Novel carboxamide and sulfonamide pesticidal compounds

Abstract

Compounds of the formula (I) wherein the substituents are as defined in claim 1 and the agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of those compounds can be used as insecticides. # imgabs0 #

Description

[0001] The present invention relates to pesticidal, in particular insecticidal, carboxamide compounds, preferably substituted carboxamide compounds thereof, processes for their preparation, compositions comprising these compounds, and their use for controlling animal pests, including arthropods and in particular insects.

[0002] WO 2021 / 153720 describes certain alkoxybenzamide derivatives.

[0003] Certain new carboxamide compounds with pesticidal activity have been discovered.

[0004] Therefore, the present invention relates in a first aspect to a compound of formula (I), or a salt or N-oxide thereof

[0005]

[0006] in:

[0007] X is CH or N;

[0008] R 1 C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of said 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2 wherein any of the 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the C3-C6-cycloalkyl, C4-C8-bicycloalkyl and 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl, and wherein any of the phenyl or the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;

[0009] R 2is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0010] R 3 and R 4 are independently selected from hydrogen or C1-C3-alkyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent C3-C5-cycloalkyl;

[0011] R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent C3-C5-cycloalkyl;

[0012] R 7 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, phenyl, or 5-membered or 6-membered heteroaryl, wherein the cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl; wherein any of the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, S and O, and wherein any of the phenyl and the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;

[0013] R 8 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, C3-C5-cycloalkylcarbonyl or C1-C4-alkoxycarbonyl; and

[0014] R 9 is selected from halogen or C1-C3-alkyl.

[0015] Surprisingly, for practical purposes, novel compounds of formula (I) have been found to have advantageous levels of biological activity for protecting plants against insects or to have superior properties for use as active ingredients in agrochemicals, for example, higher biological activity, an advantageous spectrum of activity, increased safety (towards non-target organisms above and below ground, such as fish, birds, and bees), improved physico-chemical properties, or increased biodegradability. In particular, it has been unexpectedly discovered that certain compounds of formula (I) can exhibit advantageous safety profiles against non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumble bees. Most particularly, against the Italian honey bee (Apis mellifera).

[0016] According to a second aspect of the present invention, there is provided a composition comprising a compound of formula (I) as defined in the first aspect. Such a composition may further comprise at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

[0017] According to a third aspect of the present invention, there is provided a method for combating and controlling insects, mites, nematodes or molluscs, comprising applying an insecticide, acaricide, nematode or molluscicide effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect to the pest, a location of the pest, or a plant susceptible to attack by the pest.

[0018] According to a fourth aspect of the present invention, there is provided a method for protecting plant propagation materials from attack by insects, mites, nematodes or mollusks, comprising treating the propagation material or the site where the propagation material is planted with an effective amount of a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect.

[0019] According to a fifth aspect of the invention, the present invention makes it possible to obtain a plant propagation material, such as a seed, which comprises a compound of formula (I) as defined in the first aspect or a composition as defined in the second aspect, or is treated with or has attached thereto the compound or the composition.

[0020] Compounds of formula (I) with at least one basic center can form acid addition salts, for example, with strong inorganic acids (such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (such as unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid), or organic sulfonic acids (such as unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, for example methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula (I) having at least one acidic group can, for example, form salts with bases, for example mineral salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine.

[0021] In each case, the compounds of formula (I) according to the invention are in free form, in oxidized form (such as N-oxides), or in salt form (eg agronomically usable salt forms).

[0022] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, in the book "Heterocyclic N-oxides" by A. Albini and S. Pietra, CRC Press, Boca Raton, 1991.

[0023] The compounds of formula (I) according to the invention also include hydrates which may be formed during salt formation.

[0024] When a substituent is indicated as "optionally substituted", this means that it may or may not carry one or more substituents, which may be the same or different, e.g., one, two or three R x Substituents. For example, C1-C6 alkyl substituted with 1, 2 or 3 halogens may include, but are not limited to, -CH2Cl, -CHCl2, -CCl3, -CH2F, -CHF2, -CF3, -CH2CF3 or -CF2CH3 groups. As another example, C1-C6 alkoxy substituted with 1, 2 or 3 halogens may include, but are not limited to, CH2ClO-, CHCl2O-, CCl3O-, CH2FO-, CHF2O-, CF3O-, CF3CH2O- or CH3CF2O- groups.

[0025] As used herein, the term "halogen" or "halo" refers to fluorine (fluorine, fluoro), chlorine (chlorine, chloro), bromine (bromine, bromo) or iodine (iodine, iodo), preferably fluorine, chlorine or bromine. This also applies accordingly to halogen in combination with other meanings, such as haloalkyl, haloalkoxy and halocycloalkyl.

[0026] As used herein, amino refers to a -NH2 group.

[0027] As used herein, cyano refers to a -CN group.

[0028] As used herein, the term "hydroxyl" or "hydroxy" refers to an -OH group.

[0029] As used herein, the term "carboxylic acid" refers to a -COOH group.

[0030] As used herein, the term "C1-C n "-alkyl" refers to a saturated straight or branched hydrocarbon radical having 1 to n carbon atoms, attached via any carbon atom, such as any of the following: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, n-pentyl, 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, or 1-ethyl-2-methylpropyl.

[0031] As used herein, the term "C2-C n "-Alkenyl" refers to a straight or branched alkenyl chain moiety having from 2 to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.

[0032] As used herein, the term "C2-C n -alkynyl" refers to a straight or branched alkynyl chain moiety having from two to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.

[0033] As used herein, the term "C3-C n "-cycloalkyl" refers to a 3-membered to n-membered cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0034] As used herein, the term "C1-C n "-alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms attached via an oxygen atom (as mentioned above), for example, any one of the following groups: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy. As used herein, the term "C2-C n "-Alkenyloxy" refers to a straight or branched alkenyl chain (as mentioned above) having 1 to n carbon atoms attached via an oxygen atom.

[0035] As used herein, the term "C1-C n -alkylsulfonyl" refers to a group having the formula -S(O)2R a A group in which R a is C1-C as defined above n -alkyl.

[0036] As used herein, the term "C1-C n -alkylsulfonyl-C1-C n -alkyl" refers to a C1-C n - an alkyl group substituted with an alkylsulfonyl group (as mentioned above).

[0037] As used herein, the term "C1-C n -alkoxy-C1-C n -alkyl" refers to a C1-C n - Alkoxy-substituted alkyl (as mentioned above). Examples are methoxymethyl, methoxyethyl, ethoxymethyl and propoxymethyl.

[0038] As used herein, the term "C3-C n -cycloalkyl-C1-C n -alkyl" refers to a C3-C n - cycloalkyl substituted alkyl (as mentioned above). Examples are cyclopropylmethyl, cyclopropylethyl. Similarly, the term "C3-C n -halogenated cycloalkyl-C1-C n "-alkyl" refers to an alkyl group substituted by a cycloalkyl group, wherein the cycloalkyl group is substituted by one or more identical or different halogen atoms. Examples are 3,3-difluorobutylmethyl and 1-chlorocyclopropylmethyl.

[0039] As used herein, the term "C4-C n"-Bicycloalkyl" refers to a cyclic non-aromatic bicyclic ring system comprising two rings fused together (e.g., sharing two carbon atoms) and consisting solely of carbon and hydrogen atoms. Examples are bicyclo[1.1.1]pentanyl, bicyclo[3.1.0]hexan-6-yl, bicyclo[4.1.0]heptan-7-yl, bicyclo[3.2.0]heptan-6-yl, bicyclo[3.2.0]heptan-3-yl, octahydro-2-pentalenyl, octahydro-1-pentalenyl.

[0040] As used herein, the term "heterocycloalkyl" or "heterocyclyl" refers to a stable 3-, 4-, 5- to 6-membered non-aromatic monocyclic group comprising 1, 2, or 3 heteroatoms / groups individually selected from nitrogen, oxygen, sulfur, S=O, and SO2. The heterocyclyl group can be bonded to the rest of the molecule via a carbon atom or a heteroatom. Examples of heterocyclyl groups include, but are not limited to, epoxy, aziridinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydrothiopyranyl, piperidinyl, piperazinyl, tetrahydropyranyl, dioxolane, morpholinyl, oxazinyl, oxetane, 1,1-dioxothietane-3-yl, or δ-lactamyl. Heterocycloalkyl groups can be substituted on heteroatoms and / or carbon atoms. The term "cyanoheterocycloalkyl" refers to a carbon atom on a heterocycloalkyl group that is substituted by a cyano group.

[0041] As used herein, the term "cyano-C1-C n -alkyl" refers to a C1-C1-C1-alkyl group having 1 to n carbon atoms n -alkyl (as mentioned above), in which one of the hydrogen atoms of the group is replaced by a cyano group: for example, cyano-methyl, 2-cyano-ethyl, 2-cyano-propyl, 3-cyano-propyl, 1-(cyano-methyl)-2-ethyl, 1-(methyl)-2-cyano-ethyl, 4-cyanobutyl, etc. Similarly, the term "cyano-C3-C n -cycloalkyl" refers to a C3-C n -cycloalkyl; and the term "cyano-C3-C n -cycloalkyl-C1-C n -alkyl" refers to a cyano-C3-C n -cycloalkyl C1-C n -alkyl.

[0042] As used herein, the term "C1-C n"-haloalkyl" refers to straight-chain or branched saturated alkyl groups (as mentioned above) having 1 to n carbon atoms, attached via any carbon atom, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, for example, any of the following groups: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl , 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, or nonafluorobutyl. Accordingly, the term "C1-C2-fluoroalkyl" will refer to a C1-C2 alkyl group with 1, 2, 3, 4 or 5 fluorine atoms, such as any one of the following groups: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl. Similarly, as used herein, the term "C2-C n -haloalkenyl" or "C2-C n -haloalkynyl" refers to a C2-C n -alkenyl or C2-C n -alkynyl.

[0043] As used herein, the term "C1-C n -alkylcarbonyl" refers to a C1-C ... n -alkyl.

[0044] As used herein, the term "C1-C n -alkoxycarbonyl" refers to a C1-C ... n -alkoxy moiety.

[0045] As used herein, the term "C1-C n -cycloalkylcarbonyl" refers to a C1-C ... n -cycloalkyl.

[0046] As used herein, the term "phenyl-C1-C n -alkyl" refers to a C1-C1-substituted phenyl ring n -alkyl. Examples include benzyl. Phenyl-C1-C n - The alkyl group may be substituted on the alkyl group and / or the phenyl group.

[0047] As used herein, the term "heteroaryl" refers to a 5- or 6-membered aromatic monocyclic group containing 1, 2, 3, or 4 heteroatoms independently selected from N, O, and S. Examples of heteroaryl groups include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl. The term "heteroaryl-C1-C n -alkyl" or "heteroaryl-C3-C n -cycloalkyl" refers to a C1-C ... n -alkyl or C3-C n -cycloalkyl. Heteroaryl-C1-C n -alkyl or heteroaryl-C3-C n -Cycloalkyl may optionally be substituted on the heteroaryl, alkyl and / or cycloalkyl groups.

[0048] As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and / or preventing further pest damage, such that damage to plants or to plant-derived products is reduced.

[0049] As used herein, the term "pest" refers to insects and molluscs present in agriculture, horticulture, forestry, storage of products of plant origin (such as fruit, grain and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the pest life cycle.

[0050] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof that provides the desired effect upon single or multiple administrations.

[0051] The effective amount is readily determined by one skilled in the art by using known techniques and by observing the results obtained under similar circumstances. In determining the effective amount, many factors are considered, including, but not limited to, the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.

[0052] As used herein, the term "room temperature" or "RT" or "rt" or "ambient temperature" refers to a temperature of about 15° C. to about 35° C. For example, rt may refer to a temperature of about 20° C. to about 30° C.

[0053] The following list provides substituents R for compounds of formula (I) of the present invention. 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 Definitions of and X, including preferred definitions. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

[0054] In one embodiment of the present invention, X is selected from CH or N. In another embodiment of the present invention, X is CH. In yet another embodiment of the present invention, X is N.

