolar-S-methyl J.1.1
  • probenazole J.1.2
  • isotianil J.1 .3
  • tiadinil J.1 .4
  • prohexa- dione-calcium J.1.5
  • phosphonates fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1 .9);
  • bronopol K.1.1
  • chinomethionat K.1 .2
  • cyflufenamid K.1 .3
  • cymoxanil K.1.4
  • dazomet K.1.5
  • debacarb K.1.6
  • diclomezine K.1 .7
  • difenzoquat K.1 .8
  • difenzoquat-methylsulfate K.1.9
  • diphenylamin K.1 .10
  • fenpyrazamine K.1 .1 1
  • flumetover K.1 .12
  • flusulfamide K.1.13
  • flutianil K.1.14)
  • methasulfocarb K.1 .15
  • nitrapyrin K.1 .16
  • nitrothal-isopropyl K.1.18
  • oxathiapiprolin K.1 .19
  • tolprocarb K.1 .20
  • fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are com- briefly available.
  • fungicides described by lUPAC nomenclature, their preparation and their pesticidal activity is 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;
  • a compound II selected from the group of the azoles is preferred, especially prochloraz, prothiocona- zole, tebuconazole and triticonazole, especially prothioconazole and triticonazole.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with triticonazole as compound II are particularly preferred.
  • Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with prothioconazole as compound II are particularly preferred.
  • a compound II selected from the group of benomyl, carbendazim, epoxiconazole, fluquin- conazole, flutriafol, flusilazole, metconazole, prochloraz, prothioconazole, tebuconazole, triticonazole, pyraclostrobin, trifloxystrobin, boscalid, dimethomorph, penthiopyrad, dodemorph, famoxadone, fenpropimorph, proquinazid, pyrimethanil, tridemorph, compound ll-TFPTAP (5- chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine), maneb, mancozeb, metiram, thiram, chloro
  • a compound of formula (I) in mixture with pyraclostrobin is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with pyraclostrobin is applied, preferably in the methods for foliar treat- ment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with fluxapyroxad is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • a compound of formula (I) in mixture with an azole is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
  • the mixtures comprise as an additional component which is the compound against which the cultivated plant is resistant.
  • the ratios by weight for the respective mixtures comprising the insecticidal compound I and compound II are from 1 :500 to 500:1 , preferably from 1 :100 to 100:1 , more preferably from 1 :25 to 25:1.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
  • An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof.
  • the term "pesticidally effective amount" is defined below.
  • the compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, pow- ders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g.
  • compositions types are defined in the "Catalogue of pesticide 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, surfac-tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec-tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu-lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi-ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac-tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec-tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu-lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants,
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions 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, cyclo ⁇ hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions 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, tetrahydronaphthalene, alkyl
  • 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; polysaccharide powders, 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
  • polysaccharide powders e.g. cellulose, starch
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric 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, sul-fates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, 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 ethox- ylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
  • 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.
  • 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 al- kylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrroli- done, 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 pol- yethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxi- laries. 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 alkylisothiazoli-nones 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 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, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions cormprising 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 user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • 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.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the in- vention or partially premixed components e. g. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
  • the compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infes- tation by animal pests, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions compris- ing said mixtures as defined above.
  • the components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, 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 application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
  • Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application.
  • Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection.
  • Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting.
  • furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.
  • Foliar application refers to the application of the pesticidally active compound to plant foli- age, e.g. through spray equipment.
  • pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as
  • the term "contacting” includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
  • animal pest includes arthropods, gastropods, and nematodes.
  • Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
  • Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
  • crop refers to both, growing and harvested crops.
  • plant includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • iceberg lettuce chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cu- curbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g.
  • Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
  • Plants which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
  • rapeseed e.g. oilseed rape
  • bean carnation
  • chicory cotton
  • eggplant eucalyptus
  • flax flax
  • lentil eucalyptus
  • melon melon
  • papaya petunia
  • plum poplar
  • potato rice
  • soybean zucchini
  • sugar beet sugarcane
  • sunflower sweet pepper
  • sweet pepper tobacco, tomato
  • the one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5.
  • the mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant.
  • Such properties include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control.
  • herbicide tolerance e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance
  • mutagenesis for example Clearfield® oilseed rape being tolerant to imidazoli- nones, e.g. imazamox.
  • genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • glyphosate and glufosinate some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate
  • RoundupReady® glyphosate
  • LibertyLink® glufosinate
  • insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance.
  • Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance.
  • the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
  • plant propagation material refers to 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.
  • 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.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 g per 100 m 2 .
  • the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
  • the compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects.
  • the present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention.
  • the protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods.
  • seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • the present invention also comprises seeds coated with or containing the active compound.
  • 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 for example 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, ba- nanas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
  • Conventional seed treatment formulations include for example flowable concentrates FS, solu- tions LS, suspoemulsions (SE), 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. Preferably, the formulations are applied such that germination is not included.
  • the active substance concentrations in ready-to-use formulations are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1 -800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of the compounds of the present 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.
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • the application rates of the compounds of the invention 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, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein.
  • the amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
  • an effective and non-phytotoxic amount means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
  • plant and “plant propagation material” are defined above.
  • Plant health is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
  • yield for example increased biomass and/or increased content of valuable ingredients
  • quality for example improved content or composition of certain ingredients or shelf life
  • plant vigour for example improved plant growth and/or greener leaves ("greening effect")
  • tolerance to abiotic for example drought
  • biotic stress for example disease
  • production efficiency for example, harvesting efficiency, processability
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other.
  • Each indicator is defined in the art and can be determined by methods known to a skilled person.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant, by treating plant propagation material, preferably seeds with compounds of formula I and their mixtures.
  • the present invention also comprises plant propagation material, preferably seed, of a cultivated plant treated with compounds of formula I and their mixtures.
  • the present invention relates to a method of controlling harm- ful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant by treating the cultivated plant, part(s) of such plant or at its locus of growth with compounds of formula I and their mixtures.
  • the term cultivated plant(s) includes "modified plant(s)" and "transgenic plant(s)".
  • the term “cultivated plants” refers to "modified plants”. In one embodiment of the invention, the term “cultivated plants” refers to "transgenic plants”. "Modified plants” are those which have been modified by conventional breeding techniques.
  • the term “modification” means in relation to modified plants a change in the genome, epigenome, tran- scriptome or proteome of the modified plant, as compared to the control, wild type, mother or parent plant whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below.
  • the modification may result in the modified plant to be a different, for example a new plant vari- ety than the parental plant.
  • Transgenic plants are those, which genetic material has been modified by the use of recombinant DNA techniques that under natural circumstances can not readily be obtained by cross breeding, mutations or natural recombination, whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below as com- pared to the wild-type plant.
  • 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, preferably increase a trait as listed below as compared to the wild-type plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), or to post- transcriptional modifications of oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated, phosphorylated or farnesylated moieties or PEG moieties.
  • modification when referring to a transgenic plant or parts thereof is understood that the activity, expression level or amount of a gene product or the metabolite content is changed, e.g. increased or decreased, in a specific volume relative to a cor- responding volume of a control, reference or wild-type plant or plant cell, including the de novo creation of the activity or expression.
  • the activity of a polypeptide is increased or generated by expression or overexpresion of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant.
  • expression or “gene expression” means the transcription of a specific gene or specific genes or specific genetic construct.
  • expression or “gene expression” in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA), regulatory RNA (e.g. miRNA, RNAi, RNAa) or mRNA with or without subsequent translation of the latter into a protein.
  • expression in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA) or mRNA with or without subsequent translation of the latter into a protein. In yet another embodiment it means the transcription of a gene or genes or genetic construct into mRNA.
  • the process includes transcription of DNA and processing of the resulting mRNA product.
  • increased expression or “overexpression” as used herein means any form of expression that is additional to the original wild-type expression level.
  • polypeptide expression of a polypeptide is understood in one embodiment to mean the level of said protein or polypeptide, preferably in an active form, in a cell or organism.
  • the activity of a polypeptide is decreased by decreased expression of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant.
  • Reference herein to "decreased expression” or “reduction or substantial elimination” of expression is taken to mean a decrease in endogenous gene expression and/or polypeptide levels and/or polypeptide activity relative to control plants. It comprises further reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule.
  • reduction relate to a corresponding change of a property in an organism, a part of an organism such as a tissue, seed, root, tuber, fruit, leave, flower etc. or in a cell.
  • change of a property it is understood that the activity, expression level or amount of a gene product or the metabolite content is changed in a specific volume or in a specific amount of protein relative to a corresponding volume or amount of protein of a control, reference or wild type.
  • the overall activity in the volume is reduced, decreased or deleted in cases if the reduction, decrease or deletion is related to the reduction, decrease or deletion of an activity of a gene product, independent whether the amount of gene product or the specific activity of the gene product or both is reduced, decreased or deleted or whether the amount, stability or translation efficacy of the nucleic acid sequence or gene encoding for the gene product is reduced, decreased or deleted.
  • reduction include the change of said property in only parts of the subject of the present invention, for example, the modification can be found in compartment of a cell, like an organelle, or in a part of a plant, like tissue, seed, root, leave, tuber, fruit, flower etc. but is not detectable if the overall subject, i.e. complete cell or plant, is tested.
  • the "reduction”, “repression”, “decrease” or “deletion” is found cellular, thus the term “reduction, decrease or deletion of an activity” or “reduction, decrease or deletion of a metabolite content” relates to the cellular reduction, decrease or deletion compared to the wild type cell.
  • the terms “reduction”, “repression”, “decrease” or “deletion” include the change of said property only during different growth phases of the organism used in the inventive process, for example the reduction, repression, decrease or deletion takes place only during the seed growth or during blooming.
  • the terms include a transitional reduction, decrease or deletion for example because the used method, e.g. the antisense, RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, or ribozyme, is not stable integrated in the genome of the organism or the reduction, decrease, repression or deletion is under control of a regulatory or inducible element, e.g. a chemical or otherwise inducible promoter, and has therefore only a transient effect.
  • a regulatory or inducible element e.g. a chemical or otherwise inducible promoter
  • Reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule in modified plants is known.
  • Examples are canola i.e. double nill oilseed rape with reduced amounts of erucic acid and sinapins.
  • Such a decrease can also be achieved for example by the use of recombinant DNA technology, such as antisense or regulatory RNA (e.g. miRNA, RNAi, RNAa) or siRNA approaches.
  • RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, ribozyme, or antisense nucleic acid molecule a nucleic acid molecule conferring the expression of a domi- nant-negative mutant of a protein or a nucleic acid construct capable to recombine with and silence, inactivate, repress or reduces the activity of an endogenous gene may be used to decrease the activity of a polypeptide in a transgenic plant or parts thereof or a plant cell thereof used in one embodiment of the methods of the invention.
  • transgenic plants with reduced, repressed, decreased or deleted expression product of a nucleic acid molecule are Carica papaya (Papaya plants) with the event name X17-2 of the University of Florida, Prunus domestica (Plum) with the event name C5 of the United States Department of Agriculture - Agricultural Research Service, or those listed in rows T9-48 and T9-49 of table 9 below.
  • plants with increased resistance to nematodes for example by reducing, repressing, de- creasing or deleting of an expression product of a nucleic acid molecule, e.g. from the PCT publication WO 2008/095886.
  • the reduction or substantial elimination is in increasing order of preference at least 10%, 20%, 30%, 40% or 50%, 60%, 70%, 80%, 85%, 90%, or 95%, 96%, 97%, 98%, 99% or more reduced compared to that of control plants.
  • Reference herein to an "endogenous" gene not only refers to the gene in question as found in a plant in its natural form (i.e., without there being any human intervention), but also refers to that same gene (or a substantially homologous nucleic acid/gene) in an isolated form subsequently (re)introduced into a plant (a transgene).
  • control or “reference” are exchangeable and can be a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which was not modified or treated according to the herein described process according to the invention. Accordingly, the plant used as control or reference corresponds to the plant as much as possible and is as identical to the subject matter of the invention as possible. Thus, the control or reference is treated identically or as identical as possible, saying that only conditions or properties might be different which do not influence the quality of the tested property other than the treatment of the present invention.
  • control or reference plants are wild-type plants.
  • control or reference plants may refer to plants carrying at least one genetic modification, when the plants employed in the process of the present invention carry at least one genetic modification more than said control or reference plants.
  • control or reference plants may be transgenic but differ from transgenic plants employed in the process of the present invention only by said modification contained in the transgenic plants employed in the process of the present invention.
  • wild type or wild-type plants refers to a plant without said genetic modification. These terms can refer to a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which lacks said genetic modification but is otherwise as identical as possible to the plants with at least one genetic modification employed in the present invention. In a particular embodiment the "wild-type" plant is not transgenic.
  • the wild type is identically treated according to the herein described process according to the invention.
  • the person skilled in the art will recognize if wild-type plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild- type plants will not need selection for transgenic plants for example by treatment with a select- ing agent such as a herbicide.
  • the control plant may also be a nullizygote of the plant to be assessed.
  • nullizygote refers to a plant that has undergone the same production process as a transgenic, yet has lost the once aquired genetic modification (e.g. due to mendelian segregation)as the corresponding transgenic. If the starting material of said production process is transgenic, then nullizygotes are also transgenic but lack the additional genetic modification introduced by the production process.
  • the purpose of wild-type and nullizygotes is the same as the one for control and reference or parts thereof. All of these serve as controls in any comparison to provide evidence of the advantageous effect of the present invention.
  • any comparison is carried out under analogous conditions.
  • analogous conditions means that all conditions such as, for example, culture or growing conditions, soil, nutrient, water content of the soil, temperature, humidity or surrounding air or soil, assay conditions (such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like) are kept identical between the experiments to be compared.
  • assay conditions such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like.
  • results can be normalized or standardized based on the control.
  • the "reference”, “control”, or “wild type” is preferably a plant, which was not modified or treated according to the herein described process of the invention and is in any other property as similar to a plant, employed in the process of the present invention of the invention as possible.
  • the reference, control or wild type is in its genome, transcriptome, proteome or metabolome as similar as possible to a plant, employed in the process of the present invention of the present inven- tion.
  • the term “reference-” "control-” or “wild-type-” plant relates to a plant, which is nearly genetically identical to the organelle, cell, tissue or organism, in particular plant, of the present invention or a part thereof preferably 90% or more, e.g.
  • the "reference”, “control”, or “wild type” is a plant, which is genetically identical to the plant, cell, a tissue or organelle used according to the process of the invention except that the responsible or activity conferring nucleic acid molecules or the gene product encoded by them have been amended, manipulated, exchanged or introduced in the organelle, cell, tissue, plant, employed in the process of the present invention.
  • the reference and the subject matter of the invention are compared after standardi- zation and normalization, e.g. to the amount of total RNA, DNA, or protein or activity or expression of reference genes, like housekeeping genes, such as ubiquitin, actin or ribosomal proteins.
  • the genetic modification carried in the organelle, cell, tissue, in particular plant used in the process of the present invention is in one embodiment stable e.g. due to a stable transgenic inte- gration or to a stable mutation in the corresponding endogenous gene or to a modulation of the expression or of the behaviour of a gene, or transient, e.g. due to an transient transformation or temporary addition of a modulator such as an agonist or antagonist or inducible, e.g. after transformation with a inducible construct carrying a nucleic acid molecule under control of a inducible promoter and adding the inducer, e.g. tetracycline.
  • a modulator such as an agonist or antagonist or inducible
  • preferred plants from which "modified plants” and/or “transgenic plants” are be selected from the group consisting of cereals, such as maize (corn), wheat, barley sorghum, rice, rye, millet, triticale, oat, pseudocereals (such as buckwheat and quinoa), alfalfa, apples, banana, beet, broccoli, Brussels sprouts, cabbage, canola (rapeseed), carrot, cauliflower, cherries, chickpea, Chinese cabbage, Chinese mustard, collard, cotton, cranberries, creeping bent- grass, cucumber, eggplant, flax, grape, grapefruit, kale, kiwi, kohlrabi, melon, mizuna, mustard, papaya, peanut, pears, pepper, persimmons, pigeonpea, pineapple, plum, potato, raspberry, rutabaga, soybean, squash, strawberries, sugar beet, sugarcane, sunflower, sweet corn, tobacco, tomato, turnip, walnut, water
  • alfalfa canola (rapeseed), cotton, rice, maize, cerals (such as wheat, barley, rye, oat), soybean, fruits and vegetables (such as potato, tomato, melon, papaya), pome fruits (such as apple and pear), vine, sugarbeet, sugarcane, rape, citrus fruits (such as citron, lime, orange, pomelo, grapefruit, and mandarin) and stone fruits (such as cherry, apricot and peach), most preferably from cotton, rice, maize, cerals (such as wheat, barley, rye, oat), sorghum, squash, soybean, potato, vine, pome fruits (such as apple), citrus fruits (such as citron and orange), sugarbeet, sugarcane, rape, oilseed rape and tomatoes,, utmost preferably from cotton, rice, maize, wheat, barley, rye, oat, soybean, potato, vine
  • the cultivated plant is a gymnosperm plant, especially a spruce, pine or fir.
  • 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.
  • the invention relates to methods and uses, wherein a compound selected from the compounds of Table A, A' or A", is applied in an application type which corresponds in each case to one row of Table AP-T.
  • 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.
  • 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.
  • 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.
  • the invention relates to methods and uses, wherein a compound of for- mula I-26, is applied in an application type which corresponds in each case to one row of Table AP-T.
  • 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.
  • 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.
  • SPC specialty crops
  • SPC-FV fruiting vegetable
  • SPC-LV leafy vegetable
  • SPC-T tubers
  • ST seed treatment
  • the cultivated plants are plants, which comprise at least one trait.
  • the term "trait” refers to a property, which is present in the plant either by genetic engineering or by conventional breeding techniques. Each trait has to be assessed in relation to its respective control. Examples of traits are:
  • modified nutrient uptake preferably an increased nutrient use efficiency and/or resistance to conditions of nutrient deficiency
  • cultiva plants may also comprise combinations of the aforementioned traits, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
  • all cultivated plants may also provide combinations of the aforementioned proper- ties, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
  • Tolerance to herbicides can be obtained by creating insensitivity at the site of action of the herbicide by expression of a target enzyme which is resistant to herbicide; rapid metabolism (conjugation or degradation) of the herbicide by expression of enzymes which inactivate herbicide; or poor uptake and translocation of the herbicide.
  • Examples are the expression of enzymes which are tolerant to the herbicide in comparison to wild type enzymes, such as the expression of 5- enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is tolerant to glyphosate (see e.g. Heck et.al, Crop Sci.
  • EPSPS 5- enolpyruvylshikimate-3-phosphate synthase
  • Gene constructs can be obtained, for example, from micro-organism or plants, which are tolerant to said herbicides, such as the Agrobacterium strain CP4 EPSPS which is resistant to glyphosate; Streptomyces bacteria which are resistance to glufosinate; Arabidopsis, Daucus carota, Pseu- domonoas spp. or Zea grass with chimeric gene sequences coding for HDDP (see e.g. WO 1996/38567, WO 2004/55191 ); Arabidopsis thaliana which is resistant to protox inhibitors (see e.g. US 2002/0073443).
  • said herbicides such as the Agrobacterium strain CP4 EPSPS which is resistant to glyphosate; Streptomyces bacteria which are resistance to glufosinate; Arabidopsis, Daucus carota, Pseu- domonoas spp. or Zea grass with chimeric gene sequences
  • Tolerance to glyphosate can also be achieved by any one of the genes 2mepsps, epsps, gat4601 , goxv247 or mepsps.
  • Tolerance to glufosinate can be achieved by any one of the genes bar, pat or pat(syn).
  • the herbicide tolerant plant can be selected from cereals such as wheat, barley, rye, oat; canola, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape in particular canola, tomatoes, potatoes, sugarcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • cereals such as wheat, barley, rye, oat
  • canola, sorghum soybean
  • rice oil seed rape
  • sugar beet sugarcane
  • grapes lentils
  • sunflowers alfalfa
  • pome fruits stone fruits
  • stone fruits peanuts
  • coffee coffee
  • the cultivated plant is selected from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L. (rice), preferably from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize) and Glycine max L. (soybean).
  • the cultivated plant is Glycine max L. (soybean).
  • Examples of commercial available transgenic plants with tolerance to herbicides are the corn varieties “Roundup Ready Corn”, “Roundup Ready 2" (Monsanto), “Agrisure GT”, “Agrisure GT/CB/LL”, “Agrisure GT/RW”, practiceAgrisure 3000GT” (Syngenta), “YieldGard VT Rootworm/RR2" and “YieldGard VT Triple” (Monsanto) with tolerance to glyphosate; the corn varieties “Liberty Link” (Bayer), “Herculex I”, “Herculex RW”, “Herculex Xtra”(Dow, Pioneer), “Agrisure GT/CB/LL” and “Agrisure CB/LL/RW” (Syngenta) with tolerance to glufosinate; the soybean varieties “Roundup Ready Soybean” (Monsanto) and “Optimum GAT” (DuPont, Pioneer) with tolerance to glyphosate; the cotton varieties "Round
  • transgenic plants with herbicide tolerance are commonly known, for instance alfalfa, apple, eucalyptus, flax, grape, lentils, oil seed rape, peas, potato, rice, sugar beet, sunflower, tobacco, tomatom turf grass and wheat with tolerance to glyphosate (see e.g. US 5188642, US 4940835, US 5633435, US 5804425, US 5627061 ); beans, soybean, cotton, peas, potato, sunflower, tomato, tobacco, corn, sorghum and sugarcane with tolerance to dicamba (see e.g.
  • Plants which are capable of synthesising one or more selectively acting bacterial toxins, comprise for example at least one toxin from toxin-producing bacteria, especially those of the genus Bacillus, in particular plants capable of synthesising one or more insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as del- ta.-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g.
  • VIP vegetative insecticidal proteins
  • VIP1 , VIP2, VIP3 or VIP3A insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lec- tins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such
  • a plant is capable of producing a toxin, lectin or inhibitor if it contains at least one cell comprising a nucleic acid sequence encoding said toxin, lectin, inhibitor or inhibitor producing enzyme, and said nucleic acid sequence is transcribed and translated and if ap- intestinalte the resulting protein processed and/or secreted in a constitutive manner or subject to developmental, inducible or tissue-specific regulation.
  • -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative in- secticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ).
  • a truncated toxin is a truncated CrylA(b), which is expressed in the Bt1 1 maize from Syngen- ta Seed SAS, as described below.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • non- naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 2003/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 2003/052073.
  • genes conferring resistance to coleopteran insects include cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, and mcry3A.
  • genes conferring resistance to lepidopteran insects include cry1A, cry1A.105, crylAb, cry1Ab-Ac, crylAc, cryl C, cryl F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), and vip3Aa20.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A- 0 367 474, EP-A-0 401 979 and WO 1990/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • the plant capable of expression of bacterial toxins is selected from cereals such as wheat, barley, rye, oat; canola, cotton, eggplant, lettuce, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from cotton, soybean, maize (corn), rice, tomatoes, pota- toes, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from cotton, soybean, maize, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • cereals such as wheat, barley, rye, oat
  • canola cotton, eggplant, lettuce, sorghum, soybean, rice, oil seed rape, sugar beet
  • the cultivated plant is selected from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L. (rice), preferably from the group consisting of Gossypium hirsutum L. (cot- ton), Zea mays L. (maize) and Glycine max L. (soybean).