[0055] In one embodiment of the present invention, R 1 C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of said 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2 ; wherein any one of the 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any one of the C3-C6-cycloalkyl, C4-C8-bicycloalkyl and 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl, and wherein any one of the phenyl or the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy. Preferably, R 1C1-C3-alkyl, C1-C3-haloalkyl, C3-C5-cycloalkyl, cyano-C1-C2-alkyl, C3-C5-cycloalkyl-C1-C3-alkyl, C1-C3-alkoxy-C1-C3-alkyl, C1-C3-alkylsulfonyl-C1-C3-alkyl, cyano-C3-C5-cycloalkyl, C4-C6-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C3-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2 ; wherein any one of the 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any one of the C3-C5-cycloalkyl, C4-C6-bicycloalkyl and 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl, and wherein any one of the phenyl or 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy. More preferably, R 1 is selected from C1-C3-alkyl, C1-C3-haloalkyl, C3-C5-cycloalkyl, cyano-C1-C2-alkyl, C3-C5-cycloalkyl-C1-C3-alkyl, C1-C3-alkoxy-C1-C3-alkyl, C1-C3-alkylsulfonyl-C1-C3-alkyl, cyano-C3-C5-cycloalkyl, C4-C6-bicycloalkyl, wherein any one of the C3-C5-cycloalkyl and C4-C6-bicycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl. More preferably, R 1 Selected from C1-C3-alkyl, C1-C3-haloalkyl, C3-C5-cycloalkyl, cyano-C1-C2-alkyl, C3-C5-cycloalkyl-C1-C3-alkyl, C1-C3-alkoxy-C1-C3-alkyl, C1-C3-alkylsulfonyl-C1-C3-alkyl, cyano-C3-C5-cycloalkyl, C4-C6-dicycloalkyl, wherein any one of the C3-C5-cycloalkyl and C4-C6-dicycloalkyl is unsubstituted or substituted by 1 substituent selected from fluorine, chlorine, cyano, methyl, trifluoromethyl or difluoromethyl.

[0056] In another embodiment of the present invention, R 1is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl, or 5-membered or 6-membered heteroaryl-C1-C3-alkyl, wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5 wherein any of the 3-, 4-, 5-, or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S, or O, with the proviso that no more than one is O or S; wherein any of the 3-, 4-, 5-, or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, or C3-C6 cycloalkyl, and wherein any of the phenyl or the 5- or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, or C1-C4 alkoxy. In another embodiment of the present invention, R 1 is selected from C1-C3-alkyl, C1-C3-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C3-alkyl, C3-C6-cycloalkyl-C1-C3-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C2-alkyl or 5-membered or 6-membered heteroaryl-C1-C2-alkyl, wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein said any of the 5-membered or 6-membered heteroaryl-C1-C2-alkyl contains 1 or 2 heteroatoms independently selected from N, S or O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy.

[0057] In yet another embodiment, R 1is selected from C1-C3-alkyl, C1-C3-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C3-alkyl, cyano-C3-C6-cycloalkyl, phenyl or 5-membered or 6-membered heterocycloalkyl, wherein any of the 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein any of the 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl, and wherein any of the phenyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy. Preferably, R 1 is C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl.

[0058] In one embodiment of the present invention, R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl. Preferably, R 2 is selected from hydrogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C2-alkoxy-C1-C3-alkyl, cyano-C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl. More preferably, R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl. Still more preferably, R 2 is hydrogen or methyl. Even more preferably, R 2 It's hydrogen.

[0059] In one embodiment of the present invention, R 3 and R 4 are independently selected from hydrogen or C1-C3-alkyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a C3-C5-cycloalkyl group. 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, cyclopropyl groups are represented.

[0060] In one embodiment of the present invention, R 3 is selected from hydrogen or C1-C3-alkyl. 3 is hydrogen or methyl. More preferably, R 3It's hydrogen.

[0061] In one embodiment of the present invention, R 4 is selected from hydrogen or C1-C3-alkyl. 4 is hydrogen or methyl. More preferably, R 4 It's hydrogen.

[0062] In another embodiment of the present invention, R 3 and R 4 Together with the carbon to which they are attached they represent C3-C5-cycloalkyl.

[0063] In one embodiment of the present invention, R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent a C3-C5-cycloalkyl group. 5 and R 6 are independently selected from hydrogen or methyl; or R 5 and R 6 Together with the carbon to which they are attached, cyclopropyl groups are represented.

[0064] In one embodiment of the present invention, R 5 is selected from hydrogen or C1-C3-alkyl. 5 is hydrogen or methyl. More preferably, R 5 It's methyl.

[0065] In one embodiment of the present invention, R 6 is selected from hydrogen or C1-C3-alkyl. 6 is hydrogen or methyl. More preferably, R 6 It's hydrogen.

[0066] In another embodiment of the present invention, R 5 and R 6 Together with the carbon to which they are attached they represent a C3-C5 cycloalkyl group.

[0067] In one embodiment of the present invention, R 7is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, phenyl or 5-membered or 6-membered heteroaryl, wherein the cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl; wherein any of the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, S or O, with the proviso that no more than one is O or S; and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy. In another embodiment of the present invention, R 7 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, phenyl or 5-membered or 6-membered heteroaryl, wherein the cycloalkyl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl; and wherein any of the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, S or O, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy. Preferably, R 7 is selected from C1-C4-alkyl, C1-C4-haloalkyl, or 5-membered or 6-membered heteroaryl, wherein any of the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, S or O, and wherein any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy. More preferably, R 7 is C1-C4-haloalkyl. Even more preferably, R 7 is dichloromethyl, difluoromethyl or trifluoromethyl. Most preferably, R 7 It is trifluoromethyl.

[0068] In one embodiment of the present invention, R 8 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl. In another embodiment of the present invention, R 8 is selected from hydrogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-alkoxy-C1-C3-alkyl, cyano-C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl. Preferably, R 8is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl; more preferably, R 8 is hydrogen, methyl, ethyl, acetyl, methoxymethyl or ethoxymethyl. Even more preferably, R 8 is hydrogen, methyl, acetyl or methoxymethyl. Still even more preferably, R 8 It's hydrogen.

[0069] In yet another embodiment of the present invention, R 8 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, C3-C5-cycloalkylcarbonyl or C1-C4-alkoxycarbonyl. Preferably, R 8 is selected from hydrogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-alkoxy-C1-C3-alkyl, cyano-C1-C3-alkyl, C1-C3-alkylcarbonyl, C3-C5-cycloalkylcarbonyl or C1-C4-alkoxycarbonyl. Even more preferably, R 8 is selected from hydrogen, C1-C2-alkyl, C1-C2-alkoxy, C1-C2-alkoxy-C1-C3-alkyl, cyano-C1-C2-alkyl, C1-C2-alkylcarbonyl, C3-C5-cycloalkylcarbonyl or C1-C2-alkoxycarbonyl.

[0070] In one embodiment of the present invention, R 9 is selected from halogen or C1-C3-alkyl. 9 is chlorine, bromine, fluorine, methyl or ethyl. More preferably, R 9 is chlorine, bromine or methyl. Even more preferably, R 9 is chlorine or methyl. Still more preferably, R 9 It's chlorine.

[0071] The present invention thus makes available compounds of formula (I) having R as defined above in all combinations / permutations. 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and X

[0072] Examples according to the present invention are provided as listed below.

[0073] In one embodiment of the present invention, the compound of formula (I), or a salt or N-oxide thereof, wherein

[0074] X is CH or N;

[0075] R 1 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0076] R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0077] R 3 and R 4 are independently selected from hydrogen or C1-C3-alkyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a C3-C5 cycloalkyl group;

[0078] R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent a C3-C5 cycloalkyl group;

[0079] R 7is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, phenyl, or 5-membered or 6-membered heteroaryl, wherein the cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl; wherein any of the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, S and O, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy;

[0080] R 8 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl; and

[0081] R 9 is selected from halogen or C1-C3-alkyl.

[0082] In one embodiment, in the compound of formula (I) according to the present invention

[0083] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0084] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0085] R 5 and R 6 are independently selected from hydrogen or methyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0086] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0087] And R 1 、R 7 、R 9 and X are as defined for the compound of formula (I).

[0088] In another embodiment, in the compound of formula (I) according to the present invention

[0089] R2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0090] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0091] R 5 and R 6 independently selected from hydrogen or methyl;

[0092] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0093] And R 1 、R 7 、R 9 and X are as defined for the compound of formula (I).

[0094] In another embodiment, in the compound of formula (I) according to the present invention

[0095] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0096] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0097] R 5 and R 6 independently selected from hydrogen or methyl;

[0098] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0099] R 9 It is chlorine;

[0100] And R 1 、R 7 and X are as defined for the compound of formula (I).

[0101] In another embodiment, in the compound of formula (I) according to the present invention

[0102] R 2is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0103] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0104] R 5 and R 6 independently selected from hydrogen or methyl;

[0105] R 7 is selected from C1-C4-alkyl, C1-C4-haloalkyl, or 5-membered or 6-membered heteroaryl, wherein any of the 5-membered or 6-membered heteroaryl contains 1 heteroatom selected from N, S or O, and wherein any of the phenyl, 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl or C1-C3 alkoxy;

[0106] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0107] R 9 It is chlorine;

[0108] And R 1 and X are as defined for the compound of formula (I).

[0109] In yet another embodiment, in the compound of formula (I) according to the present invention

[0110] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0111] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0112] R 5 and R 6 independently selected from hydrogen or methyl;

[0113] R 7 is a C1-C4-haloalkyl group;

[0114] R 8is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0115] R 9 It is chlorine;

[0116] And R 1 and X are as defined for the compound of formula (I).

[0117] In yet another embodiment, in the compound of formula (I) according to the present invention

[0118] R 1 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0119] R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0120] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0121] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0122] R5 and R 6 independently selected from hydrogen or methyl;

[0123] R 7 is a C1-C4-haloalkyl group;

[0124] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0125] R 9 It is chlorine;

[0126] and X is as defined for the compound having formula (I).

[0127] In yet another embodiment, in the compound of formula (I) according to the present invention

[0128] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0129] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0130] R 5 and R 6 independently selected from hydrogen or methyl;

[0131] R 7 is trifluoromethyl;

[0132] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0133] R 9 It is chlorine;

[0134] And R 1 and X are as defined for the compound of formula (I).

[0135] In yet another embodiment, in the compound of formula (I) according to the present invention

[0136] R 1is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0137] R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0138] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0139] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0140] R 5 and R 6 independently selected from hydrogen or methyl;

[0141] R 7 is trifluoromethyl;

[0142] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0143] R 9 It is chlorine;

[0144] and X is as defined for the compound having formula (I).

[0145] In one embodiment of the present invention, the compound having formula (I) may be a compound having formula (Ia), wherein X is CH:

[0146]

[0147] And where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 As defined for compounds of formula (I).

[0148] In one embodiment, in the compound of formula (Ia) according to the present invention

[0149] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0150] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0151] R 5 and R 6 are independently selected from hydrogen or methyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0152] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl:

[0153] And R 1 、R 7 and R 9 As defined for compounds of formula (I).

[0154] In another embodiment, in the compound of formula (Ia) according to the present invention

[0155] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0156] R 3 and R4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0157] R 5 and R 6 independently selected from hydrogen or methyl;

[0158] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0159] R 9 It is chlorine;

[0160] And R 1 and R 7 As defined for compounds of formula (I).

[0161] In another embodiment, in the compound of formula (Ia) according to the present invention

[0162] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0163] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0164] R 5 and R 6 independently selected from hydrogen or methyl;

[0165] R 7 is trifluoromethyl;

[0166] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0167] R 9 It is chlorine;

[0168] And R 1 As defined for compounds of formula (I).

[0169] In another embodiment, in the compound of formula (Ia) according to the present invention

[0170] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0171] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0172] R 5 and R 6 independently selected from hydrogen or methyl;

[0173] R 7 is a C1-C4-haloalkyl group;

[0174] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0175] R 9 It is chlorine;

[0176] And R 1 As defined for compounds of formula (I).

[0177] In another embodiment, in the compound of formula (Ia) according to the present invention

[0178] R 1 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0179] R 2is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0180] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0181] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0182] R 5 and R 6 independently selected from hydrogen or methyl;

[0183] R 7 is a C1-C4-haloalkyl group;

[0184] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl; and

[0185] R 9 It's chlorine.

[0186] In another embodiment, in the compound of formula (Ia) according to the present invention

[0187] R 1is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0188] R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0189] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0190] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0191] R 5 and R 6 independently selected from hydrogen or methyl;

[0192] R 7 is trifluoromethyl;

[0193] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl; and

[0194] R 9 It's chlorine.

[0195] In another embodiment of the present invention, the compound having formula (I) may be a compound having formula (Ib), wherein X is N:

[0196]

[0197] And where R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 and R 9 As defined for compounds of formula (I).

[0198] In one embodiment, in the compound of formula (Ib) according to the present invention

[0199] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0200] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0201] R 5 and R 6 are independently selected from hydrogen or methyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0202] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0203] And R 1 、R 7 and R 9 As defined for compounds of formula (I).

[0204] In another embodiment, in the compounds of formula (Ib) according to the present invention, R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0205] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0206] R 5 and R 6 independently selected from hydrogen or methyl;

[0207] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0208] R 9 It is chlorine;

[0209] And R 1 and R 7 As defined for compounds of formula (I).

[0210] In another embodiment, in the compound of formula (Ib) according to the present invention

[0211] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0212] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0213] R 5 and R 6 independently selected from hydrogen or methyl;

[0214] R 7 is a C1-C4-haloalkyl group;

[0215] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0216] R 9 It is chlorine;

[0217] And R 1 As defined for compounds of formula (I).

[0218] In another embodiment, in the compound of formula (Ib) according to the present invention

[0219] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0220] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0221] R 5 and R 6 independently selected from hydrogen or methyl;

[0222] R 7 is trifluoromethyl;

[0223] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0224] R 9 It is chlorine;

[0225] And R 1 As defined for compounds of formula (I).

[0226] In another embodiment, in the compound of formula (Ib) according to the present invention

[0227] R 1 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0228] R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0229] R2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0230] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0231] R 5 and R 6 independently selected from hydrogen or methyl;

[0232] R 7 is a C1-C4-haloalkyl group;

[0233] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl; and

[0234] R 9 It's chlorine.

[0235] In another embodiment, in the compound of formula (Ib) according to the present invention

[0236] R 1 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2; wherein the 5-membered or 6-membered heteroaryl any of the 3-membered, 4-membered, 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6 cycloalkyl, and wherein the phenyl or any of the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4 alkoxy;

[0237] R 2is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl;

[0238] R 2 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl;

[0239] R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent a cyclopropyl group;

[0240] R 5 and R 6 independently selected from hydrogen or methyl;

[0241] R 7 is trifluoromethyl;

[0242] R 8 is hydrogen, C1-C3-alkyl, C1-C2-alkylcarbonyl or C1-C2-alkoxycarbonyl; and

[0243] R 9 It's chlorine.

[0244] Preferably, the compound according to formula (I) is selected from the compounds listed in Table A1 , A2 or Table P (below).

[0245] More preferably, the compound according to formula (I) is selected from the compounds listed in Table P (below).

[0246] The compounds of formula (I) according to the present invention may have at least two chiral centers at the carbon atoms marked with an asterisk (*) as shown in formula (Ic) below.

[0247]

[0248] Accordingly, as already indicated, compounds of formula (I) may exist in various diastereoisomeric forms, for example, (S,S)-, (S,R)-, (R,R)-, or (R,S)-configurations may exist at the carbon atoms marked with an asterisk (*) as in formula (Ic). Specifically, for compounds of formula (I), with respect to R for each compound described in Table A1, A2 or Table P (below), 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R7 、R 8 、R 9 Each of these configurations may be apparent with specific combinations of definitions of X.

[0249] In another aspect, the present invention provides a method for controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method for controlling parasites on the body of an animal in need thereof, the method comprising administering an effective amount of a compound of formula (I) as defined in the first aspect. The present invention further provides a method for preventing and / or treating a disease transmitted by parasites on the body, the method comprising administering an effective amount of a compound of formula (I) as defined in the first aspect to an animal in need thereof.

[0250] Compounds of formula (I) can be prepared by those skilled in the art according to known methods. More specifically, compounds of formula (I) and intermediates can therefore be prepared as described below in the schemes and examples. For the sake of clarity, certain stereocenters are not indicated and are not intended to limit the teachings of these schemes in any way.

[0251] According to the present invention, the compound of formula (I) (wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and X are as defined for formula (I)) can be obtained by reacting an acyl chloride or an activated acylating agent having formula (III) wherein R 1 as defined for formula (I) and G as described below) to convert a compound of formula (II) wherein R 2 、R 3 、R 5 、R 4 、R 6 、R 7 、R 8 、R 9 and X are as defined for formula (I)). This is shown in the following Scheme 1:

[0252] Solution 1

[0253]

[0254] As shown in Scheme 1, compound (IIIa) is activated to a compound of formula (III) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, when not commercially available, a compound of formula (III) wherein G is a halogen is formed by treating a compound of formula (IIIa) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as DCM or THF at a temperature between 25° C. and 170° C., preferably between 25° C. and 80° C. Optionally, treatment of (II) with a compound of formula (III) in the presence of a base such as triethylamine or pyridine produces a compound of formula (I). Alternatively, compounds of formula (I) can be prepared by treating compounds of formula (IIIa) with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) in an inert solvent (e.g., pyridine or THF), optionally in the presence of a base (e.g., triethylamine), at temperatures between rt and 180° C. to give activated species (III) (wherein G is G1 or G2). In addition, acids of formula (IIIa) can also be activated by reacting with a coupling reagent such as propanephosphonic anhydride. or O-(7-aza-1-benzotriazolyl)-N,N,N',N'-tetramethyluronium-hexafluorophosphate (HATU) to provide compounds of formula (III) (wherein G is G3 and G4), as described, for example, in Synthesis 2013, 45, 1569 and J. Prakt. Chem. 1998, 340, 581. Subsequent reaction with an amine of formula (II) provides a compound of formula (I). Alternatively, the compound of formula (II) can be converted to a compound of formula (I) by reaction with an anhydride of formula (III) (wherein G is G5), as described, for example, in WO 2010100405.

[0255] According to the present invention, the compound of formula (I) (wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and X are as defined for formula (I)) can be obtained by using a compound of formula (IV) wherein R 8 as defined for formula (I) and Q is halogen or sulfonate) to convert a compound of formula (Ia) wherein R 2 、R3 、R 5 、R 4 、R 6 、R 7 、R 9 and X are as defined for formula (I)). This is shown in Scheme 2 below:

[0256] Option 2

[0257]

[0258] As shown in Scheme 2, compound (Ia) can be converted to compound (I) by methods known to those skilled in the art and described, for example, in ACS Comb. Sci. 2016, 569; WO 202115372. For example, the reaction can be carried out in an organic solvent (such as DCM, DMF or acetonitrile) in the presence of a base (such as potassium carbonate or triethylamine). Alternatively, the reaction can be carried out with a reagent having formula (IVa). In this case, the reaction can be carried out in an organic solvent (such as DCM, DMF or acetonitrile) in the presence of a base (such as potassium carbonate or triethylamine) and with the aid of a catalyst (such as 4-(dimethylamino)pyridine) as described, for example, in WO 2021178885; Org. Process Res. Dev. 2014, 18, 205.

[0259] The compound of formula (IIa) (wherein R 3 、R 4 、R 5 、R 6 、R 7 、R 8 、R 9 and X are as defined for formula (I)) can be obtained by converting a compound having formula (V) wherein R 5 、R 6 、R 7 、R 8 、R 9 and X are as defined for formula (I)). This is shown in Scheme 3 below:

[0260] Option 3

[0261]

[0262] As shown in Scheme 3, compound (V) can be converted to compound (IIa) by methods known to those skilled in the art and described, for example, in US Pat. No. 6,437,138, US Pat. No. 6,127,386, Tetrahedron Lett. 2010, 4053. For example, the reaction can be carried out in an organic solvent such as THF, DCM, or methanol in the presence of hydrogen and a catalyst such as nickel, Raney nickel, nickel aluminide, or bis(benzonitrile)dichloropalladium[2,2′-biquinoline]-4,4′-dicarboxylic acid potassium salt (1:2). Depending on the isolation scheme, compound (IIa) can also be obtained and used in the following transformations in the form of its salts (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate, and other salts known to those skilled in the art).

[0263] A compound of formula (Va) wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I)) can be obtained by using a compound of formula (VII) wherein R 7 As defined for formula (I) and G is halogen or sulfonate (G5)) converting a compound of formula (VI) wherein R 5 、R 6 、R 9 and X are as defined for formula (I)). This is shown in the following Scheme 4:

[0264] Option 4

[0265]

[0266] As shown in Scheme 4, compound (VI) can be converted to compound (Va) by methods known to those skilled in the art and described, for example, in Angew.Chem.Int.Ed. [Applied Chemistry International Edition] 2016, 5299; J.Am.Chem.Soc. [Journal of the American Chemical Society] 2018, 5322; WO 2021153720, WO 2010150192, WO2018013774. For example, the reaction can be carried out in the presence of a base (such as triethylamine, pyridine or 1,8-diazabicyclo[5.4.0]undec-7-ene) in an inert organic solvent (such as DCM, dioxane or THF). Alternatively, as known to those skilled in the art, compound (VI) in the form of a salt (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art) can be similarly used to convert to compound (Va).

[0267] The compound of formula (VI) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I)) can be obtained by converting a compound having formula (VIII) wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in the following scheme 5:

[0268] Option 5

[0269]

[0270] As shown in Scheme 5, compound (VIII) can be converted to compound (VI) by methods known to those skilled in the art and described, for example, in WO 2002059117, J. Med. Chem. 2003, 5238, J. Med. Chem. 2003, 46, 1845, Org. Lett. 2022, 2064. For example, the reaction can be carried out in an organic solvent (such as DCM, dioxane or THF) in the presence of an organic or inorganic acid (such as hydrochloric acid, trifluoroacetic acid or p-toluenesulfonic acid). Compound (VI) can also be obtained and used in the following transformations in the form of its salts (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art).

[0271] The compound of formula (VIII) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be obtained by using an alkylating agent having the formula (Xa) (wherein R 5 and R 6 As defined for formula (I), R 10 is C1-C6-alkyl and Q is halogen, hydroxyl (Q3) or sulfonate group (Q1 or Q2)) to convert a compound of formula (IX) wherein R 9 and X are as defined for formula (I)). This is shown in Scheme 6 below.

[0272] Option 6

[0273]

[0274] As shown in Scheme 6, compound (IX) can be converted to compound (VIII) by alkylation reaction with Xa (when Q is, for example, a halogen or sulfonate Q1 or Q2) by methods known to those skilled in the art and described, for example, in J. Chem. Inform. Mod. 2020, 60, 1028; J. Med. Chem. 2003, 46, 1845; WO 2020005935. For example, the reaction can be carried out in an organic solvent (such as DMF, acetone or acetonitrile) in the presence of a base (such as cesium carbonate, sodium hydride or sodium carbonate). Alternatively, compound (IX) can be converted by the method known to those skilled in the art and described in, for example, the following method by the Mitsunobu reaction with Xa (when Q is Q3): WO2005035532; WO 2000071508; J.Med.Chem. [Journal of Medicinal Chemistry] 2020, 63, 14867. For example, the reaction can be carried out in the presence of an azodicarboxylate reagent (such as diethyl azodicarboxylate or diisopropyl azodicarboxylate) and a phosphine reagent (such as triphenylphosphine) in an organic solvent (such as toluene, THF or dichloromethane). Alternatively, compound (IX) can be converted into compound (VIII) by the alkylation reaction with aziridine (Xb) by the method known to those skilled in the art and described in, for example, WO 2008109613. For example, the reaction can be carried out in the presence of a base (such as potassium carbonate, sodium hydride or sodium carbonate) in an organic solvent (such as acetonitrile).

[0275] The compound of formula (IIb) (wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I)) can be prepared via an intermediate having formula (XIIa) wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I) and R 12 is C1-C6-alkyl) to a compound of formula (IX) wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I) and R 11 Alternatively, compound (IIb) can be obtained via an intermediate having formula (XIIb) (wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I)). This is shown in Scheme 7 below.