  • the cultivated plant is Glycine max L. (soybean).
  • Examples of commercial available transgenic plants capable of expression of bacterial toxins are the corn varieties “YieldGard corn rootworm” (Monsanto), “YieldGard VT” (Monsanto), “Her- culex RW” (Dow, Pioneer), “Herculex Rootworm” (Dow, Pioneer) and “Agrisure CRW” (Syngen- ta) with resistance against corn rootworm; the corn varieties “YieldGard corn borer” (Monsanto), precedeYieldGard VT Pro” (Monsanto), “Agrisure CB/LL” (Syngenta), “Agrisure 3000GT” (Syngenta), "Hercules I", “Hercules II” (Dow, Pioneer), “KnockOut” (Novartis), preferNatureGard” (Mycogen) and consequentStarl_ink” (Aventis) with resistance against corn borer, the corn varieties favorHerculex I" (Dow, Pioneer) and concurrentHerculex
  • transgenic plants with insect resistance are commonly known, such as yellow stemborer resistant rice (see e.g. Molecular Breeding, Volume 18, 2006, Number 1 ), lep- idopteran resistant lettuce (see e.g. US 5349124 ), resistant soybean (see e.g. US 7432421 ) and rice with resistance against Lepidopterans, such as rice stemborer, rice skipper, rice cutworm, rice caseworm, rice leaffolder and rice armyworm (see e.g. WO 2001021821 ).
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • plants which are capable of synthesising antipathogenic substances are selected from soybean, maize (corn), rice, tomatoes, potato, banana, papaya, tobacco, grape, plum and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, tomatoes, potato, banana, papaya, oil seed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • Plants which are capable of synthesising antipathogenic substances having a selective action are for example plants expressing the so-called "pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392 225) or so-called “antifungal proteins” (AFPs, see e.g. US 6864068).
  • PRPs pathogenesis-related proteins
  • AFPs antifungal proteins
  • a wide range of antifungal proteins with activity against plant pathogenic fungi have been isolated from certain plant species and are common knowledge. Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 93/05153, WO 95/33818, and EP-A-0 353 191.
  • Transgenic plants which are resistant against fungal, viral and bacterial pathogens are produced by intro- ducing plant resistance genes.
  • Numerous resistant genes have been identified, isolated and were used to improve plant resistant, such as the N gene which was introduced into tobacco lines that are susceptible to Tobacco Mosaic Virus (TMV) in order to produce TMV-resistant tobacco plants (see e.g. US 5571706), the Prf gene, which was introduced into plants to obtain enhanced pathogen resistance (see e.g. WO 199802545) and the Rps2 gene from Arabidopsis thaliana, which was used to create resistance to bacterial pathogens including Pseudomonas syringae (see e.g. WO 199528423).
  • TMV Tobacco Mosaic Virus
  • Plants exhibiting systemic acquired resistance response were obtained by introducing a nucleic acid molecule encoding the TIR domain of the N gene (see e.g. US 6630618).
  • Further examples of known resistance genes are the Xa21 gene, which has been introduced into a number of rice cultivars (see e.g. US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375), the Rcg1 gene for colletotrichum resistance (see e.g. US 2006/225152), the prpl gene (see e.g. US 5859332, WO 2008/017706), the ppv-cp gene to introduce resistance against plum pox virus (see e.g.
  • the P1 gene for potato virus Y resistance see e.g. US 5968828
  • the HA5-1 gene see e.g. US5877403 and US6046384
  • the PIP gene to indroduce a broad resistant to viruses such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PLRV) (see e.g. EP 0707069) and genes such as Arabidopsis NI 16, ScaM4 and ScaM5 genes to obtain fungal resistance (see e.g. US 6706952 and EP 1018553).
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glu- canases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 1995/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO
  • Antipathogenic substances produced by the plants are able to protect the plants against a variety of pathogens, such as fungi, viruses and bacteria.
  • Useful plants of elevated interest in connection with present invention are cereals, such as wheat, barley, rye and oat; soybean; maize; rice; alfalfa, cotton, sugar beet, sugarcane, tobacco , potato, banana, oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits, papaya, melon, lenses and lettuce, more preferably selected from soybean, maize (corn), alfalfa, cotton, potato, banana, papaya, rice, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, potato, tomato, oilseed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • Transgenic plants with resistance against fungal pathogens are, for examples, soybeans with resistance against Asian soybean rust (see e.g. WO 2008/017706); plants such as alfalfa, corn, cotton, sugar beet, oileed, rape, tomato, soybean, wheat, potato and tobacco with resistance against Phytophtora infestans (see e.g.
  • WO 1999064600 plants such as rice, wheat, barley, rye, corn, oats, potato, melon, soybean and sorghum with resistance against fusarium diseases, such as Fusarium graminearum, Fusarium sporotrichioides, Fusarium lateritium, Fusarium pseudograminearum Fusarium sam- bucinum, Fusarium culmorum, Fusarium poae, Fusarium acuminatum, Fusarium equiseti (see e.g.
  • plants such as corn, soybean, cereals (in particular wheat, rye, barley, oats, rye, rice), tobacco, sorghum, sugarcane and potatoes with broad fungal resistance (see e.g. US 5689046, US 6706952, EP 1018553 and US 6020129).
  • Transgenic plants with resistance against bacterial pathogens are, for examples, rice with resistance against Xylella fastidiosa (see e.g. US 6232528); plants, such as rice, cotton, soybean, potato, sorghum, corn, wheat, balrey, sugarcane, tomato and pepper, with resistance against bacterial blight (see e.g. WO 2006/42145, US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375); tomato with resistance against Pseudomonas syringae (see e.g. Can. J. Plant Path., 1983, 5: 251 -255).
  • Transgenic plants with resistance against viral pathogens are, for examples, stone fruits, such as plum, almond, apricot, cherry, peach, nectarine, with resistance against plum pox virus (PPV, see e.g. US PP15,154Ps, EP 0626449); potatoes with resistance against potato virus Y (see e.g. US 5968828); plants such as potato, tomato, cucumber and leguminosaes which are re- sistant against tomato spotted wilt virus (TSWV, see e.g. EP 0626449, US 5973135); corn with resistance against maize streak virus (see e.g. US 6040496); papaya with resistance against papaya ring spot virus (PRSV, see e.g.
  • PRSV papaya with resistance against papaya ring spot virus
  • cucurbitaceae such as cucumber, melon, watermelon and pumpkin, and solanaceae, such as potato, tobacco, tomato, eggplant, paprika and pepper, with resistance against cucumber mosaic virus (CMV, see e.g. US 6849780); cucurbitaceae, such as cucumber, melon, watermelon and pumkin, with resistance against watermelon mosaic virus and zucchini yellow mosaic virus (see e.g. US 6015942); potatoes with resistance against potato leafroll virus (PLRV, see e.g. US 5576202); potatoes with a broad resistance to viruses, such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PLRV) (see e.g. EP 0707069).
  • CMV cucumber mosaic virus
  • PLAV zucchini yellow mosaic virus
  • PVX potato virus X
  • PVY potato virus Y
  • PLRV potato leafroll virus
  • deregulated or commercially available transgenic plants with modified genetic material capable of expression of antipathogenic substances are the following plants: Carica papaya (papaya), Event: 55-1/63-1 ; Georgia University, Carica papaya (Papaya); Event: (X17-2); University of Florida, Cucurbita pepo (Squash); Event: (CZW-3); Asgrow (USA); Semi- nis Vegetable Inc. (Canada), Cucurbita pepo (Squash); Event: (ZW20); Upjohn (USA); Seminis Vegetable Inc. (Canada), Prunus domestica (Plum); Event: (C5); United States Department of Agriculture - Agricultural Research Service, Solanum tuberosum L.
  • Transgenic plants with resistance against nematodes are, for examples, soybean plants with resistance to soybean cyst nematodes.
  • U.S. Patent Nos. 5,589,622 and 5,824,876 are directed to the identification of plant genes expressed specifically in or adjacent to the feeding site of the plant after attachment by the nematode.
  • transgenic plants with reduced feeding structures for parasitic nematodes e.g. plants resistant to herbicides except of those parts or those cells that are nematode feeding sites and treating such plant with a herbicide to prevent, reduce or limit nematode feeding by damaging or destroying feeding sites (e.g. US 5866777).
  • RNAi to target essential nematode genes has been proposed, for example, in PCT Publication WO 2001/96584, WO 2001/17654, US 2004/0098761 , US 2005/0091713, US
  • Transgenic nematode resistant plants have been disclosed, for example in the PCT publications WO 2008/095886 and WO 2008/095889.
  • Plants wich are resistant to antibiotics, such as kanamycin, neomycin and ampicillin.
  • the naturally occurring bacterial nptll gene expresses the enzyme that blocks the effects of the antibiot- ics kanamycin and neomycin.
  • the ampicillin resistance gene ampR also known as blaTEMI
  • ampR is derived from the bacterium Salmonella paratyphi and is used as a marker gene in the transformation of micro-organisms and plants. It is responsible for the synthesis of the enzyme beta- lactamase, which neutralises antibiotics in the penicillin group, including ampicillin.
  • Transgenic plants with resistance against antibiotics are, for examples potato, tomato, flax, canola, oilseed rape and corn (see e.g.
  • Plant Cell Reports 20, 2001 , 610-615. Trends in Plant Science, 1 1 , 2006, 317-319. Plant Molecular Biology, 37, 1998, 287-296. Mol Gen Genet., 257, 1998, 606- 13.). Plant Cell Reports, 6, 1987, 333-336. Federal Register (USA), Vol.60, No.1 13, 1995, page 31 139. Federal Register (USA), Vol.67, No.226, 2002, page 70392. Federal Register (USA), Vol.63, No.88, 1998, page 25194. Federal Register (USA), Vol.60, No.141 , 1995, page 37870. Canadian Food Inspection Agency, FD/OFB-095-264-A, October 1999, FD/OFB-099-127-A, October 1999.
  • the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, potato, sugarcane, alfalfa, tomatoes and cereals, such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • Plants which are tolerant to stress conditions are plants, which show increased tolerance to abiotic stress conditions such as drought, high salinity, high light intensities, high UV irradiation, chemical pollution (such as high heavy metal concentration), low or high temperatures, limitied supply of nutrients (i.e. nitrogen, phosphorous) and population stress.
  • abiotic stress conditions such as drought, high salinity, high light intensities, high UV irradiation, chemical pollution (such as high heavy metal concentration), low or high temperatures, limitied supply of nutrients (i.e. nitrogen, phosphorous) and population stress.
  • transgenic plants with resistance to stress conditions are selected from rice, corn, soybean, sugarcane, alfalfa, wheat, tomato, potato, barley, rapeseed, beans, oats, sorghum and cotton with tolerance to drought (see e.g.
  • the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, sugar beet, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, sugarcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • Altered maturation properties are for example delayed ripening, delayed softening and early maturity.
  • transgenic plants with modified maturation properties are, selected from tomato, melon, raspberry, strawberry, muskmelon, pepper and papaya with delayed ripening (see e.g. US 5767376, US 7084321 , US 6107548, US 5981831 , WO 1995035387, US
  • the plant is selected from fruits, such as tomato, vine, melon, papaya, banana, pepper, raspberry and strawberry; stone fruits, such as cherry, apricot and peach; pome fruits, such as apple and pear; and citrus fruits, such as citron, lime, orange, pomelo, grapefruit, and mandarin T more preferably from tomato, vine, apple, banana, orange and straw- berry, most preferably tomatoes.
  • fruits such as tomato, vine, melon, papaya, banana, pepper, raspberry and strawberry
  • stone fruits such as cherry, apricot and peach
  • pome fruits such as apple and pear
  • citrus fruits such as citron, lime, orange, pomelo, grapefruit, and mandarin T more preferably from tomato, vine, apple, banana, orange and straw- berry, most preferably tomatoes.
  • Content modification is synthesis of modified chemical compounds (if compared to the corresponding control plant) or synthesis of enhanced amounts of chemical (if compounds compared to the corresponding control plant) and corresponds to an increased or reduced amount of vitamins, amino acids, proteins and starch, different oils and a reduced amount of nicotine.
  • Further transgenic plants with altered content are, for example, potato and corn with modified amylopectin content (see e.g. US 6784338, US 20070261 136); canola, corn, cotton, grape, catalpa, cattail, rice, soybean, wheat, sunflower, balsam pear and vernonia with a modified oil content (see e.g.
  • the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, potato, tomato, oilseed rape, flax and cereals such as wheat, barley, rye and oat, most preferably soybean, maize (corn), rice, oilseed rape, potato, tomato, cotton, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • soybean, maize (corn) rice, cotton, sugarcane, potato, tomato, oilseed rape, flax and cereals
  • wheat, barley, rye and oat most preferably soybean, maize (corn), rice, oilseed rape, potato, tomato, cotton, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
  • transgenic plants with enhanced nitrogen assimilatory and utilization capacities are selected from for example, canola, corn, wheat, sunflower, rice, tobacco, soybean, cotton, alfalfa, tomato, wheat, potato, sugar beet, sugar cane and rapeseed (see e.g. WO 1995/00991 1 , WO 1997/030163, US 6084153, US 5955651 and US 6864405).
  • Plants with improved phosphorous uptake are, for example, tomato and potato (see e.g. US 7417181 ).
  • the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
  • Transgenic plants with male steriliy are preferably selected from canola, corn, tomato, rice, Indian mustard, wheat, soybean and sunflower (see e.g. US 6720481 , US 6281348, US 5659124, US 6399856, US 7345222, US 7230168, US 6072102, EP1 135982, WO 2001/092544 and WO 1996/040949).
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
  • Plants, which produce higher quality fiber are e.g. transgenic cotton plants.
  • the such improved quality of the fiber is related to improved micronaire of the fiber, increased strength, improved staple length, improved length unifomity and color of the fibers (see e.g. WO 1996/26639, US 7329802, US 6472588 and WO 2001/17333).
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • cultivated plants may comprise one or more traits, e.g.
  • Examples of commercial available transgenic plants with two combined properties are the corn varieties “YieldGard Roundup Ready” and YieldGard Roundup Ready 2" (Monsanto) with glyphosate tolerance and resistance to corn borer; the corn variety “Agrisure CB/LL” (Syntenta) with glufosinate tolerance and corn borer resistance; the corn variety “Yield Gard VT Root- worm/RR2” with glyphosate tolerance and corn rootworm resistance; the corn variety “Yield Gard VT Triple” with glyphosate tolerance and resistance against corn rootworm and corn borer; the corn variety "Herculex I” with glufosinate tolerance and lepidopteran resistance (Cry1 F), i.e.
  • Examples of commercial available transgenic plants with three traits are the corn variety "Herculex I / Roundup Ready 2" with glyphosate tolerance, gluphosinate tolerance and lepidopteran resistance (Cry1 F), i.e. against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Plus / Roundup Ready 2" (Monsanto) with glyphosate tolerance, corn rootworm resistance and corn borer resistance; the corn variety “Agrisure GT/CB/LL” (Syngenta) with tolerance to glyphosate tolerance, tolerance to gluphosinate and corn borer resistance; the corn variety "Herculex Xtra” (Dow, Pioneer) with glufosinate tolerance and lepidopteran resistance (Cry1 F + Cry34/35Ab1 ), i.e.
  • the commercial transgenic plant is a soybean variety with glyphosate tolerance and lepidopteran resistance, preferably with one trait of glyphosate tolerance and two traits of lepidopteran resistance.
  • the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4 (cp4epsps gene), more preferably it is based on the transgenic event MON89788.
  • the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably it is based on the transgenic event MON87701.
  • the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
  • Pseudoplusia includens is a synonym for Chrysodeixis includens.
  • the commercial transgenic plant is "Intacta RR2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
  • "Intacta RR2 Pro” is used as a synonym for "IntactaTM Roundup ReadyTM 2 Pro” soybean variety.
  • the invention relates to methods according to the invention wherein the cultivated plant is a soybean variety with glyphosate tolerance and lepidopteran resistance.
  • the invention relates to methods according to the invention, wherein the glyphosate tolerance is through the expression of the cp4epsps gene, or wherein the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis, or wherein both the glyphosate tolerance is through the expression of the cp4epsps gene and the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis.
  • the invention relates to methods according to the invention, wherein the glyphosate tolerance is based on the transgenic event MON89788, or wherein the lepidopteran resistance is based on the transgenic event MON87701 , or wherein both the glyphosate tolerance is based on the transgenic event MON89788 and the lepidopteran resistance is based on the transgenic event MON87701 .
  • the invention relates to methods according to the invention, wherein the lepidopteran resistance is against a species selected from the group of velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens, Chrysodeixis in- cludens ).
  • the invention relates to methods according to the invention, wherein the cultivated plant is "Intacta RR2 PRO" soybean (Monsanto), which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soy- bean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
  • major soybean pests velvetbean caterpilar, soy- bean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera
  • the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
  • stinkbug species preferably Euschistus heros
  • Spodoptera frugiperda preferably Spodoptera frugiperda
  • Helicoverpa preferably Helicoverpa.
  • the commercial transgenic plant is a soybean variety selected from “Roundup Ready 2 Yield”, “Intacta RR2 Pro” and “Vistive Gold” (all Monsanto), or “Stearidonic Acid (SDA) Omega-3” (higher content of SDA in soybean, Monsanto).
  • the trait is Bacillus thuringiensis Cry1A.105 and cry2Ab2 and Vector PV-GMIR13196, for Mon87751 soybean (Monsanto).
  • the commercial transgenic plant is a soybean variety with herbicide tolerance and lepidopteran resistance, wherein the control of Lepidopteran pest is based on Bt CrylAc and Cryl F toxins.
  • the insect-resistant and herbicide-tolerant soybean is DAS81419 (see Table A1 , entry A1 -334).
  • the plant has one trait of glyphosate tolerance and two traits of lepidopteran resistance.
  • the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4, more preferably it is based on the transgenic event MON89788.
  • the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudo- plusia includens), more preferably it is based on the transgenic event MON87701.
  • the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
  • Pseudoplusia includens is a synonym for Chrysodeixis includens.
  • the commercial transgenic plant is "Intacta RR2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
  • the commercial transgenic plant is a corn variety which has above- ground insect protection from “Genuity VT Triple PRO” or “Herculex Xtra” or both of them, and herbicide tolerance from “Roundup Ready 2" and Liberty Link, preferably corn varieties selected from “Genuity SmartStax", “Genuity VT Triple PRO” and “Genuity VT Double PRO” (all Monsanto), optionally as RIB (refuge-in-bag) solution.
  • the commercial transgenic corn plant variety has a drought tolerance trait, preferably "Genuity DroughtGard”.
  • the trait is double-stranded ribonucleic acid (dsRNA), Bacillus thuringiensis Cry3Bb1 protein and vector PV-ZMIR10871 for MON8741 1 corn.
  • the commercial transgenic plant is a cotton variety selected from “Boll- gard II” (insect protection), "Roundup Ready Flex” (herbicide tolerance) and “Bollgard II with Roundup Ready Flex” (both), all Monsanto.
  • the cultivated plants are plants, which comprise at least one trait of insect resistance (preferably by expression of bacterial toxins) and at least one trait selected from
  • the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express bacterial toxins, which provides resistance against animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis.
  • the plant is preferably selected from cotton, rice, maize, wheat, barley, rye, oat, soybean, potato, vine, apple, pear, citron and orange.
  • the plant is soybean.
  • the invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification as compared to the respective non-modified control plant, wherein the plant is soybean, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-82 as defined in Table A,. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A', more specifically compound 1-1 1 , more specifically compound 1-16, more spe- cifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .
  • the cultivated plants are plants, which are tolerant to the action of herbicides. Further guidance for specific combinations within this utmost preferred embodiment can be found in Table A1 .
  • compounds of formula I and their mixtures may additionally comprise a herbicide III, to which the plant is tolerant.
  • a herbicide III to which the plant is tolerant.
  • compounds of formula I and their mixtures may additionally comprise glyphosate.
  • the cultivated plant is a cultivated plant tolerant to glufonsinate
  • compounds of formula I and their mixtures may additionally comprise glufonisate.
  • the cultivated plant is a cultivated plant tolerant to a imidazolione herbicide
  • compounds of formula I and their mixtures may additionally comprise at least one imidazolione- herbicide.
  • the imidazolionone-herbicide is selected from imazamox, imazethapyr, ima- zapic, imazapyr, imazamethabenz or imazaquin.
  • the cultivated plant is a cultivated plant tolerant to dicamba
  • compounds of formula I and their mixtures may additionally comprise dicamba.
  • the cultivated plant is a cultivated plant tolerant to sethoxidim
  • compounds of formula I and their mixtures may additionally comprise sethoxidim.
  • compounds of formula I and their mixtures may additionally comprise cycloxidim.
  • the present invention also relates to ternary mixtures, comprising a compound of formula I, an insecticide II and a herbicide III.
  • the present invention also relates to ternary mixtures comprising two insecticides and a fungicide.
  • the present invention also relates to ternary mixtures comprising two fungicides and one insecticide.
  • the present invention also relates to ternary mixtures com- prising an insectide, a fungicide and a herbicide.
  • the cultivated plant is selected from the group of plants as mentioned in the paragraphs and tables of this disclosure, preferably as mentioned above.
  • the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance for example by expression of one or more bacterial toxins, fungal resistance or viral resistance or bacterial resistance by expression of one or more anti- pathogenic substances, stress tolerance, nutrient uptake, nutrient use efficiency, content modification of chemicals present in the cultivated plant compared to the corresponding control plant.
  • the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance by expression of one or more bacterial toxins, fungal re- sistance or viral resistance or bacterial resistance by expression of one or more antipathogenic substances, stress tolerance, content modification of one or more chemicals present in the cultivated plant compared to the corresponding control plant.
  • the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express one or more bacterial toxins, which provides resistance against one or more animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis.
  • the cultivated plant is preferably selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), cotton, rice and cereals such as wheat, barley, rye and oat.
  • the cultivated plants are plants, which are given in table 1.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with compounds of formula I and their mixtures, wherein the plant is a plant, which is rendered tolerant to herbicides, more preferably to herbicides such as glutamine synthetase inhibitors, 5-enol-pyrovyl- shikimate-3-phosphate-synthase inhibitors, acetolactate synthase (ALS) inhibitors, protoporphy- rinogen oxidase (PPO) inhibitors, auxine type herbicides, most preferably to herbicides such as glyphosate, glufosinate, imazapyr, imazapic, imazamox, imazethapyr, imazaquin, imaza- methabenz methyl, dicamba and 2,4-D.
  • herbicides such as glutamine synthetase inhibitors, 5-eno
  • the present invention relates to a method of controlling harmful pests, especially insects, by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with compounds of formula I and their mixtures compounds of formula I or their mixtures, wherein the plant corresponds to a row of table A1 .