[0276] Option 7

[0277]

[0278] As shown in Scheme 7, compound (XI) can be converted into intermediate (XIIa) (wherein R 12is C1-C6-alkyl or benzyl): WO 2003051276; WO 2005082859; Biochem.Pharm. [Biochemical Pharmacology] 2007, 73, 1558; WO 2010024430, WO 2016128529. For example, the reaction can be carried out in an organic solvent (such as DMF, THF or acetonitrile) in the presence of a base (such as cesium carbonate, sodium hydride, potassium carbonate or sodium carbonate). Next, intermediate (XIIa) can be converted into compound (IIb) by a deprotection reaction under acidic conditions. For example, the reaction can be carried out in an organic solvent (such as dioxane, ethyl acetate (EtOAc), THF, DCM or acetonitrile) in the presence of an organic or inorganic acid (such as hydrochloric acid, trifluoroacetic acid or p-toluenesulfonic acid). Compound (IIb) can also be obtained and used in the following conversion in its salt form (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art). This is described, for example, in WO 2016128465, WO 2005082859, and WO 2010024430. Alternatively, compound (XI) can be converted into intermediate (XIIb) by reaction with an azide salt as known to those skilled in the art and described, for example, in Bioorg.Chem. [Biological Organic Chemistry] 2021, 108, 104654; J.Med.Chem. [Journal of Medicinal Chemistry] 2003, 46, 453. For example, the reaction can be carried out in the presence of sodium azide, potassium azide or lithium azide in an organic solvent (e.g., acetone, DMF, dimethyl sulfoxide, THF, dioxane) or a mixture of an organic solvent and water. Next, intermediate (XIIb) can be converted to compound (IIb) by partial reduction of the azide. For example, the reaction can be carried out in an organic solvent (such as ethanol, methanol, THF, EtOAc) or a mixture of an organic solvent and water in the presence of hydrogen and a catalyst (such as a palladium substance, palladium on carbon or a platinum substance). This is described, for example, in J. Med. Chem. [Journal of Medicinal Chemistry] 2003, 46, 453; Tetrahedron [Tetrahedron] 2005, 61, 2217. Alternatively, the reaction can be carried out in a mixture of water and an organic solvent (such as THF, dioxane or toluene) in the presence of triphenylphosphine, as described, for example, in WO 2002036734.

[0279] A compound having formula (XI) (wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I) and R 11 is halogen) can be obtained by converting a compound having formula (XIII) wherein R 5 、R6 、R 7 、R 9 and X are as defined for formula (I)). This is shown in Scheme 8 below.

[0280] Option 8

[0281]

[0282] As shown in Scheme 8, compound (XIII) can be converted to compound (XI) by a benzyl halogenation reaction as known to those skilled in the art and described, for example, in Bioorg. Med. Chem. [Biological Organic and Medicinal Chemistry] 2008, 16, 3309; CN 101407462, Org. Lett. [Organic Express] 2020, 22, 4553; WO 2014207052, CN107501171. For example, the reaction can be carried out in an organic solvent (such as carbon tetrachloride, chloroform, acetonitrile, toluene or chlorobenzene) in the presence of a halogenating agent (such as N-chlorosuccinimide, N-bromosuccinimide, bromine, chlorine, 1,3-dibromo-5,5-dimethylhydantoin or tribromoisocyanuric acid) in the presence of a substoichiometric amount of azobisisobutyronitrile or 1,1′-azobis(cyclohexanecarbonitrile).

[0283] A compound of formula (XIII) (wherein R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I)) can be obtained by using a compound of formula (VII) wherein R 7 as defined for formula (I) and G is halogen or sulfonate) to convert a compound of formula (XIV) wherein R 5 、R 6 、R 9 and X are as defined for formula (I)) (Scheme 9).

[0284] Option 9

[0285]

[0286] As shown in Scheme 9, compound (XIV) can be converted into compound (XIII) by methods known to those skilled in the art and, for example, described in Angew.Chem.Int.Ed. [Applied Chemistry International Edition] 2016, 5299; J.Am.Chem.Soc. [Journal of the American Chemical Society] 2018, 5322; WO 2021153720, WO 2010150192, WO2018013774, WO 2021153720. For example, the reaction can be carried out in the presence of a base (such as triethylamine, pyridine or 1,8-diazabicyclo [5.4.0] undec-7-ene) in an inert organic solvent (such as DCM, dioxane or THF). Alternatively, as known to those skilled in the art, compound (XIV) in the form of a salt (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art) can be similarly used to be converted into compound (XIII).

[0287] A compound of formula (XIV) wherein R 5 、R 6 、R 9 and X are as defined for formula (I)) can be obtained by converting a compound having formula (XV) wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 10 below.

[0288] Plan 10

[0289]

[0290] As shown in Scheme 10, compound (XV) can be converted to compound (XIV) by methods known to those skilled in the art and described, for example, in WO 2002059117, J. Med. Chem. 2003, 5238, J. Med. Chem. 2003, 46, 1845, Org. Lett. 2022, 2064, WO 2019244066. For example, the reaction can be carried out in an organic solvent (such as DCM, dioxane or THF) in the presence of an organic or inorganic acid (such as hydrochloric acid, trifluoroacetic acid or p-toluenesulfonic acid). Compound (XIV) can also be obtained and used in the following transformations in the form of its salts (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art).

[0291] A compound of formula (XV) wherein R5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be obtained by using an alkylating agent having the formula (Xa) (wherein R 5 and R 6 As defined for formula (I), R 10 is C1-C6-alkyl and Q is halogen, hydroxyl or sulfonate group) to convert a compound of formula (XVI) wherein R 9 and X are as defined for formula (I)). This is shown in Scheme 11 below.

[0292] Plan 11

[0293]

[0294] As shown in Scheme 11, compound (XVI) can be converted to compound (XV) by an alkylation reaction with Xa (when Q is, for example, a halogen or sulfonate Q1 or Q2) by methods known to those skilled in the art and described, for example, in J. Chem. Inform. Mod. 2020, 60, 1028; J. Med. Chem. 2003, 46, 1845; WO 2020005935; CN 113563238. For example, the reaction can be carried out in an organic solvent (such as DMF, acetone or acetonitrile) in the presence of a base (such as cesium carbonate, sodium hydride or sodium carbonate). Alternatively, compound (XVI) can be converted by a Mitsunobu reaction with Xa (when Q is equal to OH) by methods known to those skilled in the art and described, for example, in Journal of Medicinal Chemistry 2016, 59, 5356; WO 2005035532; WO 2000071508; Journal of Medicinal Chemistry 2020, 63, 14867. For example, the reaction can be carried out in an organic solvent (such as toluene, THF or dichloromethane) in the presence of an azodicarboxylate reagent (such as diethyl azodicarboxylate or diisopropyl azodicarboxylate) and a phosphine reagent (such as triphenylphosphine). Alternatively, compound (XVI) can be converted to compound (XV) by an alkylation reaction with aziridine (Xb) by methods known to those skilled in the art and described, for example, in J. Org. Chem. 2013, 78, 3867; Journal of Chemical Research (2008), (5), 297; JP 04208254. For example, the reaction can be carried out in an organic solvent such as acetonitrile in the presence of a base such as potassium carbonate, sodium hydride or sodium carbonate.

[0295] The compound of formula (Ia) (wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 and X are as defined for formula (I)) can be obtained by using a compound of formula (VII) wherein R 7 As defined for formula (I) and Q is halogen or sulfonate) converting a compound of formula (XVII) wherein R 1 、R 2 、R 3 、R4 、R 5 、R 6 、R 9 and X are as defined for formula (I)). This is shown in Scheme 12 below.

[0296] Plan 12

[0297]

[0298] As shown in Scheme 12, compound (XVII) can be converted to compound (Ia) by methods known to those skilled in the art and, for example, described in Angew.Chem.Int.Ed. [Applied Chemistry International Edition] 2016, 5299; J.Am.Chem.Soc. [Journal of the American Chemical Society] 2018, 5322; WO 2021153720, WO 2010150192, WO2018013774, WO 2021153720. For example, the reaction can be carried out in the presence of a base (such as triethylamine, pyridine or 1,8-diazabicyclo [5.4.0] undec-7-ene) in an inert organic solvent (such as DCM, dioxane or THF). Alternatively, as known to those skilled in the art, compound (XVII) in the form of a salt (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art) can be similarly used to convert to compound (Ia).

[0299] The compound of formula (XVII) (wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 and X are as defined for formula (I)) can be obtained by converting a compound having formula (XVIII) wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 13 below.

[0300] Plan 13

[0301]

[0302] As shown in Scheme 13, compound (XVIII) can be converted into compound (XVII) by methods known to those skilled in the art and, for example, described in WO 2002059117, J.Med.Chem. [Journal of Medicinal Chemistry] 2003, 5238, J.Med.Chem. [Journal of Medicinal Chemistry] 2003, 46, 1845, Org.Lett. [Organic Letters] 2022, 2064, WO2019244066. For example, the reaction can be carried out in an organic solvent (such as DCM, dioxane or THF) in the presence of an organic or inorganic acid (such as hydrochloric acid, trifluoroacetic acid or p-toluenesulfonic acid). Compound (XVII) can also be obtained and used in the following conversions in its salt form (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate and other salts known to those skilled in the art).

[0303] A compound of formula (XVIII) wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be prepared by using an acyl chloride or an activated acylating agent having the formula (III) (wherein R 1 as defined for formula (I) and G as described below) to convert a compound of formula (XIX) wherein R 2 、R 3 、R 4 、R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 14 below.

[0304] Plan 14

[0305]

[0306] As shown in Scheme 14, compound (IIIa) is activated to a compound of formula (III) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, when not commercially available, a compound of formula (III) wherein G is a halogen is formed by treating the compound of formula (IIIa) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as DCM or THF at a temperature between 25° C. and 170° C., preferably between 25° C. and 80° C. Optionally, treatment of (XIX) with a compound of formula (III) in the presence of a base such as triethylamine or pyridine produces a compound of formula (XVIII). Alternatively, compounds of formula (XVIII) can be prepared by treating compounds of formula (IIIa) with dicyclohexylcarbodiimide (DCC) or 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) in an inert solvent (e.g., pyridine or THF), optionally in the presence of a base (e.g., triethylamine) at temperatures between rt and 180° C. to give activated species (III) (wherein G is G1 or G2). In addition, acids of formula (IIIa) can also be activated by coupling with a coupling reagent such as propanephosphonic anhydride. or O-(7-aza-1-benzotriazolyl)-N,N,N',N'-tetramethyluronium-hexafluorophosphate (HATU) to provide compounds of formula (III) (wherein G is G3 and G4), as described, for example, in Synthesis [Synthesis] 2013, 45, 1569 and J. Prakt. Chemie [Practical Chemistry Journal] 1998, 340, 581. Subsequent reaction with an amine of formula (XIX) provides a compound of formula (XVIII). Alternatively, the compound of formula (XIX) can be converted to a compound of formula (XVIII) by reaction with an anhydride of formula (III) (wherein G is G5), as described, for example, in WO 2010100405.

[0307] A compound of formula (XIXa) wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be converted into a compound of formula (VIII) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 15 below.

[0308] Plan 15

[0309]

[0310] As shown in Scheme 15, compound (VIII) can be converted to compound (XIXa) by methods known to those skilled in the art and described, for example, in US Pat. No. 6,437,138, US Pat. No. 6,127,386, Tetrahedron Lett. 2010, 4053. For example, the reaction can be carried out in an organic solvent such as THF, DCM, or methanol; in the presence of hydrogen and a catalyst such as nickel, Raney nickel, nickel aluminide, or bis(benzonitrile)dichloropalladium[2,2′-biquinoline]-4,4′-dicarboxylic acid potassium salt (1:2). Depending on the isolation scheme, compound (XIXa) can also be obtained and used in the following transformations in the form of its salts (e.g., hydrochloride, hydrobromide, trifluoroacetate, p-toluenesulfonate, and other salts known to those skilled in the art).

[0311] Alternatively, a compound of formula (XIXa) wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be obtained by reacting the intermediate of formula (XXa) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) to a compound of formula (XX) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I), R 11 is a halogen and R 10 This is shown in Scheme 16 below.

[0312] Plan 16

[0313]

[0314] As shown in Scheme 16, compound (XX) can be converted to intermediate (XXa) by reaction with an azide salt as known to those skilled in the art and described, for example, in Bioorg. Chem. [Biological Organic Chemistry] 2021, 108, 104654; J. Med. Chem. [Journal of Medicinal Chemistry] 2003, 46, 453. For example, the reaction can be carried out in the presence of sodium azide, potassium azide or lithium azide in an organic solvent (such as acetone, DMF, dimethyl sulfoxide, THF, dioxane) or a mixture of an organic solvent and water. Next, intermediate (XXa) can be converted to compound (XIXa) by partial reduction of the azide. For example, the reaction can be carried out in the presence of hydrogen and a catalyst (such as a palladium substance, palladium carbon or a platinum substance) in an organic solvent (such as ethanol, methanol, THF, EtOAc) or a mixture of an organic solvent and water. This is described, for example, in J. Med. Chem. 2003, 46, 453; Tetrahedron 2005, 61, 2217. Alternatively, the reaction can be carried out in a mixture of water and an organic solvent such as THF, dioxane or toluene in the presence of triphenylphosphine, as described, for example, in WO2002036734.

[0315] A compound having the formula (XX) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl and R 11 is halogen) can be converted into a compound of formula (XX) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 17 below.

[0316] Plan 17

[0317]

[0318] As shown in Scheme 17, compound (XV) can be converted to compound (XX) by a benzyl halogenation reaction known to those skilled in the art and described, for example, in Bioorg. Med. Chem. 2008, 16, 3309; CN101407462, Org. Lett. 2020, 22, 4553; WO 2014207052, CN107501171. For example, the reaction can be carried out in an organic solvent (such as carbon tetrachloride, chloroform, acetonitrile, toluene or chlorobenzene) in the presence of a halogenating agent (such as N-chlorosuccinimide, N-bromosuccinimide, bromine, chlorine, 1,3-dibromo-5,5-dimethylhydantoin or tribromoisocyanuric acid), optionally in the presence of a substoichiometric amount of azobisisobutyronitrile or 1,1′-azobis(cyclohexanecarbonitrile).

[0319] The compound of formula (XIXb) (wherein R 3 、R 5 、R 6 and X are as defined for formula (I), R 9 is H or as defined for formula (I), and R 10 is C1-C6-alkyl) can be converted into a compound of formula (XXI) (wherein R 3 、R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 18 below.

[0320] Plan 18

[0321]

[0322] As shown in Scheme 18, compound (XXI) can be converted to compound (XIXb) by methods known to those skilled in the art as reductive amination and described, for example, in WO 2018148626, Bioorg. Med. Chem. Lett. [Biological and Medicinal Chemistry Express] 2003, 13, 1725; J. Org. Chem. [Journal of Organic Chemistry] 2020, 85, 6626. For example, the reaction can be carried out as follows: in an organic solvent (such as methanol, ethanol, acetic acid, dimethylformamide or chloroform), in the presence of ammonia, ammonium acetate, ammonium formate, ammonium chloride, hydroxylamine or hydroxylamine hydrochloride; with an optional base (such as triethylamine, pyridine, sodium acetate or potassium carbonate); followed by a reducing agent such as sodium cyanoborohydride, zinc or zinc substances, or with the aid of a catalytic amount of a metal substance (such as palladium on carbon, nickel or cobalt) in a hydrogen atmosphere. The conversion can optionally be carried out in two separate operations (i.e., imine or oxime formation and reduction), wherein the transient imine or oxime intermediate is isolated. Alternatively, the conversion can be carried out by a transamination reaction as described, for example, in Org. Process Res. Dev. 2014, 18, 788; Green Chem. 2017, 19, 474. For example, the reaction can be carried out as follows: in an aqueous buffer solution with a pH range between 4 and 10, optionally in the presence of an organic cosolvent (e.g., methanol, ethanol, acetonitrile, isopropanol, THF, dimethyl sulfoxide); in the presence of isopropylamine and a catalytic system consisting of pyridoxal phosphate and a transaminase (e.g., omega transaminase).

[0323] The compound of formula (XIX) (wherein R 3 、R 5 、R 6 and X are as defined for formula (I), R 9 is H or as defined for formula (I), and R 10 is C1-C6-alkyl) can be obtained by using an alkylating agent having the formula (Xa) (wherein R 5 and R 6 As defined for formula (I), R 10 is C1-C6-alkyl and Q is halogen, hydroxyl or sulfonate group) to convert a compound of formula (XXII) wherein R 3 and X are as defined for formula (I) and R 9 is H or as defined for formula (I). This is shown in Scheme 19 below.

[0324] Plan 19

[0325]

[0326] As shown in Scheme 19, compound (XXII) can be converted into compound (XXI) by an alkylation reaction with Xa (when Q is, for example, a halogen or sulfonate Q1 or Q2) by methods known to those skilled in the art and described, for example, in: J. Chem. Inform. Mod. 2020, 60, 1028; J. Med. Chem. 2003, 46, 1845; WO 2020005935; CN 113563238; Helvetica Chimica Acta 1989, 72, 1216; ACS Chemical Biology 2017, 12, 2570, J. Am. Chem. Soc. 2012, 134(4), 2216. For example, the reaction can be carried out in the presence of a base (such as cesium carbonate, sodium hydride or sodium carbonate) in an organic solvent (such as DMF, acetone or acetonitrile). Alternatively, compound (XXII) can be converted by a method known to those skilled in the art and described, for example, in the following by a Mitsunobu reaction with Xa (when Q is equal to OH (Q3)): WO 2005035532; WO 2000071508; J.Med.Chem. [Journal of Medicinal Chemistry] 2020, 63, 14867; Bioorg.Med.Chem.Lett. [Biological Organic and Medicinal Chemistry Express] 2012, 22, 1633. For example, the reaction can be carried out in the presence of an azodicarboxylate reagent (such as diethyl azodicarboxylate or diisopropyl azodicarboxylate) and a phosphine reagent (such as triphenylphosphine) in an organic solvent (such as toluene, THF or dichloromethane). Alternatively, compound (XXII) can be converted into compound (XXI) by alkylation reaction with aziridine (Xb) by methods known to those skilled in the art and, for example, described in WO 2008109613. For example, the reaction can be carried out in the presence of a base (such as potassium carbonate, sodium hydride or sodium carbonate) in an organic solvent (such as acetonitrile).

[0327] The compound of formula (XIXb) (wherein R 3 、R 4 、R 5 、R 6 and X are as defined for formula (I), R 9 is H or as defined for formula (I) and R 10 is C1-C6-alkyl) can be obtained via intermediate (XXIV) (wherein R 3 、R 4 、R 5 、R 6 and X are as defined for formula (I), R9 is H or as defined for formula (I) and R 10 is C1-C6-alkyl) and intermediate (XXIII) (wherein R 3 、R 4 、R 5 、R 6 and X are as defined for formula (I), R 9 is H or as defined for formula (I) and R 10 is C1-C6-alkyl) to a compound of formula (XXI) wherein R 3 、R 5 、R 6 and X are as defined for formula (I), R 9 is H or as defined for formula (I) and R 10 This is shown in Scheme 20 below.

[0328] Plan 20

[0329]

[0330] As shown in Scheme 20, compound (XXI) can be converted to compound (XIXb) by a stepwise method known to those skilled in the art and described, for example, in J. Org. Chem. 2020, 85, 6626 and J. Am. Chem. Soc. 2019, 141, 7980. The procedures in this stepwise method should be subject to special safety considerations, as described in the Supplementary Information section of J. Am. Chem. Soc. 2019, 141, 7980. Additional useful information can be found in Org. Process Res. Dev. 2012, 16, 2051 and Managing Hazardous Reactions and Compounds in Process Chem. 2014, 87. For example, the conversion of compound (XXII) to intermediate (XXIV) can be carried out in an organic solvent such as THF, diethyl ether, dioxane or toluene in the presence of an intermediate having formula R 4- MgZ Grignard reagent (where R 4As defined for formula (I) and Z is a halide) in the presence of. Next, the conversion of intermediate (XXIV) to intermediate (XXIII) can be obtained in an organic solvent (such as methylene chloride) in the presence of sodium azide and an acidic substance (such as trifluoroacetic acid) in a temperature range between -20 ° C and 50 ° C. For example, the conversion of intermediate (XXIII) to compound (XIXb) can be obtained in an organic solvent (such as THF, dioxane or diethyl ether) in the presence of a reducing agent (such as lithium aluminum hydride) in a temperature range between -20 ° C and 50 ° C. Alternatively, the conversion of intermediate (XXIII) to compound (XIXb) can be carried out in an organic solvent (such as ethanol, methanol, THF, EtOAc) or a mixture of an organic solvent and water in the presence of hydrogen and a catalyst (such as a palladium substance, palladium carbon or a platinum substance). This is described, for example, in J. Med. Chem. 2003, 46, 453; Tetrahedron 2005, 61, 2217. Alternatively, the reaction can be carried out in a mixture of water and an organic solvent such as THF, dioxane or toluene in the presence of triphenylphosphine, as described, for example, in WO 2002036734.

[0331] A compound of formula (XXV) wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 is C1-C6-alkyl) can be converted into a compound of formula (VIII) (wherein R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 21 below.

[0332] Plan 21

[0333]

[0334] As shown in Scheme 21, compound (VIII) can be converted to compound (XXV) by methods known to those skilled in the art and described, for example, in J. Org. Chem. 2003, 68, 7133; ACSMed. Chem. Lett. 2014, 5, 373; WO 2018098206; WO 2018227067. For example, the reaction can be carried out by reacting with ethylmagnesium bromide or ethylmagnesium chloride in an organic solvent (such as diethyl ether, THF, dioxane or methyltetrahydrofuran) in the presence of titanium (IV) isopropoxide at a temperature range of -85°C to 100°C, followed by the addition of a Lewis acid (such as boron trifluoride etherate).

[0335] A compound of formula (XIXa) wherein R 3 、R 4 、R 5 、R 6 and X are as defined for formula (I), R 9 is a halogen and R 10 is C1-C6-alkyl) can be converted into a compound of formula (XIXc) (wherein R 3 、R 4 、R 5 、R 6 、R 9 and X are as defined for formula (I) and R 10 This is shown in Scheme 21 below.

[0336] Plan 22

[0337]

[0338] As shown in Scheme 22, compound (XIXc) can be converted to compound (XIXa) by methods known to those skilled in the art and described, for example, in Synthesis 2022, 341. For example, the reaction can be carried out in an organic solvent (such as acetic acid, dichloroethane, acetonitrile, hexafluoroisopropanol or a mixture of hexafluoroisopropanol / acetic acid) in the presence of a substoichiometric amount of a palladium species (such as palladium (II) acetate, palladium (II) trifluoroacetate or palladium dichloride) in the optional presence of copper (II) acetate or silver (I) acetate, and in the presence of a halide source (such as N-chlorosuccinimide, N-bromosuccinimide, copper dichloride, bromine or chlorine) at a temperature range of between -20°C and 150°C.

[0339] Depending on the procedure or reaction conditions, the reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0340] These reactants can be reacted with each other as is (e.g., without the addition of a solvent or diluent). However, in most cases, it is advantageous to add an inert solvent or diluent or a mixture of these. If the reaction is carried out in the presence of a base, an excess of the base (e.g., triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) can also serve as a solvent or diluent.

[0341] These reactions are advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in a range between ambient temperature and about +80°C.

[0342] Depending on the reaction conditions and the choice of starting materials, which are appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step, or to replace several substituents with other substituents according to the invention in one and the same reaction step.

[0343] The salts of the compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0344] Salts of compounds of the formula (I) can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0345] Salts of compounds of formula (I) can be converted in a manner known per se into other salts, acid addition salts of compounds of formula (I), for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0346] Depending on the procedure or reaction conditions, those compounds of formula (I) which have salt-forming properties can be obtained in free form or in the form of salts.

[0347] Depending on the number, the absolute and relative configuration of the asymmetric carbon atoms present in the molecule and / or on the configuration of the non-aromatic double bonds present in the molecule, the compounds of the formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers and also to all possible isomer mixtures, and the above and below are to be understood as such in each case, even if stereochemical details are not explicitly mentioned in each case.

[0348] Diastereomeric mixtures or racemic mixtures of compounds of formula (I) in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example by fractional crystallization, distillation and / or chromatography.

[0349] Enantiomeric mixtures obtainable in an analogous manner (e.g. racemates) can be resolved into the optical antipodes by known methods, for example by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by formation of inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example by reacting the basic end product racemate with an optically active acid (e.g. a carboxylic acid, for example camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example by fractional crystallization on the basis of their different solubilities, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents (e.g. a basic reagent).

[0350] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0351] N-oxides can be prepared by reacting a compound of formula (I) with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem. 1989, 32 (12), 2561-73 or WO 2000 / 15615.