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating plant propagation materials, preferably seeds with compounds of formula I and their mixtures selected from endosulfan, ethiprole and fipronil, wherein the plant corresponds to row of table A1.
  • the invention relates to a method for increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I, wherein the plant corresponds to a row of table A1.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula I, which is selected from the compounds 1-1 to I-82 as defined in Table A, wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , table 1 or table 2.
  • the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A'.
  • the properties of the mentioned plants are present in addition to the insecticidal trait.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I, wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , wherein the compound of formula I is compound 1-1 1 .
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , wherein the compound of formula I is compound 1-16.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 wherein the compound of formula I is compound I-26.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 wherein the compound of formula I is compound 1-31 .
  • Table A1
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I and its mixtures, wherein the plant is a plant, which express at least one insecticidal toxin, preferably a toxin from Bacillus speicies, more preferably from Bacillus thuringiensis.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating plant propagation materials, preferably seeds with the compound of formula I or its mixtures as defined above, prefera- bly wherein the plant corresponds to a row of table A2 or table 3.
  • the compound of formula I is compound 1-1 1 .
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21.
  • the compound of formula I is compound I-26. .
  • the compound of formula I is compound 1-31 .
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures wherein the plant corresponds to a row of table A2 or table 3. .
  • the compound of formula I is compound 1-1 1.
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21.
  • the compound of formula I is compound I-26.
  • the compound of formula I is compound 1-31 .
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3.
  • the compound of formula I is compound 1-1 1.
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21.
  • the compound of formula I is compound I-26. .
  • the compound of formula I is compound 1-31 .
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation materials, preferably seeds of cultivated plants of cultivated crops with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3.
  • the com- pound of formula I is compound 1-1 1.
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21.
  • the compound of formula I is compound I-26. .
  • the compound of formula I is compound 1-31 .
  • Table A2
  • A2-4 Lepidoptera COT102 (SYN- Gossypium hirsu- available, Syngenta Seeds, resistance IR102-7) tum L. (cotton) Inc.
  • a * refers to contestZhuxian B", WO2001021821 , Molecular Breeding, Volume 18, Number 1 / August 2006.
  • the cultivated plant has an arthropodicidal, preferably insecticidal, trait, it often occurs that the pest that should be combatted becomes resistant to that trait.
  • Resistance may be defined as 'a heritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product to achieve the expected level of control when used according to the label recommendation for that pest species'.
  • IRAC Iron Resistance therefore means that the original activitiy of a pesticide against the target organisms (arthropods, insects) decreases or is even lost, due to genetic or metabolic adaptation of the target organism.
  • Resistant to an insecticide is understood to mean resistant to at least one insecticide or insecticidal trait, i.e. the insect may be resistant to only one, but also to several insecticides or insecticidal traits.
  • the resistance is against an insecticidal effect which is due to a genetic modification of a plant (modified or transgenic plant), which caused a resistance of the plant or crop to certain pests, especially insect pests, in susceptible insects.
  • insecticidal proteins especially those mentioned herein, es- pecially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as 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., and so on.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • insecticidal proteins of bacteria colonizing nematodes for example Photorhabdus spp. or Xenorhabdus spp., and so on.
  • the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one insecti- cidal trait, and wherein the harmful insects are resistant to that at least one insecticidal trait of the plant.
  • the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one lepidopteran or coleopteran trait, and wherein the harmful insects are resistant to that lepidopteran or coleopteran insecticidal trait of the plant.
  • a compound of formula (I) or a mixture thereof wherein the plant has at least one lepidopteran or coleopteran trait, and wherein the harmful insects are resistant to that lepidopteran or coleopteran insecticidal trait of the plant.
  • the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant having the insecticidal trait corresponds to a row of table A2 or Table 3 or Table A1 , and wherein the harmful insects are resistant to an insecticidal trait of the plant.
  • the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
  • stinkbug species preferably Euschistus heros
  • Spodoptera frugiperda preferably Spodoptera frugiperda
  • Helicoverpa preferably Helicoverpa.
  • the compound of formula (I) may optionally be mixed with one or more further pesticides.
  • Methods and uses of the invention as described herein may also involve a step of assessing whether insects are resistant to certain insecticides.
  • This step will in general involve collecting a sample of insects from the area (e.g. crop, field, habitat) to be treated, before actually applying a compound of formula (I), and testing (for example using any suitable phenotypic, biochemical or molecular biological technique applicable) for resistance/sensitivity.
  • the plants may have more traits and/or events, e.g. those described in Table A1 .
  • the cultivated plant is preferably selected from the group consisting of soybean, cotton and maize, wherein the plant has been made tolerant to the action of certain herbicides as described above. It is particularly preferred that the cultivated plant is selected from the group consisting of soybean, cotton and maize, wherein the plant has been made tolerant to the action of glyphosate herbicides.
  • the cultivated plant is a plant, which has been made tolerant to the action of glyphosate herbicides.
  • the plant may have been made tolerant to other herbicides and/or resistant to certain insects, and/or the plant may have been genetically modified otherwise, e.g. in terms of abiotic stress tolerance, altered growth/yield, disease resistance, modified product quality or pollination control system.
  • Third embodiment of the invention is a plant, which has been made tolerant to the action of glyphosate herbicides.
  • the plant may have been made tolerant to other herbicides and/or resistant to certain insects, and/or the plant may have been genetically modified otherwise, e.g. in terms of abiotic stress tolerance, altered growth/yield, disease resistance, modified product quality or pollination control system.
  • the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
  • Insect resistance in particular lepidopteran resistance is of growing importance in GMO crops.
  • the cultivated plant is soybean, which has been made resistant to lepidoperan insects.
  • the soybean may have been made tolerant to certain herbicides and/or resistant to other insects, and/or the soybean may have been genetically modified otherwise, e.g. in terms of abiotic stress tolerance, altered growth/yield, disease resistance, modified product quality or pollination control system.
  • the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a lepidopteran insect resistant soybean and corresponds to a row of table A1 , A2 or table 3.
  • Lepidopteran resistance of soybeans is typically achieved by introducing a gene selected from the group consisting of: crylAc (gene source: Bacillus thuringiensis subsp. Kurstaki strain HD73), cry1 F (gene source: Bacillus thuringiensis var. aizawai), cry1A.105 (gene source: Bacillus thuringiensis subsp.
  • soybeans may be modified e.g. in terms of herbicide tolerance by introducing a suitable gene such as pat (gene source: Strepto- myces viridochromogenes), which provides glufosinate tolerance or cp4 epsps (aroA:CP4) (gene source: Agrobacterium tumefaciens strain CP4), which provides glyphosate tolerance.
  • pat gene source: Strepto- myces viridochromogenes
  • aroA:CP4 gene source: Agrobacterium tumefaciens strain CP4
  • the soybeans are additionally modified in terms of glyphosate tolerance by introduc- ing the gene cp4 epsps (aroA:CP4).
  • the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with c compounds of formula (I) and their mixtures, wherein the plant is a lepidopteran insect resistant soybean, which has been modified by intro- ducing at least one gene or at least one gene combination, which corresponds to a row of table C.
  • the present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is Gossypium hirsutum L. (cotton) or Zea mays L. (maize) and comprises at least one gene selected from the group consisting of dvsnf7, cry1A, cry1Ab-Ac, cry1 C, cry2Ab2, cry2Ae, mocryl F; or
  • Glycine max L. (soybean), Triticum aestivum (wheat) or Oryza sativa L. (rice) and comprises at least one gene selected from the group consisting of cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, mcry3A, cry1A, cry1A.105, crylAb, cry1Ab-Ac, crylAc, cry1 C, cry1 F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), vip3Aa20.
  • the present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is modified by at least one gene according to one row of table D2.
  • the compound of formula I is selected from the compounds 1-1 to I-82 as defined in Table A curat wherein the plant corresponds to a row of table76.
  • the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in
  • the compound of formula I is compound 1-1 1 .
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21 .
  • the compound of formula I is compound I-26.
  • the compound of formula I is compound 1-31 .
  • Further preferred embodiments of the invention are those methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
  • the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula I is fipronil and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
  • the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula I is ethiprole and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
  • the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula lcompound is chlorfenapyr and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
  • the present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is modified by at least one gene as described in the follow- ing.
  • the compound of formula I is selected from the compounds 1-1 to I-82 as defined in Table A, wherein the plant corresponds to a row of table76.
  • the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A'.
  • the compound of formula I is compound 1-1 1 .
  • the compound of formula I is compound 1-16.
  • the compound of formula I is compound 1-21 .
  • the compound of formula I is compound I-26.
  • the compound of formula I is compound 1-31 .
  • further embodiments of the invention are those methods of controlling harmful in- sects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with a compound of formula (I) or a mixture thereof according to the invention, wherein the plant expresses one or more genes selected from aad, ACCase, ALS, AMY797E, APH4, bar, barnase, barstar, bla, bxn, cDHDPS, CP, cmv-cp, CrylAb, CrylAc, Cry1A.105, Cry1 F, Cry1 Fa2, Cry2Ab, Cry34Ab1 , Cry35Ab1 , Cry3A, Cry3Bb1 , Cry9C, dam, DHFR, fad2, fanl , FH, flcrylAb, GAT4601 , GAT4602, gmFAD2-1 , GM-HRA, goxv247, gus,
  • the compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO 2007/006670, WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein.
  • the characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points.
  • HPLC/MS High Performance Liquid Chromatography / mass spectrometry
  • Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds.
  • the presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):
  • the species used is Anticarsia gem- matalis (H ibner) [Thermesia elegantula (Herrich-Schaffer, 1869)], Noctuidae. 5 plants/plot are infested with 3 larvae (stage L2) using a entomological metallic tweezers, totaling 15 larvae per repetition. Larvae used in this trial are e.g. provided by BASF rearing laboratory, Campinas, Brazil.
  • a second infestation is held seven days after application in the same plants and using the same larval numbers.
  • a third infestation might be done if necessary in order to observe residual activi- ty.
  • the mortality (number) and eating damage (%) are evaluated with 01 , 02, 05, 07, 14 and 21 DAA (days after application), comparing to untreated control plants.

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Abstract

The present invention relates to agricultural methods for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification, using anthranilamide compounds of formula (I) wherein R1, R2, R3, R4, R5, R6 and k are as defined in the description; and mixtures thereof. In particular, the invention relates to methods of controlling harmful insects on special soybean varieties. In particular, the invention relates to methods of controlling harmful insects, which are resistant to an insecticidal trait of the plant.

Description

Use of N-thio-anthranilamide compounds on cultivated plants
The present invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification (hereinafter abbreviated as "cultivated plant") as compared to the respective non-modified control plant, comprising the application of a pesti- cidally active compound of formula I
Figure imgf000002_0001
wherein
R1 is selected from the group consisting of H, F, CI, Br and CN;
R2 is selected from the group consisting of F, CI, Br, I, CH3;
R3 is selected from the group consisting of Br, CI, CHF2, CF3 and OCH2F;
R4 is CI or CF3;
R5, R6 are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl, Cs-Cs-cycloalkyl, or
R5 and R6 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,
k is O or l ;
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;
to a cultivated plant, parts of such plant, plant propagation material, or at its locus of growth.
The term "compound of formula (I) or a stereoisomer, salt, tautomer or N-oxide thereof" is un- derstood to include a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide, even if not mentioned explicitly.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavourable environmental or toxicological effects whilst still allowing effective pest control. Another problem underlying the invention is the desire for compositions that improve the health of a plant, a process which is commonly and hereinafter referred to as "plant health". The term plant health comprises various sorts of improvements of plants that are not connected to the control of pests and which do not embrace the reduction of negative conse- quences of harmful insects. The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e.g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect"), quality (e.g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
It was therefore the object of the present invention to provide a method, which solves the problems as outlined above and which especially reduces the dosage rate and/or promotes the health of a plant.
Surprisingly, it has now been found that the use of a compound of formula (I) as defined above in cultivated plants displays a synergistic effect between the trait of the cultivated plant and the applied compound of formula (I). In a first embodiment, cultivated plants are plants that have at least one insecticidal trait. It is a wide-spread problem that insects, that are combatted with insectides, develop resistance, i.e. they become less or not all anymore susceptible to the insecticidal effect.
Surprisingly, it has now been found that compounds of formula (I) are useful in methods of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth, wherein the plant has at least one insecticidal trait, and wherein the harmful insects are resistant to an insecticidal trait of the plant.
In a second embodiment, cultivated plants are specific plants that have at least one herbicidal and at least one insecticidal trait, preferably soybeans, more preferably the soybeans known as"lntacta RR2 PRO" soybean (Monsanto). Surprisingly, it has now been found that compounds of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
In a third embodiment, cultivated plants are plants that have at least one trait or trait
combination which has not yet been described in connection with the use of compounds of formula (I) on cultivated plants, e.g. as listed in Table A14 or Table B2.
Surprisingly, it has now been found that compounds of formula (I) are also useful in methods of controlling harmful insects by treating those mentioned cultivated plants, parts of such plants or their locus of growth.
Compounds of formula I
WO2007/006670, WO2013/024009, WO2013/024010 and WO2013/174645 describe N-thio- anthranilamide compounds with a sulfilimine or sulfoximine group and their use as pesticides. WO2014/053395 describes the use of N-thio-anthranilamide compounds on certain cultivated plants.
The compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein. 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.
However, although the anthranilamide compounds of formula (I) themselves have been described in methods and uses for controlling harmful pests on certain cultivated plants, there are further cultivated plants on which the compounds of formula (I) are surprisingly effective.
The compounds of formula (I) as well as the terms "compounds for methods according to the (present) invention", "compounds according to the (present) invention" or "compounds of formula (I)" or "compound(s) II", which all compound(s) are applied in methods and uses according to the present invention comprise the compound(s) as defined herein as well as a known stereoisomer, salt, tautomer or N-oxide thereof (including a polymorphic crystalline form, a co-crystal or a solvate of a compound or a stereoisomer, salt, tautomer or N-oxide thereof).
The term "composition(s) according to the invention" or "composition(s) of the present invention" encompasses composition(s) comprising at least one compound of formula (I) or mixtures of the compounds of formula (I) with other pesticidally active compound(s) II for being used and/or applied in methods according to the invention as defined above.
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).
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.
In general, suitable "agriculturally useful salts" or "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 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 Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-Ci-C4-alkyl, hydroxy-Ci- C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise me- thylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trime- thylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2- hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammonium, furthermore phosphonium ions, sul- fonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4- alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of the formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
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 ste- reoisomer, salt, tautomer or N-oxide thereof, with one or more other molecules (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. The remarks made below as to preferred embodiments of the variables (substituents) of the compounds of formulae (I) 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.
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 alkoxyalkyi) denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 or 1 to 4 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-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1 -ethyl-1 -methylpropyl and 1 -ethyl-2-methyl propyl.
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 "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 bicy- clic cycloaliphatic radical having usually from 3 to 10 carbon atoms ("C3-Cio-cycloalkyl"), preferably 3 to 8 carbon atoms ("Cs-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, bicy- clo[2.2.1]heptyl, bicyclo[3.1 .1 ]heptyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl and bicy- clo[3.2.1 ]octyl.
The term "alkenyl" as used herein denotes in each case a monounsaturated straight-chain or branched hydrocarbon radical having usually 2 to 7 carbon atoms ("C2-C7-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.
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 "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 "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group usually having usually froml 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. Ci-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 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2-trimethylpropoxy, 1 ,2,2- trimethylpropoxy, 1 -ethyl-1 -methylpropoxy or 1 -ethyl-2-methylpropoxy.
The term "alkoxyalkyl" as used herein denotes in each case alkyl usually comprising 1 to 4 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4 carbon atoms as defined above. "Ci-C4-Alkoxy-Ci-C6-alkyl" is a Ci-C4-alkyl group, as defined above, in which one hydrogen atom is replaced by a Ci-C4-alkoxy group, as defined above. Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (1 -methylpropoxy)- methyl, (2-methylpropoxy)methyl, CH2-OC(CH3)3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n- propoxy)-ethyl, 2-(1 -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 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-a I kylsu If i nyl " 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, at- tached via a sulfinyl [S(O)] group. The term "Ci-C6-alkylsulfinyl" refers to a Ci-C6-alkyl group, as defined above, attached via a sulfinyl [S(O)] group. Ci-C2-alkylsulfinyl is methylsulfinyl or ethyl- sulfinyl. Ci-C4-alkylsulfinyl is additionally, for example, n-propylsulfinyl, 1 -methylethylsulfinyl (isopropylsulfinyl), butylsulfinyl, 1 -methylpropylsulfinyl (sec-butylsulfinyl), 2-methylpropylsulfinyl (isobutylsulfinyl) or 1 ,1 -dimethylethylsulfinyl (tert-butylsulfinyl). Ci-C6-alkylsulfinyl 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 -dimethylbutylsulfinyl, 1 ,2-dimethylbutylsulfinyl, 1 , 3-d imethyl butylsulfi nyl , 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3- dimethylbutylsulfinyl, 1 -ethylbutylsulf inyl , 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 ethyl- sulfonyl. 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). C1-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 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, haloalkylcar- bonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloal- koxycarbonyl.
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. thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyra- zole, 1 ,3,4-oxadiazole, 1 ,3,4-thiadiazole, 1 ,3,4-triazole, 1 ,2,4-oxadiazole, 1 ,2,4-thiadiazole, 1 ,2,4-triazole, 1 ,2,3-triazole, 1 ,2,3,4-tetrazole, benzo[b]thiophene, benzo[b]furan, indole, ben- zo[c]thiophene, benzo[c]furan, isoindole, benzoxazole, benzthiazole, benzimidazole, benzisoxa- zole, benzisothiazole, benzopyrazole, benzothiadiazole, benztriazole, dibenzofuran, dibenzothi- ophene, carbazole, pyridine, pyrazine, pyrimidine, pyridazine, 1 ,3,5-triazine, 1 ,2,4-triazine, 1 ,2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1 ,8-naphthyridine, 1 ,5-naphthyridine, 1 ,6-naphthyridine, 1 ,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxazolidine or thiazolidine, oxirane or oxetane.
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; 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, sul- fur, 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)-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.
The compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein.
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) 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 are methods and uses of compounds of formula (I), wherein the compound of formula (I) is as preferred in the following embodiments.
In one embodimentof the, R1 is selected from the group consisting of CI, Br and CN.
In a further embodiment, R1 is CI.
In a further embodiment, R1 is CN.
In one embodiment, R2 is selected from the group consisting of CI, Br and CH3 (Me).
In a further embodiment, R2 is CI.
In a further embodiment, R2 is CH3.
In one embodiment, the invention relates to methods and uses, in which in the compound of formula I
R1 is selected from the group consisting of Br, CI, CN, preferably CI;
R2 is selected from the group consisting of CI, CH3; preferably CH3.
In a preferred embodiment, R1 is CI, and R2 is CH3.
In a further embodiment, R1 is CI, and R2 is CI.
In a further embodiment, R1 is CN, and R2 is CH3.
In one embodiment, k is 0 in the compounds of formula (I):
Figure imgf000010_0001
wherein R1, R2, R3, R4, R5, R6 are as defined herein. In one embodiment, k is 1 in the compounds of formula (I):
Figure imgf000011_0001
wherein R1, R2, R3, R4, R5, R6 are as defined herein.
In one embodiment, the invention relates to methods and uses, in which in the compound of formula I
R3 is CF3 or Br, preferably CF3.
R4 is CI.
Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula IB:
Figure imgf000011_0002
wherein the variables R1, R3, R5, R6 and k are as defined herein. Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula IC:
Figure imgf000012_0001
wherein the variables R1, R2, R5, R6 and k are as defined herein.
Preferred are methods and uses of compounds of formula (I), in which the compound of formula I is a compound of formula ID:
Figure imgf000012_0002
wherein the variables R1, R2, R5, R6 and k are as defined herein.
In one embodiment, the invention relates to methods and uses, in which in the compound of formula I
R1 is selected from the group consisting of Br, CI, CN, preferably CI;
R2 is selected from the group consisting of CI, CH3; preferably CH3;
R3 is CF3 or Br, preferably CF3;
R4 is CI.
In a preferred embodiment, the invention relates to methods and uses of compounds of formula (I), in which R5 and R6 are selected independently of one another from the group consisting of hydrogen, Ci-C4-alkyl and Cs-Cs-cycloalkyl.
In a further preferred embodiment, the invention relates to methods and uses of compounds of formula (I), in which R5 and R6 are selected from Ci-C4-alkyl, preferably selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, more preferably methyl, ethyl, isopropyl, most preferably ethyl.
In an analogously preferred embodiment, the invention relates to methods and uses of compounds of formula (IB), in which R5 and R6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
In an analogously preferred embodiment, the invention relates to methods and uses of compounds of formula (IC), in which R5 and R6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
In an analogously preferred embodiment, the invention relates to methods and uses of compounds of formula (ID), in which R5 and R6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably methyl, ethyl, isopropyl, most preferably ethyl.
In another embodiment, R5 and R6 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.
In a preferred embodiment, R5 and R6 are identical, and preferably selected from methyl, ethyl, and isopropyl.
A group of especially preferred compounds of formula I in the methods and uses according to the invention are compounds 1-1 to I-82 of formula IA which are listed in the table A.