[0352] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0353] If appropriate, the compounds of formula (I) and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.

[0354] Tables A1 to A2 below show specific compounds of the present invention.

[0355] According to the compound of following table A1 to A2 can be prepared according to above-described method.The following example is intended to illustrate the present invention and show preferred compound with formula (I).In any one of following table A1 to A2, the existence of one or more possible asymmetric carbon atoms in compound with formula (I) according to the present invention means that these compounds can exist with chiral isomer form (for example, enantiomer or diastereomer).

[0356] The compounds of formula (I) according to Tables A1 to A2 below can be prepared according to the methods described herein. The following examples are intended to illustrate the invention and show preferred compounds of formula (I) in the form of compounds of formula (I-A1) and (I-A2).

[0357] Table A1 provides 864 compounds of formula (I-A1), wherein R 3 、R 4 is hydrogen, R 5 is methyl, R 6 is hydrogen and where R 1 、R 2 、R 7 、R 8 、R 9 and X are as defined in Table A1.

[0358]

[0359] Table A1: R 1 、R 2 、R 7 、R 8 、R 9 Definition of substituents of X:

[0360]

[0361]

[0362]

[0363]

[0364]

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382]

[0383]

[0384]

[0385]

[0386]

[0387]

[0388]

[0389]

[0390]

[0391]

[0392] Table A2 provides 150 compounds of formula (I-A2), wherein R 2 、R 8 is hydrogen, R 7 is trifluoromethyl, R 9 is chlorine and where R1 、R 3 、R 4 、R 5 、R 6 and X are as defined in Table A2.

[0393]

[0394] Table A2: R 1 、R 3 、R 4 、R 5 、R 6 Definition of substituents of X:

[0395]

[0396]

[0397]

[0398]

[0399]

[0400]

[0401] The compounds of formula (I) according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control. Even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive as well as resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e., by destroying the pests immediately or only after a certain period of time (e.g., during molting), or indirectly, for example, by reducing egg laying and / or hatching rates.

[0402] Examples of the animal pests mentioned above are:

[0403] From the order of the Acarina, for example: Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarussiro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp.), Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsonetus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.), Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.;

[0404] From the order of the Phycoptes, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

[0405] From the order Coleoptera, for example: Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotoma spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephala spp., Dermestes spp.), Diabrotica spp., Diloboderus abderus, Epilachna spp., Eremnus spp., Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, Megascelis spp., Meligethes aeneus, Melolontha spp.), Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp., Popillia spp., Psylliodes spp.), Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotrogas spp., Somaticus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0406] From the order Diptera, for example: Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibiohortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata), Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp.), Stomoxys spp., Tabanus spp., Tannia spp., and Tipula spp.;

[0407] From the order Hemiptera, for example: Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Acanthocoris spp., Cimex spp., Clavigralla tomentosicollis, Creontiades spp., Dichelops furcatus, Edessa spp., Euchistus spp., Eurydema pulchrum, Acrosternum ... nobilellus), rice stink bug species, grass stink bug species, tropical scale bug species, cabbage stink bug (Murgantia histrionic), new long-margin stink bug species, tobacco blind bug (Nesidiocoris tenuis), green stink bug species, Nysius simulans, island stink bug, skin stink bug species, wall stink bug species, red assassin bug species, cocoa stink bug, chestnut stink bug (Scaptocoris castanea), black stink bug species (Scotinophara spp.), Thyanta spp., trypanosoma species, cassava web stink bug (Vatiga illudens);

[0408] Acyrthosium pisum, Adalges species, Agalliano ensigera, Targuiron vein psyllid, Aleurodicus species, Aleurocanthus species, sugarcane hole whitefly, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, lemon leafhopper, Nephrodisiac species, Aphididae, Aphid species, Aspidiotus species, eggplant groove aphid, Bactericera cockerelli, Aleurodicus species, Brachycaudus species, cabbage aphid, Cavariella species, Cavariella aegopodii Scop.), wax scale species, black-brown round shield scale, orange-brown round shield scale, leafhopper species, large white leafhopper (Cofana spectra), Cryptophyllum species, leafhopper species, brown soft scale, corn yellow-winged leafhopper, naked whitefly species, citrus psyllid, wheat aphid, western round tail aphid species, small green leafhopper species, apple aphid, grape leafhopper species, Gascardia species, red eucalyptus psyllid (Glycaspis brimblecombei), cabbage constrictor aphid (Hyadaphis pseudobrassicae), large tail aphid species (Hyalopterus spp.), Hyperomyzus pallidus, lemon green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax striatellus species, water-hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphids spp., Cicadas spp., Metcalfa pruinosa, Wheat Aphid, Wheat Waxhopper, Aphids spp., Neotoxoptera sp., Black Leafhopper spp., Nilaparvata spp., Pear Green Aphid, Odonaspis ruthae, Sugarcane Cotton Aphid, Bayberry Whitefly, Caulis Psyllid, Shield Scale spp., Gall Aphid spp., Corn Waxhopper, Planthopper spp., Hoppian Aphid, Phylloxera spp.), Mosella species, Morus alba species, Mealybug species, Pseudatomoscelis seriatus, Psyllid species, Pulvinaria aethiopica, Toothed Shield Scale species, Quesada gigas, Recilia dorsalis, Aphid species, Black-helmeted Scale species, Leafhopper species, Schizophrenia species, Sitobion spp., White-backed Planthopper, Spissistilus festinus, Tarophagus proserpina, Aphid species, Whitefly species, Tridiscus sporoboli, Trionymus spp., African Psyllid, Scale, Flame Leafhopper, Zyginidia scutellaris);.

[0409] From the order Hymenoptera, for example: Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Pogonomyrmex spp., Slenopsis invicta, Solenopsis spp. and Vespa spp.;

[0410] From the order Isoptera, for example: Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ant (Solenopsis geminate);

[0411] From the order of the Lepidoptera, for example: Long-winged torrefaction moth species, Brown-banded torrefaction moth species, Clearwing moth species, Spodoptera species, Cotton leafworm, Amylois species, Muscovy bean moth, Yellow torrefaction moth species, Silver moth species (Argyresthia spp.), Banded torrefaction moth species, Spodoptera species, Cotton miner, Corn armyworm, Cabbage moth, Peach fruit moth, Grass borer species, Color torrefaction moth species, Chrysoteuchia topiaria, Grape fruit moth, Leaf roller species, Cloud torrefaction moth species, Striped torrefaction moth species, Sheath moth species, Hedge bean butterfly (Colias lesbia), Small bridge moth (Cosmophila flava), grass borer species, cabbage borer, apple fritter moth, boxwood moth, fritter moth species, boxwood moth, stem borer species, Sudan cotton bollworm, Spodoptera species, South American corn seedling borer (Elasmopalpuslignosellus), sweet potato stem borer, mealybug species, leaf fritter moth species (Epinotia spp.), salt marsh moth (Etiella acrea), bean pod borer (Etiella zinckinella), flower fritter moth species, ring needle fritter moth, yellow tussock moth species, root cutter species, Feltia jaculiferia, small borer species (Grapholita spp.), clouded broad-winged fritter moth, Heliothis species, cabbage borer, leaf cutter species (Herpetogramma spp.), American white moth, tomato codling moth, Lasmopalpus lignosellus, spiral leafminer, leafminer species, grape flower moth, Loxostege bifidalis, tussock moth species, miner species, Malacosoma spp., cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae species, fall moth species, Orniodes indica, European corn borer, super-small tortoise species, brown tortoise species, small-eyed moth, stem borer, red bell moth, coffee leafminer, one-star armyworm, potato moth, cabbage butterfly, Pieris species, diamondback moth, white nest moth species, leaf moth species, mint moth (Rachiplusia spp.) nu), western bean moth (Richia albicosta), white grain borer species (Scirpophaga spp.), stem borer species, tortoise moth species, Spodoptera species, cotton leaf roller, cyprinid species, schizontidae species, tortoise moth species, cabbage looper, tomato leafminer, and brood moth species;

[0412] From the order of the Mallophaga, for example, Damalina spp. and Trichodectes spp.;

[0413] From the order of the Orthoptera, for example, Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0414] From the order of the Psocoptera, for example, Liposcelis spp.;

[0415] From the order of the Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis;

[0416] From the order of the Thysanoptera, for example: Calliothrips phaseoli, Flower Thrips spp., Heliothrips spp., Brown-banded Thrips spp., Parthenothrips spp., Citrus Thrips spp., Bean Thrips, Banded Thrips spp., Thrips spp.;

[0417] From the order of the Thysanura, for example, Lepisma saccharina.

[0418] In a further aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant-parasitic nematodes (endoparasitic nematodes, semi-endoparasitic nematodes and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of Meloidogyne; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heteroderaglycines, Heterodera exigua and other species of Globodera; schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awlnematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus, and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora, and species of the genera Hemicriconemoides; Hirshmanniella species; Lancenematodes, species of the genus Hoploaimus; False rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus, and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes. nematodes), Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus) and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

[0419] The compounds of the present invention may also have activity against molluscs. Examples include, for example, the Pomacea family; the Arion family (A. ater, A. circumscriptus, A. hortensis, A. rufus); the Bradybaenidae family (Bradybaenidae, A. rufus); fruticum); Cepaea (Cepaea hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (Galba trunculata); Helicelia (H. itala, H. obvia); Helicidae (Helicigon) aarbustorum; Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0420] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying harmful organisms of the above-mentioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of such plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these harmful organisms.

[0421] In particular, suitable target crops are cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beets, such as sugar beets or fodder beets; fruits, such as pome, stone or soft fruit, such as apples, pears, plums, peaches, apricots, cherries or berries, such as strawberries, raspberries or blackberries; leguminous crops, such as beans, lentils, peas or soybeans; oilseed crops, such as rapeseed, mustard, poppy, olives, sunflower, coconut, castor, cocoa, beans or peanuts; cucurbits such as pumpkin, cucumber, or melon; fiber plants such as cotton, flax, hemp, or jute; citrus fruits such as oranges, lemons, grapefruits, or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, or bell peppers; lauraceae such as avocado, cinnamon, or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantago, and latex plants.

[0422] In particular embodiments, compounds of formula (I) can control mites, rust mites and spider mites in crops, trees and plants selected from vegetables (especially tomatoes and cucurbits), citrus, pome fruits, stone fruits, nuts, cotton, tropical crops, avocados, ornamentals, beans, soybeans, strawberries and grapes.

[0423] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.

[0424] For example, the present invention can be used with any of the following ornamental plant species: Ageratum species, Alonsoa species, Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger begonia, Begonia sempervirens, Begonia tubéreux), Bougainvillea species, Brachycome species, Brassica species (ornamentals), Calceolaria species, Capsicum, Catharanthus roseus, Canna species, Centaurea species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupheaignea, Dahlia species, Delphinium species, Dicentra species, Dorotheantus species. spp.), Lisianthus, Forsythia species, Fuchsia species, Geranium gnaphalium, Gerbera species, Globe amaranth, Heliotrope species, Sunflower species, Hibiscus species, Hydrangea species, Hydrangea species, Rhododendron, Impatiens species (African balsam), Amaranth species (Iresines spp.), Kalanchoe species, Lantana, March flower, Lion's ear, Lilium species, Mesembryanthemum species, Physalis species, Monarda species, Dracaena species, Marigold species, Dianthus species (carnation), Canna species, Oxalis species, Daisy species, Pelargonium species (Shieldleaf Pelargonium, Horseshoe Pelargonium), Viola species (Viola tricolor), Petunia species, Phlox species, Plecthranthus species spp.), poinsettia species, creeper species (five-leaf creeper, Parthenocissus quinquefolia), primula species, ranunculus species, azalea species, Rosa species (roses), rudbeckia species, African violet species, salvia species, Scaevola aemola, Schizanthus wisetonensis, sedum species, Solanum species, Surfinia petunia species (Surfinia spp.), marigold species, Nicotiana species, verbena species, zinnia species, and other bedding plants.

[0425] For example, the present invention can be used with any of the following vegetable species: Allium species (garlic, onion, shallot (A. oschaninii), leek, shallot, scallion), beaked parsley, celery, asparagus, beets, Brassica species (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (radicchio, endive), watermelon, Cucurbita species (cucumber, cantaloupe), Cucurbita species (zucchini, Indian pumpkin), Cynara species (artichoke, cardoon), carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), pea, radish, edible rhubarb, Rosemary species, sage species, black salsify, eggplant, spinach, Valerian species (V. eriocarpa), and broad beans.

[0426] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.

[0427] The compounds of formula (I) may be particularly suitable for controlling: mites, spider mites and rust mites, for example, Acarus spp.; ... caballi; Demodex canis; Demodex goat; Demodex equi; Demodex ovis; Demodex spp.; Demodex suis; Dermanyssus galli; Dermanyssus spp.; Tetranychus spp.; Tetranychus wei; Pear gall mite; Ribes gall mite; Dermanyssus spp.; Grape gall mite; Tetranychus spp.; Halotydeus destructor; Semitarsonemus spp.; Sarcoptes spp.; Chicken chick mite; Yak mite; Sarcoptes spp.; Neoschongastia xerothermobia; Neotrombicula autumnalis; Neotrombicula desaleri; Cat ear mite; Otodectes spp.; Coffee mite; Holly mite ilicis); Micrognathus species; Chelicerata species; Cystoma spp.; Cystoma spp.; Cystoma spp.; Woodfowl spp.; Dog ear scabies; Otodactylus species; Panonychus citrus; Panonychus species; Apple spp.; Citrus rust; Psoralea species; Phytoseiidae species; Pneumonyssoides caninum; Polyphagous tarsonemus; Polyphagous tarsonemus species; Psorergates ovis; Psorergates species; Rabbit itch mites; Horse itch mites; Sheep itch mites; Psorergates species; Psorergates species; Psorergates ovis; Psorergates species; Psorergates equine; Psorergates ovis; Psorergates species; Psorergates spp. ... rupicaprae); Sarcoptes species; Sarcoptes suis; Scabies scabiei; Scabies scabiei species; Scabies scabiei species; Tarsonemus species; Tetranychus cinnabarinus; Tetranychus kanzawa; Tetranychus species; Tetranychus urticae; Tetranychus urticae; Chigger mites; Tylops scabiei species; Varroa jacobsoni; Varroa species; Vasates lycopersici; and Zetzellia mali.

[0428] In embodiments, compounds of formula (I) may control one or more of: citrus gall mite; tomato needle-spinning gall mite (Aculus lycopersici); Peet's needle-spinning gall mite; Steinni's needle-spinning gall mite; purple-red short-palped mite; short-palped mite species; fruit moss mite; hornbeam spider mite; Eriophyes species; pear gall mite; Eriophyes piri; Eriophyes species; grape gall mite; African true spider mite; oriental true spider mite; small clawed mites in grasslands; citrus rust mite; apple rust mite; grape rust mite; citrus rue rust mite; polyphagous tarsoneme; cinnabarinus spider mite; Kanzawa's spider mite; Tetranychus species; and two-spotted spider mite.

[0429] In another embodiment, the compounds of formula (I) may be particularly useful for controlling one or more of: Citrus Gall Mite; Pitt's Needle Gall Mite; Purple-Palcipedulous Mite; Brevipalpus spp.; Eriophyes piri; Grape Gall Mite; African True Spider Mite; Oriental True Spider Mite; Small Clawed Mite; Apple Panonychus; Grape Rust Mite; Citrus Rust Mite; Lateral Polyphagous Tarsoneme; Cinnabarinus Tetranychus; Kanzawa's Tetranychus; Tetranychus spp.; and Two-spotted Tetranychus.

[0430] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques so as to enable them to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0431] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, e.g., insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), e.g., Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, e.g., Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysteroid inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0432] In the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining different domains of those proteins (see, e.g., WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0433] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0434] Methods for producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0435] The toxins included in the transgenic plants render the plants tolerant to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0436] Transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are known and some of them are commercially available. Examples of such plants are: (Zea mays variety expressing Cry1Ab toxin); YieldGard (maize variety expressing Cry3Bb1 toxin); YieldGard (Zea mays varieties expressing Cry1Ab and Cry3Bb1 toxins); (Zea mays variety expressing Cry9C toxin); Herculex (a maize variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate-ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0437] Further examples of such genetically modified crops are:

[0438] 1. Bt11 maize, from Syngenta Seeds SAS, 27 Chemin de l'Hobit, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate-ammonium.

[0439] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize is resistant to attack by the European corn borer (Ostrinia nubilalis and Sesamia inermis) by transgenic expression of the toxin Cry1Ab. Bt176 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate-ammonium.

[0440] 3. MIR604 maize, from Syngenta Seeds, 27 Rue de Hobbit, F-31790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant is rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055, modified by insertion of a cathepsin-G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0441] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0442] 5. IPC 531 cotton, from Monsanto Europe SA, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0443] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate.

[0444] 7. NK603×MON 810 maize, from Monsanto Europe, 270-272 Boulevard Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventionally bred hybrid maize variety, constructed by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, conferring herbicide tolerance. (contains glyphosate), and also the Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0445] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.

[0446] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology so that they can synthesize selectively acting antipathogenic substances, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP 0392225). Examples of such antipathogenic substances and transgenic plants that can synthesize such antipathogenic substances are known, for example, from EP 0392225, WO 95 / 33818, and EP 0353191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

[0447] Crops can also be modified to enhance resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0448] Crops also include those with enhanced resistance to nematodes, such as Heterodera glycines.

[0449] Crops with tolerance to abiotic stress include those with enhanced tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.

[0450] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP 0392225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors that are involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0451] Further areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0452] The present invention provides a compound of the first aspect for use in therapy. The present invention provides a compound of the first aspect for use in controlling parasites in or on an animal. The present invention further provides a compound of the first aspect for use in controlling parasites on the body of an animal. The present invention further provides a compound of the first aspect for use in preventing and / or treating a disease transmitted by parasites on the body. According to this particular aspect of the present invention, the use may not include a method of treating the human or animal body by surgery or therapy.

[0453] The present invention provides the use of the compound of the first aspect for the manufacture of a medicament for controlling parasites in or on the body of an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a medicament for controlling parasites on the body of an animal. The present invention further provides the use of the compound of the first aspect for the manufacture of a medicament for preventing and / or treating diseases transmitted by parasites on the body.

[0454] The present invention provides a use of the compound of the first aspect in controlling parasites in or on the body of an animal. The present invention further provides a use of the compound of the first aspect in controlling parasites on the body of an animal.

[0455] When used in the context of parasites in or on animals, the term "control" means reducing the number of pests or parasites, eliminating pests or parasites and / or preventing further infestation by pests or parasites.

[0456] When used in the context of parasites in or on animals, the term "treat" means to inhibit, slow, halt or reverse the progression or severity of existing symptoms or disease.

[0457] The term "prevent" when used in the context of parasites in or on animals means avoiding the development of symptoms or disease in the animal.

[0458] When used in the context of parasites in or on animals, the term "animal" may refer to both mammals and non-mammals, such as birds or fish. In the case of a mammal, it can be a human or a non-human mammal. Non-human mammals include, but are not limited to, livestock animals and pets. Livestock animals include, but are not limited to, cattle, camels, pigs, sheep, goats, and horses. Pets include, but are not limited to, dogs, cats, and rabbits.

[0459] As used herein, the term "parasite" refers to an unwanted organism that lives in or on a host animal and benefits by obtaining nutrients at the host animal's expense. An "endoparasite" is a parasite that lives inside the host animal. An "ectoparasite" is a parasite that lives on the host animal's body. Ectoparasites include, but are not limited to, ticks, insects, and crustaceans (e.g., sea lice). The subclass Acarina (or Acari) includes ticks and mites. Ticks include, but are not limited to, members of the genus Rhipicaphalus, such as Rhipicaphalus microplus (Boophilus microplus) and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the genera: Dermestes, such as Dermestes calves; Psoralea, such as Psoralea goatii; Cheyletus; Dermatophagia; for example, Dermanyssus gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcophagia, such as Sarcophagia scabiei; and Psoralea. Insects include, but are not limited to, members of the orders Siphonaptera, Diptera, Trichoderma, Lepidoptera, Coleoptera, and Homoptera. Members of Siphonaptera include, but are not limited to, Ctenocephatides cati and Ctenocephatides canis. Members of Diptera include, but are not limited to, species of the genus Musca; skin flies, such as horse flies and sheep flies; biting flies; gadflies, such as Tabunus species and Tabunus species; black horn flies, such as Haematobia; Stomoxys; Lucilia; midges; and mosquitoes. Members of the order Trichoderma include, but are not limited to, blood-sucking lice and chewing lice, for example, wool lice (Bovicola Ovis) and cattle feather lice.

[0460] The term "effective amount," when used in the context of parasites in or on an animal, refers to an amount or dosage of a compound of the invention, or a salt thereof, which, when administered to an animal in a single dose or multiple doses, provides the desired effect in or on the animal. An effective amount can be readily determined by the attending diagnostician (being one skilled in the art) by using known techniques and by observing results obtained in similar circumstances. In determining an effective amount, the attending diagnostician considers a number of factors, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or condition involved; the extent or severity of the disease or condition; the individual's response; the specific compound to be administered; the mode of administration; the bioavailability characteristics of the administered formulation; the dosage regimen selected; the use of concomitant medications; and other relevant circumstances.

[0461] The compounds of the present invention can be given to animals by any route with the desired effect, including but not limited to topical, oral, parenteral and subcutaneous. Topical administration is preferred. Preparations suitable for topical administration include, for example, solutions, emulsions and suspensions, and can be poured, dotted, sprayed, sprayed, or immersed in the form of a spray race. In an alternative, the compounds of the present invention can be given by ear tags or collars.

[0462] Salt forms of the compounds of the present invention include both pharmaceutically acceptable salts and veterinarily acceptable salts, which may be different from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and common methods for preparing them are well known in the art. See, for example, Gould, PL, "Salt selection for basic drugs", International Journal of Pharmaceutics, 33:201-217 (1986); Bastin, RJ et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4:427-435 (2000); and Berge, SM et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66:1-19, (1977). It will be appreciated by those skilled in the art that the compound of the present invention easily changes into salt using technology and conditions known to those of ordinary skill in the art, and can be used as salt (such as hydrochloride) to separate.In addition, it will be appreciated by those skilled in the art that the compound of the present invention easily changes into corresponding free alkali, and can be used as corresponding free alkali to separate from corresponding salt.

[0463] The present invention may also provide methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their locus, or a surface or substrate by painting, rolling, spraying, coating, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such compositions to substrates such as nonwoven or fabric materials in the form of (or that can be used in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0464] In one embodiment, the method for controlling this type of harmful organism comprises applying the composition of the present invention of pesticidal effective amount to target harmful organism, their place or surface or substrate, so that on this surface or substrate, effective retained pesticidal activity is provided.This application can be carried out by brushing, rolling, spraying, coating or dipping pesticidal composition of the present invention.By way of example, the IRS application of surface (such as wall, ceiling or floor surface) is considered by the method of the present invention, so that effective retained pesticidal activity is provided on this surface.In another embodiment, it is considered to use this type of composition for the residual control of the harmful organism on substrate, and this substrate is as the fabric material in the form of netting, covering, bedding, curtain and tent (or can be used in the manufacture of these articles).

[0465] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers (such as cotton, raffia, jute, flax, sisal, burlap or wool) or synthetic fibers (such as polyamide, polyester, polypropylene, polyacrylonitrile, etc.). Polyester is particularly suitable. Methods for treating textiles are known, for example, WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0466] A further area of use of the compositions according to the invention may be the field of tree injection / trunk treatment for all ornamental trees as well as all kinds of fruit and nut trees.

[0467] In the field of tree injection / trunk treatment, the compounds according to the invention may be particularly suitable for combating wood-boring insects from the orders Lepidoptera and from the orders Coleoptera mentioned above, in particular against the wood-boring insects listed in the following Tables A and B:

[0468] Table A. Examples of economically important exotic wood-boring insects.

[0469]

[0470] Table B. Examples of economically important native wood-boring insects.

[0471]

[0472]

[0473]

[0474]

[0475] The present invention can also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, ticks, cicadas, southern wheat stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0476] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., the marked beetle, C. lurida), Rhizotrogus spp. (e.g., the European beetle, R. majalis), Cotinus spp. (e.g., the Green June beetle, C. nitida), Popillia spp. (e.g., the Japanese beetle, P. japonica), Phyllophaga spp. (e.g., the May / June beetle), Ataenius spp. (e.g., the Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g., the Asiatic garden beetle, A. septempunctata), beetle, M. castanea, and Tomarus genera), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0477] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Spodoptera frugiperda), cutworms, weevils (Species of the genus Cryptorhynchus, such as S. venatus verstitus and S. parvulus), and grass borers (such as species of the genus Herpetogramma and the tropical grass borer, Herpetogramma phaeopteralis).