Figure imgf000013_0001
Table A
R R2 R3 R5 R6 k R R2 R3 R5 R6 k
1-1 CI CHs CFs CHs CHs 0 1-10 CI CI CN CHs CHs 0
I-2 CI CHs CHF2 CHs CHs 0 1-1 1 CI CHs CFs C2H5 C2H5 0
I-3 CI CHs Br CHs CHs 0 1-12 CI CHs CHF2 C2H5 C2H5 0
I-4 CI CHs CI CHs CHs 0 1-13 CI CHs Br C2H5 C2H5 0
I-5 CI CHs CN CHs CHs 0 1-14 CI CHs CI C2H5 C2H5 0
I-6 CI CI CFs CHs CHs 0 1-15 CI CHs CN C2H5 C2H5 0
I -7 CI CI CHF2 CHs CHs 0 1-16 CI CI CFs C2H5 C2H5 0
I-8 CI CI Br CHs CHs 0 1-17 CI CI CHF2 C2H5 C2H5 0
I-9 CI CI CI CHs CHs 0 1-18 CI CI Br C2H5 C2H5 0 R R2 R3 R5 R6 k R R2 R3 R5 R6 k
1-19 CI CI CI C2H5 C2H5 0 1-51 CI CI CN CHs CHs 1
I-20 CI CI CN C2H5 C2H5 0 I-52 CI CHs CFs C2H5 C2H5 1
1-21 CI CHs CFs CH(CHs)2 CH(CHs)2 0 I-53 CI CHs CHF2 C2H5 C2H5 1
I-22 CI CHs CHF2 CH(CHs)2 CH(CHs)2 0 I-54 CI CHs Br C2H5 C2H5 1
I-23 CI CHs Br CH(CHs)2 CH(CHs)2 0 I-55 CI CHs CI C2H5 C2H5 1
I-24 CI CHs CI CH(CHs)2 CH(CHs)2 0 I-56 CI CHs CN C2H5 C2H5 1
I-25 CI CHs CN CH(CHs)2 CH(CHs)2 0 I-57 CI CI CFs C2H5 C2H5 1
I-26 CI CI CFs CH(CHs)2 CH(CHs)2 0 I-58 CI CI CHF2 C2H5 C2H5 1
I-27 CI CI CHF2 CH(CHs)2 CH(CHs)2 0 I-59 CI CI Br C2H5 C2H5 1
I-28 CI CI Br CH(CHs)2 CH(CHs)2 0 I-60 CI CI CI C2H5 C2H5 1
I-29 CI CI CI CH(CHs)2 CH(CHs)2 0 1-61 CI CI CN C2H5 C2H5 1
I-30 CI CI CN CH(CHs)2 CH(CHs)2 0 I-62 CI CHs CFs CH(CHs)2 CH(CHs)2 1
1-31 Br Br CFs C2H5 C2H5 0 I-63 CI CHs CHF2 CH(CHs)2 CH(CHs)2 1
I-32 Br Br CHF2 C2H5 C2H5 0 I-64 CI CHs Br CH(CHs)2 CH(CHs)2 1
I-33 Br Br Br C2H5 C2H5 0 I-65 CI CHs CI CH(CHs)2 CH(CHs)2 1
I-34 Br Br CI C2H5 C2H5 0 I-66 CI CHs CN CH(CHs)2 CH(CHs)2 1
I-35 Br Br CN C2H5 C2H5 0 I-67 CI CI CFs CH(CHs)2 CH(CHs)2 1
I-36 Br Br CFs CH(CHs)2 CH(CHs)2 0 I-68 CI CI CHF2 CH(CHs)2 CH(CHs)2 1
I-37 Br Br CHF2 CH(CHs)2 CH(CHs)2 0 I-69 CI CI Br CH(CHs)2 CH(CHs)2 1
I-38 Br Br Br CH(CHs)2 CH(CHs)2 0 I-70 CI CI CI CH(CHs)2 CH(CHs)2 1
I-39 Br Br CI CH(CHs)2 CH(CHs)2 0 1-71 CI CI CN CH(CHs)2 CH(CHs)2 1
I-40 Br Br CN CH(CHs)2 CH(CHs)2 0 I-72 Br Br CFs C2H5 C2H5 1
1-41 CN CI CFs CH(CHs)2 CH(CHs)2 1 I-73 Br Br CHF2 C2H5 C2H5 1
I-42 CI CHs CFs CHs CHs 1 I-74 Br Br Br C2H5 C2H5 1
I-43 CI CHs CHF2 CHs CHs 1 I-75 Br Br CI C2H5 C2H5 1
I-44 CI CHs Br CHs CHs 1 I-76 Br Br CN C2H5 C2H5 1
I-45 CI CHs CI CHs CHs 1 I-77 Br Br CFs CH(CHs)2 CH(CHs)2 1
I-46 CI CHs CN CHs CHs 1 I-78 Br Br CHF2 CH(CHs)2 CH(CHs)2 1
I-47 CI CI CFs CHs CHs 1 I-79 Br Br Br CH(CHs)2 CH(CHs)2 1
I-48 CI CI CHF2 CHs CHs 1 I-80 Br Br CI CH(CHs)2 CH(CHs)2 1
I-49 CI CI Br CHs CHs 1 1-81 Br Br CN CH(CHs)2 CH(CHs)2 1
I-50 CI CI CI CHs CHs 1 I-82 CN CI CFs CH(CHs)2 CH(CHs)2 1
In one embodiment, a compound selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as in Ta ble A' is the compound I in the methods and uses according to the invention.
In a further embodiment, a compound selected from compounds I-52, I-57, I-62, I-67, I-72 as i Table A" is the compound I in the methods and uses according to the invention.
Table A' R R2 R3 R5 R6 k
R R2 R3 R5 R6 k 1-21 CI CHs CFs CH(CHs)2 CH(CHs)2 0
1-1 1 CI CHs CFs C2H5 C2H5 0 I-26 CI CI CFs CH(CHs)2 CH(CHs)2 0
1-16 CI CI CFs C2H5 C2H5 0 1-31 Br Br CFs C2H5 C2H5 0 Table A" R R2 R3 R5 R6 k
I-62 CI CHs CFs CH(CHs)2 CH(CHs)2 1
I-67 CI CI CFs CH(CHs)2 CH(CHs)2 1
Figure imgf000015_0003
I-72 Br Br CFs C2H5 C2H5 1
In one embodiment, 1-1 1 is the compound I in the methods and uses according to the invention, In one embodiment, 1-16 is the compound I in the methods and uses according to the invention, In one embodiment, 1-21 is the compound I in the methods and uses according to the invention, In one embodiment, I-26 is the compound I in the methods and uses according to the invention, In one embodiment, 1-31 is the compound I in the methods and uses according to the invention.
It is understood that also derivatives of the compounds of formula (I) are encompassed by the present invention, e.g. methods and uses of compounds of formula Γ, and methods and uses of c
Figure imgf000015_0001
wherein the variables R1, R2, R3, R4 are as defined herein and are preferably Γ-1 or Γ-2.
It is understood that also quinazolinone derivatives of the compounds of formula (I) are
passed by the present invention, e.g. methods and uses of compounds of formula I".
Figure imgf000015_0002
wherein the variables R1, R2, R3, R4 are as defined herein and are preferably l"-1 or l"-2. Pests
In the methods according to the invention, the compounds of formula I are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
insects from the order of Lepidoptera, for example Achroia grisella, Acleris spp. such as A. fimbriana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sarcitella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticar- sia (=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugel- la, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca vi- ridigrisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bon- agota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indi- cus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eurytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Dalaca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Diatraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus ligno- sellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Herpetogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseu- dospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Leguminivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leu- coma salicis, Leucoptera spp. such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malaco- soma spp. such as M. americanum, M. californicum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mamstra brassicae, Manduca spp. such as M. quin- quemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Mon- ochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Oper- ophtera brumata, Orgyia pseudotsugata, Oria spp., Orthaga thyrisalis, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paranthrene regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma saucia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathy- pena scabra, Platynota spp. such as P. flavedana, P. idaeusalis, P. stultana; Platyptilia cardui- dactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xy- lostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ven- tralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura concinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga cerealella, Spargan- othis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. Iittoralis, S. Iitura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima am- pelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pel- lionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga tapetzella, Trichoplu- sia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubi- galis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulen- ta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aula- cophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Cal- lopistria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Ceroto- ma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryp- torhynchus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eu- tinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hy- pera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lath- ridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decem- lineata; Leptispa pygmaea, Limonius califomicus, Lissorhoptrus oryzophilus, Lixus spp., Lu- perodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Maladera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melol- ontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monocha- mus spp. such as M. altematus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhyn- chus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha re- curva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Pop- illia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psylliodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda Candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Stemechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Za- brus spp. such as Z. tenebrioides;
insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipiens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inor- nata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasineura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermatobia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphilus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fusci- pes, G. morsitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppo- bosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifo- lii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Musci- na stabulans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. anti- qua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calci- trans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodi- plosis japonensis, Tipula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchae- tothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagines, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A. schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cockerelli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis te- galensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Ci- mex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperidum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbulus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Di- aphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops eatus, Diconoco- ris hewetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empoasca spp. such as E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp. such as E. lanig- erum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Euschistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffe- ae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodis- ca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, lcerya spp. such as /. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecani- um spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lep- toglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. praten- sis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriola- ta, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocal- lis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Mo- nelliopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cerasi, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neomegalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. virescens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Para- bemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corni, P. persicae; Pemphigus spp. such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoccus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvi- naria pyriformis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudo- coccus spp. such as P. comstocki; Psylla spp. such as P. mail; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastro- coccus spp., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. padi; Saga- todes spp., Sahlbergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scapto- coris spp., Scaphoides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insu- laris, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, At- ta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sexdens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. florida- nus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocos- mus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinen- sis, Paratrechina longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp;
Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. america- na, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus; Pests from the Class Arachnida for example Acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. mi- croplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacificus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizoglyphus spp., Sarcoptes spp. such asS. Scabiei; and Family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pelekassi; Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllo- coptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni; Family Tar- sonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Stenotarsonemus spp. Steneotarsonemus spinki; Family Tenuipalpidae including Brevi- palpus spp. such as B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eute- tranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as T. cinnabarinus, T. evansi, T. kanzawai, Ύ, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macro- nyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyropha- gus putrescentiae; Family Acaridae including Acarus siro; Family Araneida including Latrodec- tus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glycines, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. Ion- gicaudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hem- icycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, Hop- loaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as L. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylencho- rhynchus spp. such as T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp. such as T. semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species;
Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as /. minor, I. Snyder, Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis; Blat- tella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Peri- planeta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Su- pella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis, Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp. such as C. felis, C. can is, Xenopsylla cheopis, Pulex irritans, Tricho- dectes canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica,
Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;
Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp., Pests from the class Symphyla for example Scutigerella immaculata,
Insects from the order Dermaptera, for example Forficula auricularia,
Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
Insects from the order Phthiraptera, for example Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; 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.,
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, 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, Diphyl- lobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocu- laris, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum 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, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
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 species: Thysanoptera : Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips pa Imi and Thrips tabaci. Mixtures of the present invention are particularly useful for controlling insects of the orders Lepidoptera, Coleoptera, Hemiptera and Thysanoptera.
The 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, white- flies, scale insects, cicadas (Hemiptera), ants, bees, wasps, sawflies (Hymenoptera), crickets, grasshoppers, locusts (Orthoptera), and also Arachnoidea, such as arachnids (Acarina).
Compounds (II)
In one embodiment of the invention, the compounds of formula I are employed as a solo prod- uct.
One typical problem arising in the field of pest control lies in the need to reduce the dosage rates of the active ingredient in order to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control.
The present invention also relates to methods for controlling pests and/or increasing the plant health of a cultivated plant, comprising in the application of a mixture of a compound of formula I and a pesticide II to a cultivated plant, parts of such plant, plant propagation material, or at its locus of growth.
Therefore, in another embodiment of the invention, the compounds of formula I are employed in combination (e.g. a mixture) with one or more compounds II which is a preferably a further in- secticide or a fungicide.
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: 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
M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofu- ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, for example 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, me- carbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxyde- meton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phos- phamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyri- daphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thi- ometon, triazophos, trichlorfon and vamidothion;
M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
M.3 Sodium channel modulators from the class of M.3A pyrethroids, for example 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, hep- tafluthrin, imiprothrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluth- rin, tetramethrin, tralomethrin and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonicotinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thia- cloprid and thiamethoxam; or the compounds M.4A.2: (2E-)-1 -[(6-Chloropyridin-3-yl)methyl]-N'- nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7- methyl-8-nitro-5-propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, for example spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin; M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydroprene, ki- noprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, for example M.9B pymetrozine, or M.9C floni- camid;
M.10 Mite growth inhibitors, for example M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
M.1 1 Microbial disruptors of insect midgut membranes, for example 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: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase, for example M.12A diafenthiuron, or M.12B or- ganotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, for example chlorfenapyr, DNOC or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novalu- ron, noviflumuron, teflubenzuron or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin;
M.17 Moulting disruptors, Dipteran, as for example cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
M.19 Octopamin receptor agonists, as for example amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, for example M.20A hydramethyl- non, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, for example M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers, for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4- (difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid deriva- tives, for example spirodiclofen, spiromesifen or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, for example 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, for example cyenopyrafen or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, as for example flubendia- mide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluor-1 -
(trifluormethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid and M.28.2: (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.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 - cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (pro- posed ISO name: cyclaniliprole), or the compound M.28.4: 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 M.28.5i) N-[2-(5-Amino-1 ,3,4- thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1 -(3-chloro-2-pyridinyl)-1 H-pyrazole-5- carboxamide; M.28.5j) 3-Chloro-1 -(3-chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(1 -cyano-1 - methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4- dichloro-6-(methylcarbamoyl)phenyl]-1 -(3,5-dichloro-2-pyridyl)-1 H-pyrazole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1 -dimethylethyl)amino]carbonyl]-6-methylphenyl]-1 -(3-chloro-2- pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; or
M.28.6: cyhalodiamide; or;
M.29. insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, flu- ensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butox- ide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the com- pounds
M.29.3: 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
M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, or the compound
M.29.5: 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, 1-1582); or
a compound selected from the group of M.29.6, wherein the compound is selected from M.29.6a) to M.29.6k): M.29.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide; M.29.6d) (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6f) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide; M.29.6g) (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide; M.29.6h) (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide; M.29.6i) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro- propanamide.); M.29.6j) N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- thioacetamide; or M.29.6k) N-[1 -[(6-chloro-3-pyndyl)methyl]-2-pyndylidene]-2,2,2-trifluoro-N'- isopropyl-acetamidine; or the compounds
M.29.8: fluazaindolizine; or the compounds
M.29.9.a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 - oxothietan-3-yl)benzamide; or M.29.9.b): fluxametamide; or
M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 , 2,2,3,3,3- hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]-benzamide; M.29.1 1 .d) N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1.e) N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide; M.29.1 1.f) 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1.g) 3-fluoro-N-[2- fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1.h) 2-chloro-N-[3- [[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.29.1 1.i) 4-cyano-N- [2-cyano-5-[[2,6-dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.j) 4-cyano-3-[(4-cyano-2-methyl- benzoyl)amino]-N-[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)propyl]phenyl]-2- fluoro-benzamide; M.29.1 1.k) N-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1 - (trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;
M.29.1 1 .1) N-[5-[[2-bromo-6-chloro-4-[2,2,2-trifluoro-1 -hydroxy-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;
M.29.1 1 .m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.29.1 1 .n) 4-cyano-N- [2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)- propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1 .o) 4-cyano-N-[2-cyano-5-[[2,6- dichloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl- benzamide; M.29.1 1 .p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; or a compound selected from the group of M.29.12, wherein the compound is selected from
M.29.12a) to M.29.12m): M.29.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.29.12.b) 2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.c) 2-[6-[2- (3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.d) N-Methylsulfonyl-6-[2-(3- pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12. e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol- 5-yl]pyridine-2-carboxamide; M.29.12.f) N-Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12. g) N-Methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12.h) N,2-Dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12. i) N-Ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12J) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3- methylthio-propanamide; M.29.12.k) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3- methylthio-propanamide; M.29.12.1) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio- propanamide; M.29.12.m) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio- propanamide; or the compounds
M.29.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 , 2,3,5, 6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; or M.29.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compounds
M.29.16a) 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1 - (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1 - [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
M.29.16e) N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.29.16f) 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.29.16g) 1 -[1 -(1 -cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole- 4-carboxamide; M.29.16h) N-methyl-1 -(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; M.29.16i) 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; or M.29.16j) 1 -(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide, or
M.29.17 a compound selected from the compounds M.29.17a) to M.29.17j): M.29.17a) N-(1 - methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17b) N-cyclopropyl-2-(3- pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N-cyclohexyl-2-(3-pyridinyl)-2H-indazole-4- carboxamide; M.29.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; M.29.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide;
M.29.171) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; M.29.17g) N- [(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17h) N-(2,2- difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.29.17i) 2-(3-pyridinyl )-N-(2- pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.29.17j) N-[(5-methyl-2-pyrazinyl)methyl]-2- (3-pyridinyl)-2H-indazole-5-carboxamide, or
M.29.18 a compound selected from the compounds M.29.18a) to M.29.18d): M.29.18a) N-[3- chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfanyl)propanamide; M.29.18b) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3-(3,3,3-trifluoropropylsulfinyl)propanamide;
M.29.18c) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N- ethyl-propanamide; M.29.18d) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-3-[(2,2- difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide; or the compound
M.29.19 sarolaner, or the compound
M.29.20 lotilaner.
The commercially available compounds of the group M listed above may be found in The Pes- ticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html. Another online data base for pesticides providing the ISO common names is
http://www.alanwood.net/pesticides.
The M.4 neonicotinoid cycloxaprid is known from WO2010/069266 and WO201 1/069456, the neonicotinoid M.4A.2, sometimes also to be named as guadipyr, is known from
WO2013/003977, and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from WO2007/101369. The metaflumizone analogue M.22B.1 is described in CN10171577 and the analogue M.22B.2 in CN102126994. The phthalamides M.28.1 and M.28.2 are both known from WO2007/101540. The anthranilamide M.28.3 is described in WO2005/077934. The hydra- zide compound M.28.4 is described in WO2007/043677. The anthranilamide M.28.5i) is de- scribed in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and
M.28.5I) in WO2012/034403. The diamide compound M.28.6 can be found in WO2012/034472. The spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.29.4 from WO2008/06791 1. The tri- azoylphenylsulfide M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707. The compounds M.29.6a) to M.29.6i) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in
WO2013/129688. The nematicide M.29.8 is known from WO2013/055584. The isoxazoline M.29.9.a) is described in WO2013/050317. The isoxazoline M.29.9.b) is described in
WO2014/126208. The pyridalyl-type analogue M.29.10 is known from WO2010/060379. The carboxamides broflanilide and M.29.1 1.b) to M.29.1 1.h) are described in WO2010/018714, and the carboxamides M.29.1 1 i) to M.29.1 1.p) in WO2010/127926. The pyridylthiazoles M.29.12.a) to M.29.12.C) are known from WO2010/006713, M.29.12.d) and M.29.12.e) are known from WO2012/000896, and M.29.12.f) to M.29.12.m) from WO2010/129497. The compounds M.29.14a) and M.29.14b) are known from WO2007/101369. The pyrazoles M.29.16.a) to M.29.16h) are described in WO2010/034737, WO2012/084670, and WO2012/143317, respectively, and the pyrazoles M.29.16i) and M.29.16j) are described in US 61/891437. The pyridinyl- indazoles M.29.17a) to M.29.17.j) are described in WO2015/038503. The pyridylpyrazoles M.29.18a) to M.29.18d) are described in US2014/0213448. The isoxazoline M.29.19 is described in WO2014/036056. The isoxazoline M.29.20 is known from WO2014/090918.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with fipronil is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with ethiprole is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with chlorfenapyr is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with teflubenzuron is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with chlorfenapyr and teflubenzuron is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'. In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with dinotefuran is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with chlorantraniliprole is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with cyantraniliprole is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with pyrethroids, preferably alpha-cypermethrin, is applied, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
The following mixtures are preferred:
With regard to the methods and uses of the present invention, in an embodiment of the invention, the pesticide II is selected from the group of fipronil, alpha-cypermethrin, dinotefuran, chlorfenapyr, teflubenzuron and sulfoxaflor.
With regard to the methods and uses of pesticidal mixtures of the present invention, a compound II selected from group M.2 (GABA-gated chloride channel antagonists) as defined above is preferred, in particular group M.2B (fiproles), especially preferred ethiprole and fipronil.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with fipronil as compound II are particularly preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, a compound II selected from group M.3 (Sodium channel modulators) as defined above is preferred, in particular group M.3A (pyrethroids), especially preferred alpha-cypermethrin and cyhalothrin.. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with alpha-cypermethrin as compound II are particularly preferred.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with cyhalothrin as compound II are particularly preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, a compound II selected from group M.4A (Neonicotinoids) as defined above is preferred, in particular clothianidin, dinotefuran, imidacloprid, thiacloprid, or thiamethoxam.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with thiamethoxam as compound II are especially preferred.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with clothianidin as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with dinotefuran as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with imidacloprid as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with thiacloprid as compound II are also preferred. Mixtures of compounds of formula I with sulfoxaflor as compound II are also preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is selected from group M.5 (Nicotinic acetylcholine receptor allosteric activators) and is preferably spinosad or spinetoram.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is selected from group M.6 (Chloride channel activators) and is preferably an avermectin.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with abamectin as compound II are especially preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is selected from group M.9 (Selective homopteran feeding blockers) and is preferably pymetrozine or flonicamid. Mixtures of compounds of formu- la I as individualized herein, e.g. in Table A, Table A' or Table A", with pymetrozine as compound II are especially preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with flonicamid as compound II are especially preferred. With regard to the methods and uses of pesticidal mixtures of the present invention, in an em- bodiment of the invention, the compound II is selected from group M.13 (Uncouplers of oxidative phosphorylation via disruption of the proton gradient) and is preferably chlorfenapyr. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with chlorfenapyr as compound II are especially preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an em- bodiment of the invention, the compound II is selected from group M.16 (Inhibitors of the chitin biosynthesis type 1 ) and is preferably buprofezin.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is selected from group M.22 (Voltage-dependent sodium channel blockers) and is preferably metaflumizone.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is selected from group M.23 (Inhibitors of the of acetyl CoA carboxylase) and is preferably a Tetronic or Tetramic acid derivative, spirodiclofen, spi- romesifen or spirotetramat.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with Tetronic Acid as compound II are preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with Tetramic Acid as compound II are also preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with Tetramic Acid as compound II are also preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an em- bodiment of the invention, the compound II is selected from group M.26 (Ryanodine receptor- modulators) and is preferably chlorantraniliprole or cyantraniliprole. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with chlorantraniliprole as compound II are especially preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with cyantraniliprole as compound II are especially preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, in an embodiment of the invention, the compound II is sulfoxaflor. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with sulfoxaflor as compound II are especially preferred.
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 fungicides. The following list of fungicides, in conjunction with which the com- pounds of the present invention can be used, is intended to illustrate the possible combinations but does not limit them:
A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1 .4), enestroburin (A.1.5), fenamin- strobin (A.1 .6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1.9), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxy.strobin (A.1.13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1 .16), tri- floxystrobin (A.1 .17), 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-
2- methoxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1 .19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21 ), fenamidone (A.1 .21 ), methyl-/S/-[2-[(1 ,4-dimethyl-5-phenyl- pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1 .22), 1 -[3-chloro-2-[[1 -(4- chlorophenyl)-1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.23), 1 -[3-bromo- 2-[[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.24), 1 -[2-[[1 - (4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1 .25), 1 -[2- [[1 -(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .26), 1 - [2-[[1 -(2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-on (A.1.27), 1 -[2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol^ one (A.1.28), 1 -[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.29), 1 -[3-cyclopropyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]- 4-methyl-tetrazol-5-one (A.1 .30), 1 -[3-(difluoromethoxy)-2-[[2-methyl-4-(1 -methylpyrazol-
3- yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5-one (A.1.31 ), 1 -methyl-4-[3-methyl-
2- [[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]tetrazol-5-one (A.1.32), 1 -methyl-4- [3-methyl-2-[[1 -[3-(trifluoromethyl)phenyl]-ethylideneamino]oxymethyl]phenyl]tetrazo
(A.1.33), (Z,2E)-5-[1 -(2,4-dichlorophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-A/,3-dimethyl-pent-3- enamide (A.1.34), (Z,2E)-5-[1 -(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-A/,3-dimethyl- pent-3-enamide (A.1 .35), (Z,2E)-5-[1 -(4-chloro-2-fluoro-phenyl)pyrazol-3-yl]oxy-2- methoxyimino-A/,3-dimethyl-pent-3-enamide (A.1.36),
- inhibitors of complex III at Qi site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(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 (A.2.3), [(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 (A.2.4), [(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 (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3- (1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate (A.2.6); (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 (A.2.7), (3S,6S,7R,8R)-8-benzyl-3-[3-[(isobutyryloxy)methoxy]-4- methoxypicolinamido]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8);
inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)-
3- difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl- N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl- pyrazole-4-carboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3- (difluoromethyl)-l -methyl-pyrazole-4-carboxamide (A.3.27);
other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1.1 ), bitertanol (B.1.2), bromuconazole (B.1.3), cyproconazole (B.1 .4), difenoconazole (B.1 .5), diniconazole (B.1.6), diniconazole-M (B.1 .7), epoxiconazole (B.1.8), fenbuconazole (B.1 .9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1 .12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole (B.1 .15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21 ), propiconazole (B.1.22), prothioconazole
(B.1.23), simeconazole (B.1 .24), tebuconazole (B.1.25), tetraconazole (B.1 .26), triadimefon (B.1.27), triadimenol (B.1 .28), triticonazole (B.1 .29), uniconazole (B.1 .30), 1 -[re/-(2S;3R)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1 .31 ), 2- [re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1.32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1 .33) , 1 -[4- (4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35),
2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .37), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .38), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .39), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.40), 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1.51 ); imidazoles: imazalil (B.1.42), pefurazoate (B.1 .43), prochloraz (B.1.44), triflumizol (B.1 .45); pyrimidines, pyridines and piperazines: fenarimol (B.1.46), nuarimol (B.1 .47), pyrifenox (B.1.48), triforine (B.1 .49), [3- (4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .50);
Delta14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1 .6), oxadixyl (C.1.7); others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1 .4), fenpiclonil (F.1 .5), fludioxonil (F.1.6);
- G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1 .4);
lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 ); fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(di- fluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5- yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3, 5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesul- fonate (G.5.3);
H) Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture (H.1.1 ), copper acetate (H.1 .2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1.5), sulfur (H.1 .6);
thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin (1.1 .1 ), polyoxin B (1.1 .2);
melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
acibenzolar-S-methyl (J.1.1 ), probenazole (J.1.2), isotianil (J.1 .3), tiadinil (J.1 .4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1 .9);
K) Unknown mode of action
bronopol (K.1.1 ), chinomethionat (K.1 .2), cyflufenamid (K.1 .3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclomezine (K.1 .7), difenzoquat (K.1 .8), difenzoquat-methylsulfate (K.1.9), diphenylamin (K.1 .10), fenpyrazamine (K.1 .1 1 ), flumetover (K.1 .12), flusulfamide (K.1.13), flutianil (K.1.14), methasulfocarb (K.1 .15), nitrapyrin (K.1 .16), nitrothal-isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1 .20), oxin-copper (K.1 .21 ), proquinazid
(K.1.22), tebufloquin (K.1 .23), tecloftalam (K.1.24), triazoxide (K.1 .25), 2-butoxy-6-iodo- 3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop- 2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.27), 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-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .28), 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1.29), N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1.30), N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine (K.1.32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)- phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3-tri- methylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6- tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester (K.1 .35), 3-[5-(4-methylphenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1 .39), 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 (K.1.40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)- [(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .42), 2-[2- [(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8- fluoro-2-methyl-3-quinolyl)oxy]phen-yl]propan-2-ol (K.1 .44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihydroisoquinolin-1 -yl)quinoline (K.1 .45), 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 - yl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline
(K.1.47), 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine (K.1 .48).
The fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are com- mercially available.
The fungicides described by lUPAC nomenclature, their preparation and their pesticidal activity is 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, WO2012/168188, WO 2007/006670, WO 201 1/77514; W013/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/024010 and WO 13/047441 , WO 13/162072, WO 13/092224, WO 1 1/135833).
The following compounds are preferred in mixtures with compounds of formula (I):
With regard to the methods and uses of pesticidal mixtures of the present invention, a compound II selected from the group of the azoles is preferred, especially prochloraz, prothiocona- zole, tebuconazole and triticonazole, especially prothioconazole and triticonazole.
Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A or Table A", with triticonazole as compound II are particularly preferred. Mixtures of compounds of formula I as individualized herein, e.g. in Table A, Table A' or Table A", with prothioconazole as compound II are particularly preferred.
With regard to the methods and uses of pesticidal mixtures of the present invention, preferred is a compound II selected from the group of benomyl, carbendazim, epoxiconazole, fluquin- conazole, flutriafol, flusilazole, metconazole, prochloraz, prothioconazole, tebuconazole, triticonazole, pyraclostrobin, trifloxystrobin, boscalid, dimethomorph, penthiopyrad, dodemorph, famoxadone, fenpropimorph, proquinazid, pyrimethanil, tridemorph, compound ll-TFPTAP (5- chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine), maneb, mancozeb, metiram, thiram, chlorothalonil, dithianon, flusulfamide,metrafenone, fluxap- yroxad (Ν-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide), bixafen, penflufen, sedaxane, isopyrazam. Especially preferred is pyraclostrobin and fluxapy- roxad.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with pyraclostrobin is applied, preferably in the methods for seed treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the plant propagation material of the cultivated plant, preferably seeds, wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with pyraclostrobin is applied, preferably in the methods for foliar treat- ment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with fluxapyroxad is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'.
In a preferred embodiment, in the methods and uses according to the invention, a compound of formula (I) in mixture with an azole is applied, preferably in the methods for foliar treatment, i.e. methods, wherein the compound of formula (I) or a mixture thereof is applied to the cultivated plant, parts of the cultivated plant or to their habitat wherein the compound of formula (I) is preferably selected from the compounds 1-1 to I-82 as defined in Table A, more specifically compound 1-1 1 , more specifically compound 1-16, more specifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 as defined in Table A'. Surprisingly, it has now been found that the use of compounds of formula I and their mixtures as defined herein in cultivated plants displays a synergistic effect between the trait of the cultivated plant and the applied compounds of formula I and their mixtures.
In a particular preferred embodiment, the mixtures comprise as an additional component which is the compound against which the cultivated plant is resistant.
In general, the ratios by weight for the respective mixtures comprising the insecticidal compound I and compound II are from 1 :500 to 500:1 , preferably from 1 :100 to 100:1 , more preferably from 1 :25 to 25:1.
We have found that the application of compounds of formula I and their mixtures (in case of the mixtures, the simultaneous, that is joint or separate, application of the compound I and com- pound II or successive application of the compound I and compound II) on cultivated plants allows enhanced control of animal pests, compared to the control rates that are possible by application of compounds of formula I and their mixtures on non-cultivated plants.
Formulations
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof. An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below. The compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, pow- ders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (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 articles (e.g. LN), as well as gel formulations for the treatment of plant propa- gation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide 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, surfac-tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec-tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu-lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi-ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions 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, cyclo^hexanol; 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; polysaccharide powders, 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 amphoteric 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, sul-fates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, 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 ethox- ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth- oxylates.
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. Examples 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 al- kylpolyglucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrroli- done, 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 pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxi- laries. 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 alkylisothiazoli-nones 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, pol- yacrylates, biological or synthetic waxes, and cellulose ethers.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). 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 cormprising 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 de-vice, 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.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the in- vention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
Application methods
The compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infes- tation by animal pests, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
The compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions compris- ing said mixtures as defined above. The components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, 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 application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foli- age, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as
http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
The term "crop" refers to both, growing and harvested crops.
The term "plant" includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rape- seed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cu- curbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias, geranium/pelargoniums, pansies and impati- ens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice. In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagen- ized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. Several plants have been rendered tolerant to herbicides by mutagenesis, for example Clearfield® oilseed rape being tolerant to imidazoli- nones, e.g. imazamox. Alternatively, genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate). Furthermore, insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance. Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for the respective Bt toxins. Genetically modified plants with insect resistance are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity®, and Intacta®. Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance. In general, all relevant modified plants in connection with singular or stacked traits as well as detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http://www.isaaa.org/gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http://cera-gmc.org/GMCropDatabase). It has surprisingly been found that the pesticidal activity of the compounds of the present invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
The term "plant propagation material" refers to 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 "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.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application 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.
For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
The compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes. The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The present invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is for example 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, ba- nanas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
Conventional seed treatment formulations include for example flowable concentrates FS, solu- tions LS, suspoemulsions (SE), 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. Preferably, the formulations are applied such that germination is not included.
The active substance concentrations in ready-to-use formulations, which may be obtained after two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
In a preferred embodiment a FS formulation is used for seed treatment. Typically, 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 the compounds of the present 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. In the treatment of seed, the application rates of the compounds of the invention 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, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
The compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
As used herein "an effective and non-phytotoxic amount" means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil. The terms "plant" and "plant propagation material" are defined above.
"Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by methods known to a skilled person.
Plant health
In a preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant, by treating plant propagation material, preferably seeds with compounds of formula I and their mixtures.
The present invention also comprises plant propagation material, preferably seed, of a cultivated plant treated with compounds of formula I and their mixtures.
In another preferred embodiment, the present invention relates to a method of controlling harm- ful insects and/or increasing the health of a cultivated plant, in particular the yield of a cultivated plant by treating the cultivated plant, part(s) of such plant or at its locus of growth with compounds of formula I and their mixtures. The term cultivated plant(s) includes "modified plant(s)" and "transgenic plant(s)".
In one embodiment of the invention, the term "cultivated plants" refers to "modified plants". In one embodiment of the invention, the term "cultivated plants" refers to "transgenic plants". "Modified plants" are those which have been modified by conventional breeding techniques. The term "modification" means in relation to modified plants a change in the genome, epigenome, tran- scriptome or proteome of the modified plant, as compared to the control, wild type, mother or parent plant whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below.
The modification may result in the modified plant to be a different, for example a new plant vari- ety than the parental plant.
"Transgenic plants" are those, which genetic material has been modified by the use of recombinant DNA techniques that under natural circumstances can not readily be obtained by cross breeding, mutations or natural recombination, whereby the modification confers a trait (or more than one trait) or confers the increase of a trait (or more than one trait) as listed below as com- pared to the wild-type plant.
In one embodiment, 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, preferably increase a trait as listed below as compared to the wild-type plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), or to post- transcriptional modifications of oligo- or polypeptides e.g. by glycosylation or polymer additions such as prenylated, acetylated, phosphorylated or farnesylated moieties or PEG moieties.
In one embodiment under the term "modification" when referring to a transgenic plant or parts thereof is understood that the activity, expression level or amount of a gene product or the metabolite content is changed, e.g. increased or decreased, in a specific volume relative to a cor- responding volume of a control, reference or wild-type plant or plant cell, including the de novo creation of the activity or expression.
In one embodiment the activity of a polypeptide is increased or generated by expression or overexpresion of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant. The term "expression" or "gene expression" means the transcription of a specific gene or specific genes or specific genetic construct. The term "expression" or "gene expression" in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA), regulatory RNA (e.g. miRNA, RNAi, RNAa) or mRNA with or without subsequent translation of the latter into a protein. In another embodiment the term "expression" or "gene expression" in particular means the transcription of a gene or genes or genetic construct into structural RNA (rRNA, tRNA) or mRNA with or without subsequent translation of the latter into a protein. In yet another embodiment it means the transcription of a gene or genes or genetic construct into mRNA.
The process includes transcription of DNA and processing of the resulting mRNA product. The term "increased expression" or "overexpression" as used herein means any form of expression that is additional to the original wild-type expression level.
The term "expression of a polypeptide" is understood in one embodiment to mean the level of said protein or polypeptide, preferably in an active form, in a cell or organism.
In one embodiment the activity of a polypeptide is decreased by decreased expression of the gene coding for said polypeptide which confers a trait or confers the increase of a trait as listed below as compared to the control plant. Reference herein to "decreased expression" or "reduction or substantial elimination" of expression is taken to mean a decrease in endogenous gene expression and/or polypeptide levels and/or polypeptide activity relative to control plants. It comprises further reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule.
The terms "reduction", "repression", "decrease" or "deletion" relate to a corresponding change of a property in an organism, a part of an organism such as a tissue, seed, root, tuber, fruit, leave, flower etc. or in a cell. Under "change of a property" it is understood that the activity, expression level or amount of a gene product or the metabolite content is changed in a specific volume or in a specific amount of protein relative to a corresponding volume or amount of protein of a control, reference or wild type. Preferably, the overall activity in the volume is reduced, decreased or deleted in cases if the reduction, decrease or deletion is related to the reduction, decrease or deletion of an activity of a gene product, independent whether the amount of gene product or the specific activity of the gene product or both is reduced, decreased or deleted or whether the amount, stability or translation efficacy of the nucleic acid sequence or gene encoding for the gene product is reduced, decreased or deleted.
The terms "reduction", "repression", "decrease" or "deletion" include the change of said property in only parts of the subject of the present invention, for example, the modification can be found in compartment of a cell, like an organelle, or in a part of a plant, like tissue, seed, root, leave, tuber, fruit, flower etc. but is not detectable if the overall subject, i.e. complete cell or plant, is tested. Preferably, the "reduction", "repression", "decrease" or "deletion" is found cellular, thus the term "reduction, decrease or deletion of an activity" or "reduction, decrease or deletion of a metabolite content" relates to the cellular reduction, decrease or deletion compared to the wild type cell. In addition the terms "reduction", "repression", "decrease" or "deletion" include the change of said property only during different growth phases of the organism used in the inventive process, for example the reduction, repression, decrease or deletion takes place only during the seed growth or during blooming. Furthermore the terms include a transitional reduction, decrease or deletion for example because the used method, e.g. the antisense, RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, or ribozyme, is not stable integrated in the genome of the organism or the reduction, decrease, repression or deletion is under control of a regulatory or inducible element, e.g. a chemical or otherwise inducible promoter, and has therefore only a transient effect.
Methods to achieve said reduction, decrease or deletion in an expression product are known in the art, for example from the international patent application WO 2008/034648, particularly in paragraphs [0020.1.1 .1 ], [0040.1 .1.1], [0040.2.1 .1] and [0041 .1 .1.1].
Reducing, repressing, decreasing or deleting of an expression product of a nucleic acid molecule in modified plants is known. Examples are canola i.e. double nill oilseed rape with reduced amounts of erucic acid and sinapins.
Such a decrease can also be achieved for example by the use of recombinant DNA technology, such as antisense or regulatory RNA (e.g. miRNA, RNAi, RNAa) or siRNA approaches. In particular RNAi, snRNA, dsRNA, siRNA, miRNA, ta-siRNA, cosuppression molecule, ribozyme, or antisense nucleic acid molecule, a nucleic acid molecule conferring the expression of a domi- nant-negative mutant of a protein or a nucleic acid construct capable to recombine with and silence, inactivate, repress or reduces the activity of an endogenous gene may be used to decrease the activity of a polypeptide in a transgenic plant or parts thereof or a plant cell thereof used in one embodiment of the methods of the invention. Examples of transgenic plants with reduced, repressed, decreased or deleted expression product of a nucleic acid molecule are Carica papaya (Papaya plants) with the event name X17-2 of the University of Florida, Prunus domestica (Plum) with the event name C5 of the United States Department of Agriculture - Agricultural Research Service, or those listed in rows T9-48 and T9-49 of table 9 below. Also known are plants with increased resistance to nematodes for example by reducing, repressing, de- creasing or deleting of an expression product of a nucleic acid molecule, e.g. from the PCT publication WO 2008/095886.
The reduction or substantial elimination is in increasing order of preference at least 10%, 20%, 30%, 40% or 50%, 60%, 70%, 80%, 85%, 90%, or 95%, 96%, 97%, 98%, 99% or more reduced compared to that of control plants. Reference herein to an "endogenous" gene not only refers to the gene in question as found in a plant in its natural form (i.e., without there being any human intervention), but also refers to that same gene (or a substantially homologous nucleic acid/gene) in an isolated form subsequently (re)introduced into a plant (a transgene). For example, a transgenic plant containing such a transgene may encounter a substantial reduction of the transgene expression and/or substantial reduction of expression of the endogenous gene. The terms "control" or "reference" are exchangeable and can be a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which was not modified or treated according to the herein described process according to the invention. Accordingly, the plant used as control or reference corresponds to the plant as much as possible and is as identical to the subject matter of the invention as possible. Thus, the control or reference is treated identically or as identical as possible, saying that only conditions or properties might be different which do not influence the quality of the tested property other than the treatment of the present invention.
It is possible that control or reference plants are wild-type plants. However, "control" or "reference" may refer to plants carrying at least one genetic modification, when the plants employed in the process of the present invention carry at least one genetic modification more than said control or reference plants. In one embodiment control or reference plants may be transgenic but differ from transgenic plants employed in the process of the present invention only by said modification contained in the transgenic plants employed in the process of the present invention.
The term "wild type" or "wild-type plants" refers to a plant without said genetic modification. These terms can refer to a cell or a part of a plant such as an organelle like a chloroplast or a tissue, in particular a plant, which lacks said genetic modification but is otherwise as identical as possible to the plants with at least one genetic modification employed in the present invention. In a particular embodiment the "wild-type" plant is not transgenic.
Preferably, the wild type is identically treated according to the herein described process according to the invention. The person skilled in the art will recognize if wild-type plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild- type plants will not need selection for transgenic plants for example by treatment with a select- ing agent such as a herbicide.
The control plant may also be a nullizygote of the plant to be assessed. The term "nullizygotes" refers to a plant that has undergone the same production process as a transgenic, yet has lost the once aquired genetic modification (e.g. due to mendelian segregation)as the corresponding transgenic. If the starting material of said production process is transgenic, then nullizygotes are also transgenic but lack the additional genetic modification introduced by the production process. In the process of the present invention the purpose of wild-type and nullizygotes is the same as the one for control and reference or parts thereof. All of these serve as controls in any comparison to provide evidence of the advantageous effect of the present invention.
Preferably, any comparison is carried out under analogous conditions. The term "analogous conditions" means that all conditions such as, for example, culture or growing conditions, soil, nutrient, water content of the soil, temperature, humidity or surrounding air or soil, assay conditions (such as buffer composition, temperature, substrates, pathogen strain, concentrations and the like) are kept identical between the experiments to be compared. The person skilled in the art will recognize if wild-type, control or reference plants will not require certain treatments in advance to the process of the present invention, e.g. non-transgenic wild-type plants will not need selection for transgenic plants for example by treatment with herbicide.
In case that the conditions are not analogous the results can be normalized or standardized based on the control.
The "reference", "control", or "wild type" is preferably a plant, which was not modified or treated according to the herein described process of the invention and is in any other property as similar to a plant, employed in the process of the present invention of the invention as possible. The reference, control or wild type is in its genome, transcriptome, proteome or metabolome as similar as possible to a plant, employed in the process of the present invention of the present inven- tion. Preferably, the term "reference-" "control-" or "wild-type-" plant, relates to a plant, which is nearly genetically identical to the organelle, cell, tissue or organism, in particular plant, of the present invention or a part thereof preferably 90% or more, e.g. 95%, more preferred are 98%, even more preferred are 99,00%, in particular 99,10%, 99,30%, 99,50%, 99,70%, 99,90%, 99,99%, 99,999% or more. Most preferable the "reference", "control", or "wild type" is a plant, which is genetically identical to the plant, cell, a tissue or organelle used according to the process of the invention except that the responsible or activity conferring nucleic acid molecules or the gene product encoded by them have been amended, manipulated, exchanged or introduced in the organelle, cell, tissue, plant, employed in the process of the present invention.
Preferably, the reference and the subject matter of the invention are compared after standardi- zation and normalization, e.g. to the amount of total RNA, DNA, or protein or activity or expression of reference genes, like housekeeping genes, such as ubiquitin, actin or ribosomal proteins.
The genetic modification carried in the organelle, cell, tissue, in particular plant used in the process of the present invention is in one embodiment stable e.g. due to a stable transgenic inte- gration or to a stable mutation in the corresponding endogenous gene or to a modulation of the expression or of the behaviour of a gene, or transient, e.g. due to an transient transformation or temporary addition of a modulator such as an agonist or antagonist or inducible, e.g. after transformation with a inducible construct carrying a nucleic acid molecule under control of a inducible promoter and adding the inducer, e.g. tetracycline.
In one embodiment preferred plants, from which "modified plants" and/or "transgenic plants" are be selected from the group consisting of cereals, such as maize (corn), wheat, barley sorghum, rice, rye, millet, triticale, oat, pseudocereals (such as buckwheat and quinoa), alfalfa, apples, banana, beet, broccoli, Brussels sprouts, cabbage, canola (rapeseed), carrot, cauliflower, cherries, chickpea, Chinese cabbage, Chinese mustard, collard, cotton, cranberries, creeping bent- grass, cucumber, eggplant, flax, grape, grapefruit, kale, kiwi, kohlrabi, melon, mizuna, mustard, papaya, peanut, pears, pepper, persimmons, pigeonpea, pineapple, plum, potato, raspberry, rutabaga, soybean, squash, strawberries, sugar beet, sugarcane, sunflower, sweet corn, tobacco, tomato, turnip, walnut, watermelon and winter squash,
more preferably from the group consisting of alfalfa, canola (rapeseed), cotton, rice, maize, cerals (such as wheat, barley, rye, oat), soybean, fruits and vegetables (such as potato, tomato, melon, papaya), pome fruits (such as apple and pear), vine, sugarbeet, sugarcane, rape, citrus fruits (such as citron, lime, orange, pomelo, grapefruit, and mandarin) and stone fruits (such as cherry, apricot and peach), most preferably from cotton, rice, maize, cerals (such as wheat, barley, rye, oat), sorghum, squash, soybean, potato, vine, pome fruits (such as apple), citrus fruits (such as citron and orange), sugarbeet, sugarcane, rape, oilseed rape and tomatoes,, utmost preferably from cotton, rice, maize, wheat, barley, rye, oat, soybean, potato, vine, apple, pear, citron and orange.
In another embodiment of the invention the cultivated plant is a gymnosperm plant, especially a spruce, pine or fir.
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.
In some embodiments, the invention relates to methods and uses, wherein a compound selected from the compounds of Table A, A' or A", is applied in an application type which corresponds in each case to one row of Table AP-T.
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.
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.
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.
In some embodiments, the invention relates to methods and uses, wherein a compound of for- mula I-26, is applied in an application type which corresponds in each case to one row of Table AP-T. 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. Also preferred is the application of the compounds and mixtures according to the invention, especially the compounds as individualized herein, e.g. in Table A, A', or A", 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 embodi- ment thereof, the application is on tubers (tuber vegetables), and especially on potato or on onion.
In one embodiment, in the methods and uses according to the invention, the following application types are used:
(Abbreviations: SPC = specialty crops; SPC-FV = fruiting vegetable; SPC-LV = leafy vegetable; SPC-T: tubers; ST = seed treatment)
Table AP-T
Figure imgf000052_0002
Figure imgf000052_0001
The cultivated plants are plants, which comprise at least one trait. The term "trait" refers to a property, which is present in the plant either by genetic engineering or by conventional breeding techniques. Each trait has to be assessed in relation to its respective control. Examples of traits are:
• herbicide tolerance,
• insect resistance by expression of bacterial toxins,
• fungal resistance or viral resistance or bacterial resistance,
• antibiotic resistance,
· stress tolerance,
• maturation alteration, • content modification of chemicals present in the cultivated plant, preferably increasing the content of fine chemicals advantageous for applications in the field of the food and/or feed industry, the cosmetics industry and/or the pharmaceutical industry,
• modified nutrient uptake, preferably an increased nutrient use efficiency and/or resistance to conditions of nutrient deficiency,
• improved fiber quality,
• plant vigor,
• modified colour,
• fertility restoration,
and male sterility.
Principally, cultivated plants may also comprise combinations of the aforementioned traits, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
Principally, all cultivated plants may also provide combinations of the aforementioned proper- ties, e.g. they may be tolerant to the action of herbicides and express bacterial toxins.
Tolerance to herbicides can be obtained by creating insensitivity at the site of action of the herbicide by expression of a target enzyme which is resistant to herbicide; rapid metabolism (conjugation or degradation) of the herbicide by expression of enzymes which inactivate herbicide; or poor uptake and translocation of the herbicide. Examples are the expression of enzymes which are tolerant to the herbicide in comparison to wild type enzymes, such as the expression of 5- enolpyruvylshikimate-3-phosphate synthase (EPSPS), which is tolerant to glyphosate (see e.g. Heck et.al, Crop Sci. 45, 2005, 329-339; Funke et.al, PNAS 103, 2006, 13010-13015; US 5188642, US 4940835, US 5633435, US 5804425, US 5627061 ), the expression of glutamine synthase which is tolerant to glufosinate and bialaphos (see e.g. US 5646024, US 5561236) and DNA constructs coding for dicamba-degrading enzymes (see e.g. US 7105724). Gene constructs can be obtained, for example, from micro-organism or plants, which are tolerant to said herbicides, such as the Agrobacterium strain CP4 EPSPS which is resistant to glyphosate; Streptomyces bacteria which are resistance to glufosinate; Arabidopsis, Daucus carota, Pseu- domonoas spp. or Zea mais with chimeric gene sequences coding for HDDP (see e.g. WO 1996/38567, WO 2004/55191 ); Arabidopsis thaliana which is resistant to protox inhibitors (see e.g. US 2002/0073443).
Tolerance to glyphosate can also be achieved by any one of the genes 2mepsps, epsps, gat4601 , goxv247 or mepsps.
Tolerance to glufosinate can be achieved by any one of the genes bar, pat or pat(syn).
Preferaby, the herbicide tolerant plant can be selected from cereals such as wheat, barley, rye, oat; canola, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape in particular canola, tomatoes, potatoes, sugarcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. More preferably, the cultivated plant is selected from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L. (rice), preferably from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize) and Glycine max L. (soybean). Particularly preferably, the cultivated plant is Glycine max L. (soybean).
Examples of commercial available transgenic plants with tolerance to herbicides, are the corn varieties "Roundup Ready Corn", "Roundup Ready 2" (Monsanto), "Agrisure GT", "Agrisure GT/CB/LL", "Agrisure GT/RW",„Agrisure 3000GT" (Syngenta), "YieldGard VT Rootworm/RR2" and "YieldGard VT Triple" (Monsanto) with tolerance to glyphosate; the corn varieties "Liberty Link" (Bayer), "Herculex I", "Herculex RW", "Herculex Xtra"(Dow, Pioneer), "Agrisure GT/CB/LL" and "Agrisure CB/LL/RW" (Syngenta) with tolerance to glufosinate; the soybean varieties "Roundup Ready Soybean" (Monsanto) and "Optimum GAT" (DuPont, Pioneer) with tolerance to glyphosate; the cotton varieties "Roundup Ready Cotton" and "Roundup Ready Flex" (Monsanto) with tolerance to glyphosate; the cotton variety "FiberMax Liberty Link" (Bayer) with tolerance to glufosinate; the cotton variety "BXN" (Calgene) with tolerance to bromoxynil; the canola varieties ..Navigator" und ..Compass" (Rhone-Poulenc) with bromoxynil tolerance; the canola varierty"Roundup Ready Canola" (Monsanto) with glyphosate tolerance; the canola variety "InVigor" (Bayer) with glufosinate tolerance; the rice variety "Liberty Link Rice" (Bayer) with glulfosinate tolerance and the alfalfa variety "Roundup Ready Alfalfa" with glyphosate tolerance. Further transgenic plants with herbicide tolerance are commonly known, for instance alfalfa, apple, eucalyptus, flax, grape, lentils, oil seed rape, peas, potato, rice, sugar beet, sunflower, tobacco, tomatom turf grass and wheat with tolerance to glyphosate (see e.g. US 5188642, US 4940835, US 5633435, US 5804425, US 5627061 ); beans, soybean, cotton, peas, potato, sunflower, tomato, tobacco, corn, sorghum and sugarcane with tolerance to dicamba (see e.g. US 7105724 and US 5670454); pepper, apple, tomato, millet, sunflower, tobacco, potato, corn, cucumber, wheat and sorghum with tolerance to 2,4-D (see e.g. US 6153401 , US 6100446, WO 2005107437, US 5608147 and US 5670454); sugarbeet, potato, tomato and tobacco with tolerance to glufosinate (see e.g. US 5646024, US 5561236); canola, barley, cotton, lettuce, melon, millet, oats, potato, rice, rye, sorghum, soybean, sugarbeet, sunflower, tobacco, tomato and wheat with tolerance to acetolactate synthase (ALS) inhibiting herbicides, such as triazolopyrim- idine sulfonamides, sulfonylureas and imidazolinones (see e.g. US 5013659, WO 2006060634, US 4761373, US 5304732, US 621 1438, US 621 1439 and US 6222100); cereals, sugar cane, rice, corn, tobacco, soybean, cotton, rapeseed, sugar beet and potato with tolerance to HPPD inhibitor herbicides (see e.g. WO 2004/055191 , WO 199638567, WO 1997049816 and US 6791014); wheat, soybean, cotton, sugar beet, rape, rice, sorghum and sugar cane with tolerance to protoporphyrinogen oxidase (PPO) inhibitor herbicides (see e.g. US 2002/0073443, US 20080052798, Pest Management Science, 61 , 2005, 277-285). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Plants, which are capable of synthesising one or more selectively acting bacterial toxins, comprise for example at least one toxin from toxin-producing bacteria, especially those of the genus Bacillus, in particular plants capable of synthesising one or more insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as del- ta.-endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lec- tins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdy- sone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or cal- cium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases.
In one embodiment a plant is capable of producing a toxin, lectin or inhibitor if it contains at least one cell comprising a nucleic acid sequence encoding said toxin, lectin, inhibitor or inhibitor producing enzyme, and said nucleic acid sequence is transcribed and translated and if ap- propriate the resulting protein processed and/or secreted in a constitutive manner or subject to developmental, inducible or tissue-specific regulation.
In the context of the present invention there are to be understood delta. -endotoxins, for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c, or vegetative in- secticidal proteins (VIP), for example VIP1 , VIP2, VIP3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701 ). An example for a truncated toxin is a truncated CrylA(b), which is expressed in the Bt1 1 maize from Syngen- ta Seed SAS, as described below. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non- naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D-recognition sequence is inserted into a CrylllA toxin (see WO 2003/018810).
Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 2003/052073.
Examples of genes conferring resistance to coleopteran insects include cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, and mcry3A.
Examples of genes conferring resistance to lepidopteran insects include cry1A, cry1A.105, crylAb, cry1Ab-Ac, crylAc, cryl C, cryl F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), and vip3Aa20.
The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A- 0 367 474, EP-A-0 401 979 and WO 1990/13651.
The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
Preferably, the plant capable of expression of bacterial toxins is selected from cereals such as wheat, barley, rye, oat; canola, cotton, eggplant, lettuce, sorghum, soybean, rice, oil seed rape, sugar beet, sugarcane, grapes, lentils, sunflowers, alfalfa, pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vegetables, such as tomatoes, potatoes, cucurbits and lettuce, more preferably, the plant is selected from cotton, soybean, maize (corn), rice, tomatoes, pota- toes, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from cotton, soybean, maize, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. More preferably, the cultivated plant is selected from the group consisting of Gossypium hirsutum L. (cotton), Zea mays L. (maize), Glycine max L. (soybean), Triticum aestivum (wheat), and Oryza sativa L. (rice), preferably from the group consisting of Gossypium hirsutum L. (cot- ton), Zea mays L. (maize) and Glycine max L. (soybean). Particularly preferably, the cultivated plant is Glycine max L. (soybean).
Examples of commercial available transgenic plants capable of expression of bacterial toxins are the corn varieties "YieldGard corn rootworm" (Monsanto), "YieldGard VT" (Monsanto), "Her- culex RW" (Dow, Pioneer), "Herculex Rootworm" (Dow, Pioneer) and "Agrisure CRW" (Syngen- ta) with resistance against corn rootworm; the corn varieties "YieldGard corn borer" (Monsanto), „YieldGard VT Pro" (Monsanto), "Agrisure CB/LL" (Syngenta), "Agrisure 3000GT" (Syngenta), "Hercules I", "Hercules II" (Dow, Pioneer), "KnockOut" (Novartis),„NatureGard" (Mycogen) and „Starl_ink" (Aventis) with resistance against corn borer, the corn varieties„Herculex I" (Dow, Pioneer) and„Herculex Xtra" (Dow, Pioneer) with resistance against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Plus" (Monsanto) with resistance against corn borer and corn rootworm; the cotton variety "Bollgard I"" (Monsanto) with resistance against tobacco budworm; the cotton varieties "Bollgard II" (Monsanto),„WideStrike" (Dow) and„VipCot" (Syngenta) with resistance against tobacco budworm, cotton bollworm, fall armyworm, beet armyworm, cabbage looper, soybean lopper and pink bollworm; the potato va- rieties "NewLeaf", "NewLeaf Y" and "NewLeaf Plus" (Monsanto) with tobacco hornworm resistance and the eggplant varieties "Bt brinjal", "Dumaguete Long Purple", "Mara" with resistance against brinjal fruit and shoot borer, bruit borer and cotton bollworm (see e.g.
US5128130). Further transgenic plants with insect resistance are commonly known, such as yellow stemborer resistant rice (see e.g. Molecular Breeding, Volume 18, 2006, Number 1 ), lep- idopteran resistant lettuce (see e.g. US 5349124 ), resistant soybean (see e.g. US 7432421 ) and rice with resistance against Lepidopterans, such as rice stemborer, rice skipper, rice cutworm, rice caseworm, rice leaffolder and rice armyworm (see e.g. WO 2001021821 ). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Preferably, plants, which are capable of synthesising antipathogenic substances are selected from soybean, maize (corn), rice, tomatoes, potato, banana, papaya, tobacco, grape, plum and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, tomatoes, potato, banana, papaya, oil seed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Plants, which are capable of synthesising antipathogenic substances having a selective action are for example plants expressing the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225) or so-called "antifungal proteins" (AFPs, see e.g. US 6864068). A wide range of antifungal proteins with activity against plant pathogenic fungi have been isolated from certain plant species and are common knowledge. Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 93/05153, WO 95/33818, and EP-A-0 353 191. Transgenic plants which are resistant against fungal, viral and bacterial pathogens are produced by intro- ducing plant resistance genes. Numerous resistant genes have been identified, isolated and were used to improve plant resistant, such as the N gene which was introduced into tobacco lines that are susceptible to Tobacco Mosaic Virus (TMV) in order to produce TMV-resistant tobacco plants (see e.g. US 5571706), the Prf gene, which was introduced into plants to obtain enhanced pathogen resistance (see e.g. WO 199802545) and the Rps2 gene from Arabidopsis thaliana, which was used to create resistance to bacterial pathogens including Pseudomonas syringae (see e.g. WO 199528423). Plants exhibiting systemic acquired resistance response were obtained by introducing a nucleic acid molecule encoding the TIR domain of the N gene (see e.g. US 6630618). Further examples of known resistance genes are the Xa21 gene, which has been introduced into a number of rice cultivars (see e.g. US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375), the Rcg1 gene for colletotrichum resistance (see e.g. US 2006/225152), the prpl gene (see e.g. US 5859332, WO 2008/017706), the ppv-cp gene to introduce resistance against plum pox virus (see e.g. US PP15,154Ps), the P1 gene (see e.g. US5968828), genes such as Blb1 , Blb2, Blb3 and RB2 to introduce resistance against Phy- tophthora infestans in potato (see e.g. US 7148397), the LRPKml gene (see e.g.
W01999064600), the P1 gene for potato virus Y resistance (see e.g. US 5968828), the HA5-1 gene (see e.g. US5877403 and US6046384), the PIP gene to indroduce a broad resistant to viruses, such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PLRV) (see e.g. EP 0707069) and genes such as Arabidopsis NI 16, ScaM4 and ScaM5 genes to obtain fungal resistance (see e.g. US 6706952 and EP 1018553). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glu- canases; the so-called "pathogenesis-related proteins"" (PRPs; see e.g. EP-A-0 392 225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 1995/33818) or protein or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO
2003/000906).
Antipathogenic substances produced by the plants are able to protect the plants against a variety of pathogens, such as fungi, viruses and bacteria. Useful plants of elevated interest in connection with present invention are cereals, such as wheat, barley, rye and oat; soybean; maize; rice; alfalfa, cotton, sugar beet, sugarcane, tobacco , potato, banana, oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries; turf; vines and vegetables, such as tomatoes, potatoes, cucurbits, papaya, melon, lenses and lettuce, more preferably selected from soybean, maize (corn), alfalfa, cotton, potato, banana, papaya, rice, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, potato, tomato, oilseed rape, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. Transgenic plants with resistance against fungal pathogens, are, for examples, soybeans with resistance against Asian soybean rust (see e.g. WO 2008/017706); plants such as alfalfa, corn, cotton, sugar beet, oileed, rape, tomato, soybean, wheat, potato and tobacco with resistance against Phytophtora infestans (see e.g. US5859332, US 7148397, EP 1334979); corn with re- sistance against leaf blights, ear rots and stalk rots (such as anthracnose leaf bligh, anthrac- nose stalk rot, diplodia ear rot, Fusarium verticilioides, Gibberella zeae and top dieback, see e.g. US 2006/225152); apples with resistance against apple scab (Venturia inaequalis, see e.g. WO 1999064600); plants such as rice, wheat, barley, rye, corn, oats, potato, melon, soybean and sorghum with resistance against fusarium diseases, such as Fusarium graminearum, Fusarium sporotrichioides, Fusarium lateritium, Fusarium pseudograminearum Fusarium sam- bucinum, Fusarium culmorum, Fusarium poae, Fusarium acuminatum, Fusarium equiseti (see e.g. US 6646184, EP 1477557); plants, such as corn, soybean, cereals (in particular wheat, rye, barley, oats, rye, rice), tobacco, sorghum, sugarcane and potatoes with broad fungal resistance (see e.g. US 5689046, US 6706952, EP 1018553 and US 6020129).
Transgenic plants with resistance against bacterial pathogens and which are covered by the present invention, are, for examples, rice with resistance against Xylella fastidiosa (see e.g. US 6232528); plants, such as rice, cotton, soybean, potato, sorghum, corn, wheat, balrey, sugarcane, tomato and pepper, with resistance against bacterial blight (see e.g. WO 2006/42145, US 5952485, US 5977434, WO 1999/09151 , WO 1996/22375); tomato with resistance against Pseudomonas syringae (see e.g. Can. J. Plant Path., 1983, 5: 251 -255).
Transgenic plants with resistance against viral pathogens, are, for examples, stone fruits, such as plum, almond, apricot, cherry, peach, nectarine, with resistance against plum pox virus (PPV, see e.g. US PP15,154Ps, EP 0626449); potatoes with resistance against potato virus Y (see e.g. US 5968828); plants such as potato, tomato, cucumber and leguminosaes which are re- sistant against tomato spotted wilt virus (TSWV, see e.g. EP 0626449, US 5973135); corn with resistance against maize streak virus (see e.g. US 6040496); papaya with resistance against papaya ring spot virus (PRSV, see e.g. US 5877403, US 6046384); cucurbitaceae, such as cucumber, melon, watermelon and pumpkin, and solanaceae, such as potato, tobacco, tomato, eggplant, paprika and pepper, with resistance against cucumber mosaic virus (CMV, see e.g. US 6849780); cucurbitaceae, such as cucumber, melon, watermelon and pumkin, with resistance against watermelon mosaic virus and zucchini yellow mosaic virus (see e.g. US 6015942); potatoes with resistance against potato leafroll virus (PLRV, see e.g. US 5576202); potatoes with a broad resistance to viruses, such as potato virus X (PVX), potato virus Y (PVY), potato leafroll virus (PLRV) (see e.g. EP 0707069).
Further examples of deregulated or commercially available transgenic plants with modified genetic material capable of expression of antipathogenic substances are the following plants: Carica papaya (papaya), Event: 55-1/63-1 ; Cornell University, Carica papaya (Papaya); Event: (X17-2); University of Florida, Cucurbita pepo (Squash); Event: (CZW-3); Asgrow (USA); Semi- nis Vegetable Inc. (Canada), Cucurbita pepo (Squash); Event: (ZW20); Upjohn (USA); Seminis Vegetable Inc. (Canada), Prunus domestica (Plum); Event: (C5); United States Department of Agriculture - Agricultural Research Service, Solanum tuberosum L. (Potato); Event: (RBMT15- 101 , SEMT15-02, SEMT15-15); Monsanto Company and Solanum tuberosum L. (Potato); Event: (RBMT21 -129, RBMT21 -350, RBMT22-082); Monsanto Company. Transgenic plants with resistance against nematodes and which may be used in the methods of the present invention are, for examples, soybean plants with resistance to soybean cyst nematodes.
Methods have been proposed for the genetic transformation of plants in order to confer in- creased resistance to plant parasitic nematodes. U.S. Patent Nos. 5,589,622 and 5,824,876 are directed to the identification of plant genes expressed specifically in or adjacent to the feeding site of the plant after attachment by the nematode.
Also known in the art are transgenic plants with reduced feeding structures for parasitic nematodes, e.g. plants resistant to herbicides except of those parts or those cells that are nematode feeding sites and treating such plant with a herbicide to prevent, reduce or limit nematode feeding by damaging or destroying feeding sites (e.g. US 5866777).
Use of RNAi to target essential nematode genes has been proposed, for example, in PCT Publication WO 2001/96584, WO 2001/17654, US 2004/0098761 , US 2005/0091713, US
2005/0188438, US 2006/0037101 , US 2006/0080749, US 2007/0199100, and US
2007/0250947.
Transgenic nematode resistant plants have been disclosed, for example in the PCT publications WO 2008/095886 and WO 2008/095889.
Plants wich are resistant to antibiotics, such as kanamycin, neomycin and ampicillin. The naturally occurring bacterial nptll gene expresses the enzyme that blocks the effects of the antibiot- ics kanamycin and neomycin. The ampicillin resistance gene ampR (also known as blaTEMI ) is derived from the bacterium Salmonella paratyphi and is used as a marker gene in the transformation of micro-organisms and plants. It is responsible for the synthesis of the enzyme beta- lactamase, which neutralises antibiotics in the penicillin group, including ampicillin. Transgenic plants with resistance against antibiotics, are, for examples potato, tomato, flax, canola, oilseed rape and corn (see e.g. Plant Cell Reports, 20, 2001 , 610-615. Trends in Plant Science, 1 1 , 2006, 317-319. Plant Molecular Biology, 37, 1998, 287-296. Mol Gen Genet., 257, 1998, 606- 13.). Plant Cell Reports, 6, 1987, 333-336. Federal Register (USA), Vol.60, No.1 13, 1995, page 31 139. Federal Register (USA), Vol.67, No.226, 2002, page 70392. Federal Register (USA), Vol.63, No.88, 1998, page 25194. Federal Register (USA), Vol.60, No.141 , 1995, page 37870. Canadian Food Inspection Agency, FD/OFB-095-264-A, October 1999, FD/OFB-099-127-A, October 1999. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, potato, sugarcane, alfalfa, tomatoes and cereals, such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Plants which are tolerant to stress conditions (see e.g. WO 2000/04173, WO 2007/131699, CA 2521729 and US 2008/0229448) are plants, which show increased tolerance to abiotic stress conditions such as drought, high salinity, high light intensities, high UV irradiation, chemical pollution (such as high heavy metal concentration), low or high temperatures, limitied supply of nutrients (i.e. nitrogen, phosphorous) and population stress. Preferably, transgenic plants with resistance to stress conditions, are selected from rice, corn, soybean, sugarcane, alfalfa, wheat, tomato, potato, barley, rapeseed, beans, oats, sorghum and cotton with tolerance to drought (see e.g. WO 2005/048693, WO 2008/002480 and WO 2007/030001 ); corn, soybean, wheat, cotton, rice, rapeseed and alfalfa with tolerance to low temperatures (see e.g. US 4731499 and WO 2007/1 12122); rice, cotton, potato, soybean, wheat, barley, rye, sorghum, alfalfa, grape, tomato, sunflower and tobacco with tolerance to high salinity (see e.g. US 7256326, US
7034139, WO 2001/030990). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications men- tioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, sugar beet, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, sugarcane, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat. Altered maturation properties, are for example delayed ripening, delayed softening and early maturity. Preferably, transgenic plants with modified maturation properties, are, selected from tomato, melon, raspberry, strawberry, muskmelon, pepper and papaya with delayed ripening (see e.g. US 5767376, US 7084321 , US 6107548, US 5981831 , WO 1995035387, US
5952546, US 5512466, WO 1997001952, WO 1992/008798, Plant Cell. 1989, 53-63. Plant Molecular Biology, 50, 2002). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from fruits, such as tomato, vine, melon, papaya, banana, pepper, raspberry and strawberry; stone fruits, such as cherry, apricot and peach; pome fruits, such as apple and pear; and citrus fruits, such as citron, lime, orange, pomelo, grapefruit, and mandarinT more preferably from tomato, vine, apple, banana, orange and straw- berry, most preferably tomatoes.
Content modification is synthesis of modified chemical compounds (if compared to the corresponding control plant) or synthesis of enhanced amounts of chemical (if compounds compared to the corresponding control plant) and corresponds to an increased or reduced amount of vitamins, amino acids, proteins and starch, different oils and a reduced amount of nicotine.
Commercial examples are the soybean varieties "Vistive II" and "Visitive III" with low- linolenic/medium oleic content; the corn variety "Mavera high-value corn" with increased lysine content; and the soybean variety "Mavera high value soybean" with yielding 5% more protein compared to conventional varieties when processed into soybean meal. Further transgenic plants with altered content are, for example, potato and corn with modified amylopectin content (see e.g. US 6784338, US 20070261 136); canola, corn, cotton, grape, catalpa, cattail, rice, soybean, wheat, sunflower, balsam pear and vernonia with a modified oil content (see e.g. US 7294759, US7157621 , US 5850026, US 6441278, US 6380462, US 6365802, US 6974898, WO 2001/079499, US 2006/0075515 and US 7294759); sunflower with increased fatty acid content (see e.g. US 6084164); soybeans with modified allergens content (so called "hypoaller- genie soybean, see e.g. US 6864362); tobacco with reduced nicotine content (see e.g. US 20060185684, WO 2005000352 and WO 2007064636); canola and soybean with increased lysine content (see e.g. Bio/Technology 13, 1995, 577 - 582); corn and soybean with altered composition of methionine, leucine, isoleucine and valine (see e.g. US 6946589, US 6905877); soybean with enhanced sulfur amino acid content (see e.g. EP 0929685, WO 1997041239); tomato with increased free amino acid contents, such as asparagine, aspartic acid, serine, threonine, alanine, histidine and glutamic acid (see e.g. US 672741 1 ); corn with enhanced amino acid content (see e.g. WO 050771 17); potato, corn and rice with modified starch content (see e.g. WO 1997044471 and US 7317146); tomato,corn, grape, alfalfa, apple, beans and peas with modified flavonoid content (see e.g. WO 2000/04175); corn, rice, sorghum, cotton, soybeans with altered content of phenolic compounds (see e.g. US 20080235829). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, potato, tomato, oilseed rape, flax and cereals such as wheat, barley, rye and oat, most preferably soybean, maize (corn), rice, oilseed rape, potato, tomato, cotton, vine, apple, pear, citron, orange and cereals such as wheat, barley, rye and oat.
Enhanced nutrient utilization is e.g. assimilation or metabolism of nitrogen or phosphorous. Preferably, transgenic plants with enhanced nitrogen assimilatory and utilization capacities are selected from for example, canola, corn, wheat, sunflower, rice, tobacco, soybean, cotton, alfalfa, tomato, wheat, potato, sugar beet, sugar cane and rapeseed (see e.g. WO 1995/00991 1 , WO 1997/030163, US 6084153, US 5955651 and US 6864405). Plants with improved phosphorous uptake are, for example, tomato and potato (see e.g. US 7417181 ). The methods of pro- ducing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
Transgenic plants with male steriliy are preferably selected from canola, corn, tomato, rice, Indian mustard, wheat, soybean and sunflower (see e.g. US 6720481 , US 6281348, US 5659124, US 6399856, US 7345222, US 7230168, US 6072102, EP1 135982, WO 2001/092544 and WO 1996/040949). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Preferably, the plant is selected from soybean, maize (corn), rice, cotton, oilseed rape, tomato, potato, vine, apple, pear, citron, orange and cereals such as wheat, barley.
Further examples of deregulated or commercially available transgenic plants with modified genetic material being male sterile are
Brassica napus (Argentine Canola:(Event: MS1 , RF1 =>PGS1 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: MS1 , RF2 =>PGS2 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: MS8xRF3 ; Bayer CropScience (Aventis CropScience(AgrEvo)); Brassica napus (Event: PHY14, PHY35 ; Bayer CropScience (formerly Plant Genetic Systems); Brassica napus (Event: PHY36 ; Bayer CropScience (formerly Plant Genetic Systems); Cichorium intybus (Chicory:(Event: RM3-3, RM3-4, RM3-6 ; Bejo Zaden BV; Zea mays L. (Maize:(Event: 676, 678, 680 ; Pioneer Hi-Bred International Inc.; Zea mays L. (Event: MS3 ; Bayer CropScience (Aventis CropScience(AgrEvo)) and Zea mays L. (Event: MS6 ; Bayer CropScience (Aventis CropScience(AgrEvo)).
Plants, which produce higher quality fiber are e.g. transgenic cotton plants. The such improved quality of the fiber is related to improved micronaire of the fiber, increased strength, improved staple length, improved length unifomity and color of the fibers (see e.g. WO 1996/26639, US 7329802, US 6472588 and WO 2001/17333). The methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. As set forth above, cultivated plants may comprise one or more traits, e.g. selected from the group consisting of herbicide tolerance, insect resistance, fungal resistance, viral resistance, bacterial resistance, stress tolerance, maturation alteration, content modification, modified nutrient uptake and male sterility (see e.g. WO 2005033319 and US 6376754).
Examples of commercial available transgenic plants with two combined properties are the corn varieties "YieldGard Roundup Ready" and YieldGard Roundup Ready 2" (Monsanto) with glyphosate tolerance and resistance to corn borer; the corn variety "Agrisure CB/LL" (Syntenta) with glufosinate tolerance and corn borer resistance; the corn variety "Yield Gard VT Root- worm/RR2" with glyphosate tolerance and corn rootworm resistance; the corn variety "Yield Gard VT Triple" with glyphosate tolerance and resistance against corn rootworm and corn borer; the corn variety "Herculex I" with glufosinate tolerance and lepidopteran resistance (Cry1 F), i.e. against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Corn Rootworm/Roundup Ready 2" (Monsanto) with glyphosate tolerance and corn rootworm resistance; the corn variety "Agrisure GT/RW" (Syngenta) with gluphosinate tolerance and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn root- worm and Mexican corn rootworm; the corn variety "Herculex RW" (Dow, Pioneer) with glufosinate tolerance and lepidopteran resistance (Cry34/35Ab1 ), i.e. against western corn rootworm, northern corn rootworm and Mexican corn rootworm; the corn variety "Yield Gard VT Rootworm/RR2" with glyphosate tolerance and corn rootworm resistance; the soybean variety "Optimum GAT" (DuPont, Pioneer) with glyphosate tolerance and ALS herbicide tolerance; the corn variety "Mavera high-value corn" with glyphosate tolerance, resistance to corn rootworm and European corn borer and high lysine trait.
Examples of commercial available transgenic plants with three traits are the corn variety "Herculex I / Roundup Ready 2" with glyphosate tolerance, gluphosinate tolerance and lepidopteran resistance (Cry1 F), i.e. against western bean cutworm, corn borer, black cutworm and fall armyworm; the corn variety "YieldGard Plus / Roundup Ready 2" (Monsanto) with glyphosate tolerance, corn rootworm resistance and corn borer resistance; the corn variety "Agrisure GT/CB/LL" (Syngenta) with tolerance to glyphosate tolerance, tolerance to gluphosinate and corn borer resistance; the corn variety "Herculex Xtra" (Dow, Pioneer) with glufosinate tolerance and lepidopteran resistance (Cry1 F + Cry34/35Ab1 ), i.e. against western corn rootworm, northern corn rootworm, Mecxican corn rootworm, western bean cutworm, corn borer, black cutworm and fall armyworm; the corn varieties "Agrisure CB/LL/RW" (Syngenta) with glufosinate tolerance, corn borer resistance (CrylAb) and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn rootworm and Mexican corn rootworm; the corn variety "Agrisure 3000GT" (Syngenta) with glyphosate tolerance + corn borer resistance (CrylAb) and lepidopteran resistance (Cry3A), i.e. against western corn rootworm, northern corn rootworm and Mexican corn rootworm. The methods of producing such transgenic plants are generally known to the person skilled in the art.
An example of a commercial available transgenic plant with four traits is„Hercules Quad-Stack" with glyphosate tolerance, glufosinate tolerance, corn borer resistance and corn rootworm resistance. Second embodiment of the invention
In one embodiment of the invention, the commercial transgenic plant is a soybean variety with glyphosate tolerance and lepidopteran resistance, preferably with one trait of glyphosate tolerance and two traits of lepidopteran resistance. Preferably, the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4 (cp4epsps gene), more preferably it is based on the transgenic event MON89788. Also preferably, the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably it is based on the transgenic event MON87701.
More preferably, the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
MON87701 . Pseudoplusia includens is a synonym for Chrysodeixis includens.
Most preferably, the commercial transgenic plant is "Intacta RR2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential. It is understood that "Intacta RR2 Pro" is used as a synonym for "Intacta™ Roundup Ready™ 2 Pro" soybean variety.
Therefore, in one embodiment, the invention relates to methods according to the invention wherein the cultivated plant is a soybean variety with glyphosate tolerance and lepidopteran resistance.
In a further embodiment, the invention relates to methods according to the invention, wherein the glyphosate tolerance is through the expression of the cp4epsps gene, or wherein the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis, or wherein both the glyphosate tolerance is through the expression of the cp4epsps gene and the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis.
In a further embodiment, the invention relates to methods according to the invention, wherein the glyphosate tolerance is based on the transgenic event MON89788, or wherein the lepidopteran resistance is based on the transgenic event MON87701 , or wherein both the glyphosate tolerance is based on the transgenic event MON89788 and the lepidopteran resistance is based on the transgenic event MON87701 .
In a further embodiment, the invention relates to methods according to the invention, wherein the lepidopteran resistance is against a species selected from the group of velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens, Chrysodeixis in- cludens ).
In a further embodiment, the invention relates to methods according to the invention, wherein the cultivated plant is "Intacta RR2 PRO" soybean (Monsanto), which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soy- bean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
In a further embodiment, the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
In another embodiment, the commercial transgenic plant is a soybean variety selected from "Roundup Ready 2 Yield", "Intacta RR2 Pro" and "Vistive Gold" (all Monsanto), or "Stearidonic Acid (SDA) Omega-3" (higher content of SDA in soybean, Monsanto). In another embodiment, the trait is Bacillus thuringiensis Cry1A.105 and cry2Ab2 and Vector PV-GMIR13196, for Mon87751 soybean (Monsanto).
In a further embodiment, the commercial transgenic plant is a soybean variety with herbicide tolerance and lepidopteran resistance, wherein the control of Lepidopteran pest is based on Bt CrylAc and Cryl F toxins. Preferably, the insect-resistant and herbicide-tolerant soybean is DAS81419 (see Table A1 , entry A1 -334).
Preferably, the plant has one trait of glyphosate tolerance and two traits of lepidopteran resistance. Preferably, the glyphosate tolerance is through expression of the EPSPS encoding gene from A. tumefaciens strain CP4, more preferably it is based on the transgenic event MON89788. Also preferably, the lepidopteran resistance is a resistance to lepidopteran pests of soybean, preferably through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudo- plusia includens), more preferably it is based on the transgenic event MON87701.
More preferably, the glyphosate tolerance is based on the transgenic event MON89788 and the trait of lepidopteran resistance is achieved through expresssion of the CrylAC encoding gene from B. thuringiensis, preferably against velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens), more preferably based on the transgenic event
MON87701 . Pseudoplusia includens is a synonym for Chrysodeixis includens.
Most preferably, the commercial transgenic plant is "Intacta RR2 PRO" soybean (Monsanto) which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa armigera), along with increased yield potential.
In a further embodiment, the commercial transgenic plant is a corn variety which has above- ground insect protection from "Genuity VT Triple PRO" or "Herculex Xtra" or both of them, and herbicide tolerance from "Roundup Ready 2" and Liberty Link, preferably corn varieties selected from "Genuity SmartStax", "Genuity VT Triple PRO" and "Genuity VT Double PRO" (all Monsanto), optionally as RIB (refuge-in-bag) solution. In a further embodiment, the commercial transgenic corn plant variety has a drought tolerance trait, preferably "Genuity DroughtGard". In an- other embodiment, the trait is double-stranded ribonucleic acid (dsRNA), Bacillus thuringiensis Cry3Bb1 protein and vector PV-ZMIR10871 for MON8741 1 corn. In a further embodiment, the commercial transgenic plant is a cotton variety selected from "Boll- gard II" (insect protection), "Roundup Ready Flex" (herbicide tolerance) and "Bollgard II with Roundup Ready Flex" (both), all Monsanto. Preferably, the cultivated plants are plants, which comprise at least one trait of insect resistance (preferably by expression of bacterial toxins) and at least one trait selected from
herbicide tolerance,
fungal resistance or viral resistance or bacterial resistance by expression of antipathogenic substances
stress tolerance,
content modification of chemicals present in the cultivated plant compared to the corresponding control plant.
Most preferably, the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express bacterial toxins, which provides resistance against animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis. Herein, the plant is preferably selected from cotton, rice, maize, wheat, barley, rye, oat, soybean, potato, vine, apple, pear, citron and orange.
In one embodiment, the plant is soybean.
In one embodiment, the invention relates to a method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification as compared to the respective non-modified control plant, wherein the plant is soybean, which method comprises applying a compound of formula I, which is selected from the compounds 1-1 to I-82 as defined in Table A,. More specifically, the compound I is selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A', more specifically compound 1-1 1 , more specifically compound 1-16, more spe- cifically compound 1-21 , more specifically compound I-26, more specifically compound 1-31 .
In an utmost preferred embodiment, the cultivated plants are plants, which are tolerant to the action of herbicides. Further guidance for specific combinations within this utmost preferred embodiment can be found in Table A1 .
If such plants are used in the methods according to the present invention, compounds of formula I and their mixtures may additionally comprise a herbicide III, to which the plant is tolerant. For example, if the cultivated plant is a cultivated plant tolerant to glyphosate, compounds of formula I and their mixtures may additionally comprise glyphosate.
For example, if the cultivated plant is a cultivated plant tolerant to glufonsinate, compounds of formula I and their mixtures may additionally comprise glufonisate.
For example, if the cultivated plant is a cultivated plant tolerant to a imidazolione herbicide, compounds of formula I and their mixtures may additionally comprise at least one imidazolione- herbicide. Herein, the imidazolionone-herbicide is selected from imazamox, imazethapyr, ima- zapic, imazapyr, imazamethabenz or imazaquin.
For example, if the cultivated plant is a cultivated plant tolerant to dicamba, compounds of formula I and their mixtures may additionally comprise dicamba.
For example, if the cultivated plant is a cultivated plant tolerant to sethoxidim, compounds of formula I and their mixtures may additionally comprise sethoxidim. For example, if the cultivated plant is a cultivated plant tolerant to cycloxidim, compounds of formula I and their mixtures may additionally comprise cycloxidim.
Thus, the present invention also relates to ternary mixtures, comprising a compound of formula I, an insecticide II and a herbicide III. In particular, the present invention also relates to ternary mixtures comprising two insecticides and a fungicide.
In another particular embodiment, the present invention also relates to ternary mixtures comprising two fungicides and one insecticide.
In another particular embodiment, the present invention also relates to ternary mixtures com- prising an insectide, a fungicide and a herbicide.
In one embodiment of the invention the cultivated plant is selected from the group of plants as mentioned in the paragraphs and tables of this disclosure, preferably as mentioned above. Preferably, the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance for example by expression of one or more bacterial toxins, fungal resistance or viral resistance or bacterial resistance by expression of one or more anti- pathogenic substances, stress tolerance, nutrient uptake, nutrient use efficiency, content modification of chemicals present in the cultivated plant compared to the corresponding control plant. More preferably, the cultivated plants are plants, which comprise at least one trait selected from herbicide tolerance, insect resistance by expression of one or more bacterial toxins, fungal re- sistance or viral resistance or bacterial resistance by expression of one or more antipathogenic substances, stress tolerance, content modification of one or more chemicals present in the cultivated plant compared to the corresponding control plant.
Most preferably, the cultivated plants are plants, which are tolerant to the action of herbicides and plants, which express one or more bacterial toxins, which provides resistance against one or more animal pests (such as insects or arachnids or nematodes), wherein the bacterial toxin is preferably a toxin from Bacillus thuriginensis. Herein, the cultivated plant is preferably selected from soybean, maize (corn), rice, cotton, sugarcane, alfalfa, potato, oilseed rape, tomatoes and cereals such as wheat, barley, rye and oat, most preferably from soybean, maize (corn), cotton, rice and cereals such as wheat, barley, rye and oat.
In another utmost preference, the cultivated plants are plants, which are given in table 1.
Sources: AgBios database and GMO-compass database (AG BIOS, P.O. Box 475, 106 St. John St. Merrickville, Ontario KOG1 NO, Canada, access: http://cera-gmc.org/, also see Bio- Techniques, Volume 35, No. 3, Sept. 2008, p. 213, and http://www.gmo- compass.org/eng/gmo/db/).
Thus, in one preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with compounds of formula I and their mixtures, wherein the plant is a plant, which is rendered tolerant to herbicides, more preferably to herbicides such as glutamine synthetase inhibitors, 5-enol-pyrovyl- shikimate-3-phosphate-synthase inhibitors, acetolactate synthase (ALS) inhibitors, protoporphy- rinogen oxidase (PPO) inhibitors, auxine type herbicides, most preferably to herbicides such as glyphosate, glufosinate, imazapyr, imazapic, imazamox, imazethapyr, imazaquin, imaza- methabenz methyl, dicamba and 2,4-D. In a more preferred embodiment, the present invention relates to a method of controlling harmful pests, especially insects, by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with compounds of formula I and their mixtures compounds of formula I or their mixtures, wherein the plant corresponds to a row of table A1 .
In a more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating plant propagation materials, preferably seeds with compounds of formula I and their mixtures selected from endosulfan, ethiprole and fipronil, wherein the plant corresponds to row of table A1.
Furthermore, the invention relates to a method for increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I, wherein the plant corresponds to a row of table A1. In another more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula I, which is selected from the compounds 1-1 to I-82 as defined in Table A, wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , table 1 or table 2. In this embodiment the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A'.
Especially, the properties of the mentioned plants are present in addition to the insecticidal trait. In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I, wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , wherein the compound of formula I is compound 1-1 1 .
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 , wherein the compound of formula I is compound 1-16.
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 wherein the compound of formula I is compound I-26.
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula I , wherein the plant has a property or a transgenic event of a plant which corresponds to a row of table A1 wherein the compound of formula I is compound 1-31 . Table A1
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
Figure imgf000102_0001
Figure imgf000103_0001
Figure imgf000104_0001
Figure imgf000105_0001
Figure imgf000106_0001
Figure imgf000107_0001
Figure imgf000108_0001
Figure imgf000109_0001
In a special embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants, plant propagation materials, or at their locus of growth with the compound of formula I and its mixtures, wherein the plant is a plant, which express at least one insecticidal toxin, preferably a toxin from Bacillus speicies, more preferably from Bacillus thuringiensis.
In one embodiment, these are the insecticidal traits, against which the insects to be controlled are resistant in the methods of the first embodiment of the present invention.
In another embodiment, these are the traits, which have not yet been described in a trait combi- nation for the the compound of formula (I) and its mixtures, accordingt to the second or third embodiment of the invention.
In a more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating plant propagation materials, preferably seeds with the compound of formula I or its mixtures as defined above, prefera- bly wherein the plant corresponds to a row of table A2 or table 3. In one sub-embodiment, the compound of formula I is compound 1-1 1 . In one sub-embodiment, the compound of formula I is compound 1-16. In one sub-embodiment, the compound of formula I is compound 1-21. In one sub-embodiment, the compound of formula I is compound I-26. . In one sub-embodiment, the compound of formula I is compound 1-31 .
In another more preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of cultivated plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures wherein the plant corresponds to a row of table A2 or table 3. . In one sub-embodiment, the compound of formula I is compound 1-1 1. In one sub-embodiment, the compound of formula I is compound 1-16. In one sub-embodiment, the compound of formula I is compound 1-21. In one sub-embodiment, the compound of formula I is compound I-26. In one sub-embodiment, the compound of formula I is compound 1-31 .
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3. In one sub-embodiment, the compound of formula I is compound 1-1 1. In one sub-embodiment, the compound of formula I is compound 1-16. In one sub-embodiment, the compound of formula I is compound 1-21. In one sub-embodiment, the compound of formula I is compound I-26. . In one sub-embodiment, the compound of formula I is compound 1-31 .
In a most preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation materials, preferably seeds of cultivated plants of cultivated crops with the compound of formula I and its mixtures, wherein the plant corresponds to a row of table A2 or table 3. In one sub-embodiment, the com- pound of formula I is compound 1-1 1. In one sub-embodiment, the compound of formula I is compound 1-16. In one sub-embodiment, the compound of formula I is compound 1-21. In one sub-embodiment, the compound of formula I is compound I-26. . In one sub-embodiment, the compound of formula I is compound 1-31 . Table A2
No description transgenic plant literature / commercial plants event
A2-1 Lepidoptera 281 -24-236 Gossypium hirsu- available, DOW AgroSciencresistance (DAS-24236-5) tum L. (cotton) es LLC
A2-2 Lepidoptera 281 -24-236 x Gossypium hirsu- available, Dow AgroSciences resistance 3006-210-23 tum L. (cotton)
A2-3 Lepidoptera 3006-210-23 Gossypium hirsu- available, DOW AgroSciencresistance (DAS-21023- tum L. (cotton) es LLC
5)
A2-4 Lepidoptera COT102 (SYN- Gossypium hirsu- available, Syngenta Seeds, resistance IR102-7) tum L. (cotton) Inc.
A2-5 Lepidoptera DAS-21023-5 Gossypium hirsu- available, DOW AgroSciencresistance x DAS-24236-5 tum L. (cotton) es LLC
A2-6 Lepidoptera Event-1 Gossypium hirsu- available, JK Agri Genetics resistance tum L. (cotton) Ltd (India)
A2-7 Lepidoptera MON531/757/1 Gossypium hirsu- available, Monsanto Comparesistance 076 tum L. (cotton) ny
A2-8 Lepidoptera 15985 (MON- Gossypium hirsu- available, Monsanto Comparesistance 15985-7) tum L. (cotton) ny
A2-9 Lepidoptera 5345 Lycopersicon available, Monsanto Comparesistance esculentum (tony
mato)
A2-10 Lepidoptera MIR162 Zea mays L. available, Syngenta Seeds, resistance (corn, maize) Inc.
A2-1 1 Lepidoptera MON89034 Zea mays L. available, Monsanto Comparesistance (corn, maize) ny
A2-12 Corn Rootworm MIR604 Zea mays L. available, Syngenta Seeds, resistance (com, maize) Inc.
A2-13 Corn Rootworm MON863 Zea mays L. available, Monsanto Comparesistance (com, maize) ny
A2-14 European Corn 176 Zea mays L. available, Syngenta Seeds, Borer resis(com, maize) Inc.
tance
A2-15 European Corn MON80100 Zea mays L. available, Monsanto CompaBorer resis(com, maize) ny
tance
A2-16 European Corn MON810 Zea mays L. available, Monsanto CompaBorer resis(com, maize) ny
tance
A2-17 Colorado potato ATBT04-6, Solanum tuavailable, Monsanto Compabeetle resis- ATBT04-27, berosum L. (pota- ny No description transgenic plant literature / commercial plants event
tance ATBT04-30, to)
ATBT04-31 ,
ATBT04-36,
SPBT02-5,
SPBT02-7
A2-18 Colorado potato BT6, BT10, Solanum tuavailable, Monsanto Compabeetle resisBT12, BT16, berosum L. (potany
tance BT17, BT18, to)
BT23
A2-19 Colorado potato RBMT15-101 , Solanum tuavailable, Monsanto Compabeetle resisSEMT15-02, berosum L. (potany
tance SEMT15-15 to)
A2-20 Colorado potato RBMT21 -129, Solanum tuavailable, Monsanto Compabeetle resisRBMT21 -350, berosum L. (potany
tance RBMT22-082 to)
A2-21 resistance to COT67B Gossypium hirsu- available, Syngenta Seeds lepidopteran tum L. (Cotton)
pests
Table 3
Literature / commer¬
No detailed description [Event] plant
cial plants
T3-1 corn rootworm resistance maize B*
T3-2 corn borer resistance maize C*
T3-3 western bean cutworm resistance maize D*
T3-4 black cutworm resistance maize E*
„Herculex I" (Dow,
T3-5 fall armyworm resistance maize Pioneer),„Herculex
Xtra" (Dow, Pioneer)
"Bollgard I" (Monsan¬
T3-6 tobacco budworm resistance cotton
to), E*
T3-7 cotton bollworm resistance cotton E*
T3-8 fall armyworm resistance cotton E*
T3-9 beet armyworm resistance cotton E*
T3-10 cabbage looper resistance cotton E*
T3-1 1 soybean lopper resistance cotton E*
T3-12 pink bollworm resistance cotton E*
T3-13 rice stemborer resistance rice A*
T3-14 striped rice borer resistance rice A*
T3-15 rice leaf roller resistance rice A* Literature / commer¬
No detailed description [Event] plant
cial plants
T3-16 yellow stemborer resistance rice A*
T3-17 rice skipper resistance rice A*
T3-18 rice caseworm resistance rice A*
T3-19 rice cutworm resistance rice A*
T3-20 rice armyworm resistance rice A*
brinjal fruit and shoot borer re¬
T3-21 eggplant F*
sistance
T3-22 cotton bollworm resistance eggplant
T3-23 tobacco hornworm resistance potato D*
US 5349124
T3-24 lepidopteran resistance lettuce
T3-25 lepidopteran resistance soybean US 7432421
A* refers to„Zhuxian B", WO2001021821 , Molecular Breeding, Volume 18, Number 1 / August 2006.
B* "YieldGard corn rootworm" (Monsanto), "YieldGard Plus" (Monsanto), "YieldGard VT" (Monsanto), "Herculex RW" (Dow, Pioneer), "Herculex Rootworm" (Dow, Pioneer), "Agrisure 0CRW" (Syngenta)
C* "YieldGard corn borer" (Monsanto),„YieldGard Plus" (Monsanto),„YieldGard VT Pro" (Monsanto), "Agrisure CB/LL" (Syngenta), "Agrisure 3000GT" (Syngenta), "Hercules I", "Hercules II" (Dow, Pioneer), "KnockOut" (Novartis),„NatureGard" (Mycogen),„Starl_ink" (Aventis)
D*"NewLeaf" (Monsanto), "NewLeaf Y" (Monsanto), "NewLeaf Plus" (Monsanto), US6100456 E* "Bollgard II" (Monsanto),„WideStrike" (Dow),„VipCot" (Syngenta)
F* US 5128130, "Bt brinjal", "Dumaguete Long Purple", "Mara"
First embodiment of the invention
In the cases, where the cultivated plant has an arthropodicidal, preferably insecticidal, trait, it often occurs that the pest that should be combatted becomes resistant to that trait.
Resistance may be defined as 'a heritable change in the sensitivity of a pest population that is reflected in the repeated failure of a product to achieve the expected level of control when used according to the label recommendation for that pest species'. (IRAC) Resistance therefore means that the original activitiy of a pesticide against the target organisms (arthropods, insects) decreases or is even lost, due to genetic or metabolic adaptation of the target organism.
"Resistant" to an insecticide is understood to mean resistant to at least one insecticide or insecticidal trait, i.e. the insect may be resistant to only one, but also to several insecticides or insecticidal traits.
In the present context of cultivated plants with at least one insecticidal trait, the resistance is against an insecticidal effect which is due to a genetic modification of a plant (modified or transgenic plant), which caused a resistance of the plant or crop to certain pests, especially insect pests, in susceptible insects.
This is to be understood to include plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those mentioned herein, es- pecially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as 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., and so on.
Therefore, in a most preferred embodiment, the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one insecti- cidal trait, and wherein the harmful insects are resistant to that at least one insecticidal trait of the plant.
Preferably, the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant has at least one lepidopteran or coleopteran trait, and wherein the harmful insects are resistant to that lepidopteran or coleopteran insecticidal trait of the plant.
In particular, the present invention relates to a method of controlling harmful insects by treating cultivated plants, parts of such plants or their locus of growth with a compound of formula (I) or a mixture thereof, wherein the plant having the insecticidal trait corresponds to a row of table A2 or Table 3 or Table A1 , and wherein the harmful insects are resistant to an insecticidal trait of the plant.
In a further embodiment, the invention relates to such methods according to the invention, wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa.
It is to be understood, that also in the mentioned methods of controlling resistant insects, the compound of formula (I) may optionally be mixed with one or more further pesticides.
Methods and uses of the invention as described herein may also involve a step of assessing whether insects are resistant to certain insecticides. This step will in general involve collecting a sample of insects from the area (e.g. crop, field, habitat) to be treated, before actually applying a compound of formula (I), and testing (for example using any suitable phenotypic, biochemical or molecular biological technique applicable) for resistance/sensitivity.
Apart from the traits and events that the plants have in the methods according to the invention, the plants may have more traits and/or events, e.g. those described in Table A1 .
For the purpose of the present invention, the cultivated plant is preferably selected from the group consisting of soybean, cotton and maize, wherein the plant has been made tolerant to the action of certain herbicides as described above. It is particularly preferred that the cultivated plant is selected from the group consisting of soybean, cotton and maize, wherein the plant has been made tolerant to the action of glyphosate herbicides.
In one embodiment, the cultivated plant is a plant, which has been made tolerant to the action of glyphosate herbicides. In addition to the tolerance to glyphosate herbicides, the plant may have been made tolerant to other herbicides and/or resistant to certain insects, and/or the plant may have been genetically modified otherwise, e.g. in terms of abiotic stress tolerance, altered growth/yield, disease resistance, modified product quality or pollination control system. Third embodiment of the invention
In a particularly preferred embodiment, the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
In a particularly preferred embodiment, the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3. In another particularly preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
In another particularly preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
In another particularly preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3.
In another particularly preferred embodiment, the present invention relates to a method of controlling harmful insects and/or increasing the health of plants by treating plant propagation material, preferably seeds with compounds of formula (I) and their mixtures wherein the plant is a glyphosate herbicide tolerant plant and corresponds to a row of table A1 , table A2 or table 3. Insect resistance, in particular lepidopteran resistance is of growing importance in GMO crops. Furthermore, it has been found that insects often become resistant to the crops, which have been modified in terms of insect resistance. In one embodiment, the cultivated plant is soybean, which has been made resistant to lepidoperan insects. In addition to the resistance to lepidop- eran insects, the soybean may have been made tolerant to certain herbicides and/or resistant to other insects, and/or the soybean may have been genetically modified otherwise, e.g. in terms of abiotic stress tolerance, altered growth/yield, disease resistance, modified product quality or pollination control system.
In a particularly preferred embodiment, the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with compounds of formula (I) and their mixtures, wherein the plant is a lepidopteran insect resistant soybean and corresponds to a row of table A1 , A2 or table 3. Lepidopteran resistance of soybeans is typically achieved by introducing a gene selected from the group consisting of: crylAc (gene source: Bacillus thuringiensis subsp. Kurstaki strain HD73), cry1 F (gene source: Bacillus thuringiensis var. aizawai), cry1A.105 (gene source: Bacillus thuringiensis subsp. Kumamotoensis), cry2Ab2 (gene source: Bacillus thuringiensis subsp. Kumamotoensis), and combinations thereof. In addition, the soybeans may be modified e.g. in terms of herbicide tolerance by introducing a suitable gene such as pat (gene source: Strepto- myces viridochromogenes), which provides glufosinate tolerance or cp4 epsps (aroA:CP4) (gene source: Agrobacterium tumefaciens strain CP4), which provides glyphosate tolerance. Preferably, the soybeans are additionally modified in terms of glyphosate tolerance by introduc- ing the gene cp4 epsps (aroA:CP4).
In a particularly preferred embodiment, the present invention therefore relates to a method of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or their locus of growth with c compounds of formula (I) and their mixtures, wherein the plant is a lepidopteran insect resistant soybean, which has been modified by intro- ducing at least one gene or at least one gene combination, which corresponds to a row of table C.
Table C
Figure imgf000116_0001
The present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is Gossypium hirsutum L. (cotton) or Zea mays L. (maize) and comprises at least one gene selected from the group consisting of dvsnf7, cry1A, cry1Ab-Ac, cry1 C, cry2Ab2, cry2Ae, mocryl F; or
Glycine max L. (soybean), Triticum aestivum (wheat) or Oryza sativa L. (rice) and comprises at least one gene selected from the group consisting of cry34Ab1 , cry35 Ab1 , cry3A, cry3Bb1 , dvsnf7, mcry3A, cry1A, cry1A.105, crylAb, cry1Ab-Ac, crylAc, cry1 C, cry1 F, cry1 Fa2, cry2Ab2, cry2Ae, cry9c, mocryl F, pinll, vip3A(a), vip3Aa20.
Preferably, the present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is modified by at least one gene according to one row of table D2.
Preferably, the compound of formula I is selected from the compounds 1-1 to I-82 as defined in Table A„ wherein the plant corresponds to a row of table76. In this embodiment the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in
Table A'.
Preferably, the compound of formula I is compound 1-1 1 .
Preferably, the compound of formula I is compound 1-16.
Preferably, the compound of formula I is compound 1-21 .
Preferably, the compound of formula I is compound I-26.
Preferably, the compound of formula I is compound 1-31 .
Table D2
No. crop gene No. crop gene
D2-1 cotton dvsnf7 D2-19 soybean dvsnf7
D2-2 cotton cry1A D2-20 soybean mcry3A
D2-3 cotton cry1Ab-Ac D2-21 soybean cry1A
D2-4 cotton cry1 C D2-22 soybean cry1A.105
D2-5 cotton cry2Ab2 D2-23 soybean crylAb
D2-6 cotton cry2Ae D2-24 soybean cry1Ab-Ac
D2-7 cotton mocryl F D2-25 soybean cry 1 Ac
D2-8 maize dvsnf7 D2-26 soybean cry1 C
D2-9 maize cry1A D2-27 soybean cry1 F
D2-10 maize cry1Ab-Ac D2-28 soybean cry1 Fa2
D2-1 1 maize cry1 C D2-29 soybean cry2Ab2
D2-12 maize cry2Ab2 D2-30 soybean cry2Ae
D2-13 maize cry2Ae D2-31 soybean cry9c
D2-14 maize mocryl F D2-32 soybean mocryl F
D2-15 soybean cry34Ab1 D2-33 soybean pinll
D2-16 soybean cry35 Ab1 D2-34 soybean vip3A(a)
D2-17 soybean cry3A D2-35 soybean vip3Aa20
D2-18 soybean cry3Bb1 D2-36 wheat cry34Ab1 No. crop gene No. crop gene
D2-37 wheat cry35 Ab1 D2-58 rice cry35 Ab1
D2-38 wheat cry3A D2-59 rice cry3A
D2-39 wheat cry3Bb1 D2-60 rice cry3Bb1
D2-40 wheat dvsnf7 D2-61 rice dvsnf7
D2-41 wheat mcry3A D2-62 rice mcry3A
D2-42 wheat cry1A D2-63 rice cry1A
D2-43 wheat cry1A.105 D2-64 rice cry1A.105
D2-44 wheat crylAb D2-65 rice crylAb
D2-45 wheat cry1Ab-Ac D2-66 rice cry1Ab-Ac
D2-46 wheat cry 1 Ac D2-67 rice cry 1 Ac
D2-47 wheat cry1 C D2-68 rice cry1 C
D2-48 wheat cry1 F D2-69 rice cry1 F
D2-49 wheat cry1 Fa2 D2-70 rice cry1 Fa2
D2-50 wheat cry2Ab2 D2-71 rice cry2Ab2
D2-51 wheat cry2Ae D2-72 rice cry2Ae
D2-52 wheat cry9c D2-73 rice cry9c
D2-53 wheat mocryl F D2-74 rice mocryl F
D2-54 wheat pinll D2-75 rice pinll
D2-55 wheat vip3A(a) D2-76 rice vip3A(a)
D2-56 wheat vip3Aa20 D2-77 rice vip3Aa20
D2-57 rice cry34Ab1
Further preferred embodiments of the invention are those methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula I is fipronil and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula I is ethiprole and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
In a more preferred embodiment, the present invention relates to methods of controlling harmful insects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with compounds of formula I or their mixtures, wherein the mixing partner of the compound of formula lcompound is chlorfenapyr and the plant expresses one or more genes selected from CP4 epsps, pat, bar, CrylAb, CrylAc, Cry3Bb1 , Cry2Ab, Cry1 F, Cry34Ab1 and Cry35Ab1 .
Furthermore, the present invention also relates to a method for controlling pests and/or increasing the plant health of a cultivated plant as compared to the respective non-modified control plant, comprising the application of compounds of formula (I) and their mixtures, to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the cultivated plant is modified by at least one gene as described in the follow- ing. Preferably, the compound of formula I is selected from the compounds 1-1 to I-82 as defined in Table A,, wherein the plant corresponds to a row of table76. In this embodiment the compound of formula I is more specifically selected from compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 as defined in Table A'.
Preferably, the compound of formula I is compound 1-1 1 .
Preferably, the compound of formula I is compound 1-16.
Preferably, the compound of formula I is compound 1-21 .
Preferably, the compound of formula I is compound I-26.
Preferably, the compound of formula I is compound 1-31 .
Therefore, further embodiments of the invention are those methods of controlling harmful in- sects and/or increasing the health of plants by treating cultivated plants, parts of such plants or at their locus of growth with a compound of formula (I) or a mixture thereof according to the invention, wherein the plant expresses one or more genes selected from aad, ACCase, ALS, AMY797E, APH4, bar, barnase, barstar, bla, bxn, cDHDPS, CP, cmv-cp, CrylAb, CrylAc, Cry1A.105, Cry1 F, Cry1 Fa2, Cry2Ab, Cry34Ab1 , Cry35Ab1 , Cry3A, Cry3Bb1 , Cry9C, dam, DHFR, fad2, fanl , FH, flcrylAb, GAT4601 , GAT4602, gmFAD2-1 , GM-HRA, goxv247, gus, hel, mCry3A, nos, NPTII, pat, PG, pinll, PMI, prsv-cp, QTPASE, rep, SAMase, spc, TE, vip3A, vip3A(a), wmv2-cp and zymv-cp.
Examples
The present invention is now illustrated in further detail by the following examples.
As stated above, the compounds of formula (I) can be prepared according to standard methods of organic chemistry, or by the processes as described in WO 2007/006670, WO2013/024007, WO2013/024008, WO2013/076092, and the unpublished applications PCT/EP2014/056164, EP13173044.2, PCT/EP2014/060082, and EP14166089.4 d, without being limited to the routes given therein.
The characterization can be done by coupled High Performance Liquid Chromatography / mass spectrometry (HPLC/MS), by NMR or by their melting points. B. Biology
Synergism can be described as an interaction where the combined effect of two or more compounds is greater than the sum of the individual effects of each of the compounds. The presence of a synergistic effect in terms of percent control, between two mixing partners (X and Y) can be calculated using the Colby equation (Colby, S. R., 1967, Calculating Synergistic and Antagonistic Responses in Herbicide Combinations, Weeds, 15, 20-22):
100
When the observed combined control effect is greater than the expected combined control effect (E), then the combined effect is synergistic.
The following tests can demonstrate the control efficacy of compounds, mixtures or compositions of this invention on specific pests. However, the pest control protection afforded by the compounds, mixtures or compositions is not limited to the species described. In certain instances, combinations of a compound of this invention with other invertebrate pest control compounds or agents are found to exhibit synergistic effects against certain important invertebrate pests.
The analysis of synergism or antagonism between the mixtures or compositions is determined using Colby's equation.
B1 : Test on GMO soybeans
Trial is carried out under greenhouse conditions on soybean (GMO plant variety, e.g. roundup, growth stage 109). 12 treatments are compared in a complete randomized blocks (4 replica- tions) with plot size of 1 m x 3 meters. Only selected plants are considered for artificial infestation and evaluations.
Due to glyphosate timing for application on GMO-soybeans, all treatments are applied in older plants (GS 109) otherwise a significant phytotoxicity is expected. Application is done, using 400 l/ha. All treatments are applied using a CO2 backpack (nozzle type TXVK-10). Temperature at the time of applications is around 25 to 30 °C and air humidity is between 30 and 100%. Soil condition is e.g. R4 (when <75% of surface is dried up) and the moisture is moist (normal). Roundup Original ® (Glyfosate-sal isopropilamina @360g/L) is used in the rate of 867 g a.i./ha. Artificial infestation is done one day after the application. The species used is Anticarsia gem- matalis (H ibner) [Thermesia elegantula (Herrich-Schaffer, 1869)], Noctuidae. 5 plants/plot are infested with 3 larvae (stage L2) using a entomological metallic tweezers, totaling 15 larvae per repetition. Larvae used in this trial are e.g. provided by BASF rearing laboratory, Campinas, Brazil.
A second infestation is held seven days after application in the same plants and using the same larval numbers. A third infestation might be done if necessary in order to observe residual activi- ty.
The mortality (number) and eating damage (%) are evaluated with 01 , 02, 05, 07, 14 and 21 DAA (days after application), comparing to untreated control plants.
Increased mortalities in combination with the application of roundup can be observed when compared to the untreated control plants:
Additionally, after 5 days after application at 12.5 g a.i./ha a reduction of feeding damage compared to the untreated controls can be observed. In another test, a non-GM soybean variety is treated with 12.5 g a.i./ha and showed less reduction in feeding damage compared to the untreated controls.

Claims

Claims
1 . A method for controlling pests and/or increasing the plant health of a cultivated plant with at least one modification as compared to the respective non-modified control plant, com- prising the application of at least one pesticide to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, wherein the pesticide is a pesticide compound of formula I):
Figure imgf000121_0001
wherein
R1 is selected from the group consisting of H, F, CI, Br and CN;
R2 is selected from the group consisting of F, CI, Br, I, CH3;
R3 is selected from the group consisting of Br, CI, CHF2, CF3 and OCH2F;
R4 is CI or CF3;
R5, R6 are selected independently of one another from the group consisting of hydrogen, CrC4-alkyl, C3-C8-cycloalkyl, or
R5 and R6 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,
k is O or l ;
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.
Method according to claim 1 or 2, in which in the compound of formula I
R3 is CF3 or Br, preferably CF3;
R4 is CI.
Method according to claim 1 , 2 or 3, in which in the compound of formula I
R1 is selected from the group consisting of Br, CI, CN, preferably CI;
R2 is selected from the group consisting of CI, CH3; preferably CH3.
Method according to claim 1 , 2 or 3, in which in the compound of formula I
R5 and R6 are selected from methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopropylmethyl, preferably ethyl or isopropyl, and wherein preferably R5 and R6 are identical.
Method according to claim 1 , 2 or 3, in which the compound of formula I is selected from the group consisting of the following compounds 1-1 1 , 1-16, 1-21 , I-26, 1-31 :
Figure imgf000122_0001
6. Method according to any of claims 1 to 5, wherein the cultivated plant is a soybean variety with glyphosate tolerance and lepidopteran resistance. 7. Method according to any of claims 1 to 6, wherein the glyphosate tolerance is through the expression of the cp4epsps gene, or wherein the lepidopteran resistance is through ex- presssion of the CrylAC encoding gene from B. thuringiensis, or wherein both the glyphosate tolerance is through the expression of the cp4epsps gene and the lepidopteran resistance is through expresssion of the CrylAC encoding gene from B. thuringiensis.
8. Method according to any of claims 1 to 7, wherein the glyphosate tolerance is based on the transgenic event MON89788, or wherein the lepidopteran resistance is based on the transgenic event MON87701 , or wherein both the glyphosate tolerance is based on the transgenic event MON89788 and the lepidopteran resistance is based on the transgenic event MON87701 .
9. Method according to any of claims 1 to 8, wherein the lepidopteran resistance is against a species selected from the group of velvetbean caterpillar (Anticarsia gemmatalis) and soybean looper (Pseudoplusia includens, Chrysodeixis includens ).
10. The method according to any of claims 1 to 9, wherein the cultivated plant is "Intacta RR2 PRO" soybean (Monsanto), which claims to offer tolerance to glyphosate herbicide and protection against major soybean pests (velvetbean caterpilar, soybean looper, soybean budborer, bean shoot borer, bollworm, corn stalk borer, Helicoverpa, e.g. Helicoverpa ar- migera), along with increased yield potential.
1 1 . Method according to any of claims 1 to 10, wherein the plant has at least one insecticidal trait, and wherein the pests are harmful insects which are resistant to that at least one insecticidal trait of the plant.
12. The method according to any of claims 1 to 1 1 , wherein the pest is selected from the group of stinkbug species (preferably Euschistus heros), Spodoptera frugiperda and Helicoverpa..
13. The method according to any of claims 1 to 12, comprising the application of a mixture of a pesticide of formula I and at least one pesticide II to a plant with at least one modification, parts of such plant, plant propagation material, or at its locus of growth, preferably wherein the pesticide II is selected from the group of fipronil, alpha-cypermethrin, dinote- furan, chlorfenapyr, teflubenzuron and sulfoxaflor.
14. The method according to any of claims 1 to 13, additionally comprising the application of a herbicide, to which the plant is tolerant.
15. Method according to any of claims 1 to 5 wherein the modification is selected from the events listed in table A1 , table A2 and table 3.
16. Seed of a cultivated plant as defined in any one of claims 5 to 15 treated with at least one pesticide as defined in any of claims 1 to 5.
PCT/EP2015/068006 2014-09-02 2015-08-05 Use of n-thio-anthranilamide compounds on cultivated plants Ceased WO2016034352A1 (en)

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WO2017189797A1 (en) * 2016-04-27 2017-11-02 Valent Biosciences Llc Synergistic bacillus thuringiensis, subsp. kurstaki and cyantraniliprole mixtures for diamondback moth, beet armyworm, sugarcane borer, and soybean looper control

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WO2013024009A1 (en) * 2011-08-12 2013-02-21 Basf Se N-thio-anthranilamide compounds and their use as pesticides
WO2014053403A1 (en) * 2012-10-01 2014-04-10 Basf Se Method of controlling insecticide resistant insects
WO2014053395A1 (en) * 2012-10-01 2014-04-10 Basf Se Use of n-thio-anthranilamide compounds on cultivated plants

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WO2014053403A1 (en) * 2012-10-01 2014-04-10 Basf Se Method of controlling insecticide resistant insects
WO2014053395A1 (en) * 2012-10-01 2014-04-10 Basf Se Use of n-thio-anthranilamide compounds on cultivated plants

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017189797A1 (en) * 2016-04-27 2017-11-02 Valent Biosciences Llc Synergistic bacillus thuringiensis, subsp. kurstaki and cyantraniliprole mixtures for diamondback moth, beet armyworm, sugarcane borer, and soybean looper control
US10278396B2 (en) 2016-04-27 2019-05-07 Valent Biosciences Llc Synergistic Bacillus thuringiensis subsp. kurstaki and cyantraniliprole mixtures for diamondback moth, beet armyworm, sugarcane borer, and soybean looper control

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