[0478] The present invention can also be used to control insect pests in turfgrasses that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0479] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.

[0480] In the hygiene field, the composition according to the invention can effectively combat surface parasites such as hard ticks, soft ticks, scabies mites, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0481] Examples of such parasites are:

[0482] From the order of the Pediculus: Haemaphysalis spp., Linognathus spp., Pediculus hominis spp., and Phtirus spp., Phitirus spp.

[0483] From the order Trichophagus: Felicola species, Brachypelago species, Ducklingia species, Cattlelicia species, Werneckiella species, Lepikentron species, Cattlelicia species, Trichopelago species and Felicola species (Felicola spp.).

[0484] From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp. spp.), Musca spp., Hydrotaea spp., Biting flies spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. spp.) and Melophagus spp.

[0485] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.

[0486] From the order of the Heteropterida, for example, Cimex spp., Triatomine spp., Triatomine spp., Panstrongylus spp.

[0487] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0488] From the subclass Acaria (family Acarida) and the orders Meta-stigmata and Meso-stigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyommas spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.

[0489] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcooptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0490] The compositions according to the invention can also be suitable for protecting materials such as wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction materials from infestation by insects.

[0491] The compositions according to the invention can be used, for example, to combat the following pests: beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinuspecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale), Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec., and Dinoderus minutus, as well as Hymenoptera, such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, and Urocerus augur, and termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes spp. indicola), Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis and Coptotermes formosanus, as well as borers such as Silverfish (Lepisma saccharina).

[0492] The compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of the compounds presented in Tables A1 to A2, or the compounds listed in Table P (below), or salts thereof are particularly suitable for controlling one or more pests selected from the group consisting of: Spodoptera species, Spodoptera species, Heliothis species, Lepidoptera species, Tuta species, Plutella xylostella species, Gnaphalidae species, Gnaphalidae species, Gnaphalidae species, Elasmopalpus species, Dalbulus species, Sternechus species, Striped flea beetle species, Scarabaeidae species, White grain borer species, Grain borer species, Leaf roller species, Tetradactylus species, Panonychus species, Yellowtail moth species. Acarina species, Psoralea ... species, species of the genus Arcus, species of the genus American stink bug, species of the genus Wall stink bug, species of the genus Green stink bug, species of Dichelops, species of the genus Lygus, species of the genus Rice-margin stink bug, species of the genus Flat shield stink bug, species of the genus Brown-winged stink bug, species of the genus Thrips, species of the genus Hardythrips, species of the genus Flower Thrips, species of the genus Flower Weevil, species of Melingethes, species of the genus Striped Flea Beetle, species of the genus Leaf Beetle, species of the genus Whitefly, species of the genus Whitefly, species of the genus Aphid and species of the genus Tuberculosis.

[0493] In preferred embodiments of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or a compound listed in Table P (below)") controls one or more pests selected from the genera: Spodoptera species, Heliothis species, Heliothis species, Cynocephalus species, Tuta species, Plutella species, Gnaphalidae species, Gnaphalidae species, Gnaphalidae species, Gnaphalidae species, Elasmopalpus species, Dalbulus species, Sternechus species, Striped flea beetle species, Acanthophaga species, White grain borer species, Graminus species, Leaf roller species, Tetradactylus species, Panonychus species, Tea yellow mite species, Coriolus species, Psoralea species, Short-palped mite species, Microclaw species, Dermatophagoides species, Brown planthopper species, White-backed planthopper species, Gray planthopper species, Blacktail leafhopper species, Leaf beetle species, Click beetle species, Hypnoidus species, Limonius species, Comb claw click beetle species, Broad chest click beetle species, Ground fly species, Amph imallon species, Arc beetle species, American stink bug species, wall stink bug species, green stink bug species, Dichelops species, Lygus species, Rice-margin stink bug species, Flat shield stink bug species, Brown-winged stink bug species, Thrips species, Hard Thrips species, Flower Thrips species, Flower Weevil species, Melingethes species, Striped Flea Beetle species, Leaf Beetle species, Whitefly species, Whitefly species, Aphid species and Tuberculosis species.

[0494] The compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of the compounds presented in Tables A1 to A2, or the compounds listed in Table P (below), or salts thereof are particularly suitable for controlling one or more pests selected from the group consisting of: Spodoptera species (e.g., Spodoptera frugiperda, Spodoptera littoralis), Helicoverpa armigera, Heliothis virescens, Aglaia oleracea, Tomato leafminer, Plutella xylostella, Codling moth, Cydia pomonella species, Species of the genus Tortricidae, bean borer, soybean silver-striped moth, small cutworm, South American corn seedling borer (Elasmopalpuslignosellus), corn yellow-winged leafhopper, species of the genus Flea Beetle, Japanese beetle, yellow stem borer, striped stem borer, rice leaf roller (Cnaphalocrosismedinalis), two-spotted spider mite, apple mites, polyphagous tarsoneme mite, citrus rust mite, species of the genus Brevipalpus, tomato spiny gall mite, brown planthopper, white-backed planthopper (Sogatella frucifera), Laodelphax striatellus, blacktail leafhopper species, corn rootworm (Diabrotica vigifera), snap beetle species, Hypnoidus bicolor, grey-headed snap beetle (Limonius canus), cabbage ground beetle, Japanese beetle, hero American stink bug (Euschistus heros), broom shield bug (Piezodorus lituratus), green rice stink bug, green-bellied stink bug (Dichelops furcatus), Lygus species, grass spider stink bug (Leptocorisa acuta), brown stink bug, tobacco thrips, tea yellow thrips, western flower thrips, cotton boll weevil, rapeseed beetle, striped flea beetle species, potato beetle, Bemisia tabaci, greenhouse whitefly, cotton aphid, and green peach aphid.

[0495] In preferred embodiments of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or a compound listed in Table P (below)") controls one or more pests selected from the following genera: Spodoptera species (e.g., Spodoptera frugiperda, Spodoptera littoralis) + TX, Helicoverpa armigera + TX, Heliothis virescens + TX, Eurycoma lutea + TX, Tomato leafminer + TX, Diamondback moth + TX, Codling moth + TX, Cydia pomonella + TX, Cydia spp. Species of the genus + TX, species of the genus Tortoise + TX, bean borer + TX, soybean silver-striped moth + TX, small blackworm + TX, South American corn seedling borer + TX, corn yellow-winged leafhopper + TX, species of the genus Flea Beetle + TX, Japanese beetle + TX, yellow stem borer + TX, striped stem borer + TX, rice leaf roller + TX, two-spotted spider mite + TX, apple mites + TX, polyphagous tarsonemes + TX, citrus rust mite + TX, species of the genus Brevipalpus + TX, tomato spiny gall mite + TX, brown planthopper + TX, white-backed planthopper + TX, gray planthopper + TX, species of the genus Blacktail + TX, corn rootworm + TX, species of the genus Hypnoidus + TX, bicolor+TX, gray-headed snapper+TX, cabbage ground beetle+TX, Japanese beetle+TX, hero American stink bug+TX, broom shield bug+TX, green rice stink bug+TX, green-bellied stink bug+TX, Lygus species+TX, grass spider stink bug+TX, brown-winged stink bug+TX, tobacco thrips+TX, tea yellow thrips+TX, western flower thrips+TX, cotton boll weevil+TX, rapeseed beetle+TX, striped flea beetle species+TX, potato beetle+TX, Bemisia tabaci+TX, greenhouse whitefly+TX, cotton aphid+TX and green peach aphid+TX.

[0496] The compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of the compounds presented in Tables A1 to A2, or the compounds listed in Table P (below), or salts thereof are particularly suitable for controlling the listed pests in the crops listed in the following table.

[0497]

[0498]

[0499]

[0500]

[0501] #like https: / / www.ams.usda.gov / services / grants / scbgp / specialty-crop Defined in

[0502] In preferred embodiments of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from compounds of Formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or a compound listed in Table P (below)") controls one or more of the following: Spodoptera species (e.g., Spodoptera frugiperda, Spodoptera littoralis), cotton bollworm, tobacco budworm, eggplant yellow moth, tomato leafminer, diamondback moth, codling moth, flower tortoise species, tortoise species, bean borer, soybean silver moth, black cutworm, South American corn borer, corn leafhopper, striped flea beetle species, Japanese beetle, yellow stem borer, striped stem borer, rice leaf roller, brown planthopper, white-backed planthopper, gray planthopper , Blacktail leafhopper species, Bemisia tabaci, greenhouse whitefly, cotton aphid and green peach aphid; such as Spodoptera species (e.g., fall armyworm, sea armyworm)+TX, cotton bollworm+TX, tobacco budworm+TX, eggplant yellow spot moth+TX, tomato leafminer+TX, diamondback moth+TX, codling moth+TX, flower-winged tortoise species+TX, tortoise species+TX, bean borer+TX, soybean silver-striped armyworm+TX, small blackworm+TX, South American corn seedling borer+TX, corn yellow-winged leafhopper+TX, striped flea beetle species+TX, Japanese beetle+TX, yellow stem borer+TX, striped stem borer+TX, rice leaf roller+TX, brown planthopper+TX, whiteback planthopper+TX, gray planthopper+TX, Blacktail leafhopper species+TX, Bemisia tabaci+TX, greenhouse whitefly+TX, cotton aphid+TX and green peach aphid+TX.

[0503] The compounds according to the present invention may have any number of benefits, including, among others, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (against non-target organisms above and below ground, such as fish, birds, and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been unexpectedly discovered that certain compounds of formula (I) can exhibit favorable safety profiles against non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumble bees. Most particularly, against the Italian honey bee (Apis mellifera).

[0504] By adding other insecticidal, acaricidal and / or fungicidal active ingredients, the activity of the compositions according to the invention can be significantly broadened and adapted to prevailing conditions. Mixtures of compounds of formula (I) with other insecticidal, acaricidal and / or fungicidal active ingredients can also have further surprising advantages, which can also be described in a broader sense as synergistic activities. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at different stages of their development, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).

[0505] Suitable active ingredients for addition are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0506] The following combinations of a compound of formula (I) with another active substance are preferred (wherein the abbreviation "TX" means "a compound selected from the group consisting of compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or a compound listed in Table P (below)"):

[0507] An adjuvant, which is selected from the following substance group: petroleum (alias) (628) + TX; avermectin + TX, acetamiprid + TX, acetamiprid + TX, flumethrin + TX, acynonapyr + TX, bifenthrin + TX, afoxolaner + TX, cotton bell carbendazim + TX, allethrin + TX, α-cypermethrin + TX, alpha-cypermethrin + TX, sulfamethoxazole + TX, cypermethrin + TX, triazolin + TX, sulfamethoxazole + TX, benzylpyrimoxane + TX, benzpyrimoxane + TX, beta-cypermethrin + TX, benzylpyrimoxane + TX, beta-cypermethrin + TX, benzylpyrimoxane + TX , bifenthrin + TX, binacarb + TX, bio-allethrin + TX, S-bio-allethrin + TX, bio-resmethrin + TX, bistrifluan + TX, fluazifop + TX, broflanilide + TX, brofluthrin + TX, bromophos-ethyl + TX, buprofezin + TX, butacarb + TX, cadusafos + TX, carbaryl + TX, butacarb + TX, batan + TX, CAS No.: 1594624-87-9+TX, CAS No.: 1922957-47-8+TX, CAS No.: 1255091-74-7+TX, CAS No.: 1365070-72-9+TX, CAS No.: 144568 3-71-5+TX, CAS No.: 1445684-82-1+TX, CAS No.: 1594626-19-3+TX, CAS No.: 1594637-65-6+TX, CAS No.: 1632218-00-8+TX, CAS No.: 1808115-49-2+TX, CAS No.: 1922957-46-7+TX, CAS No.: 1922957-48-9+TX, CAS No.: 1956329-03-5+TX, CAS No.: 1990457-52-7+TX, CAS No.: 1990457-55-0+TX, CAS No.: 1990457-57-2+TX, CAS No.: 1990457-66-3+TX、CAS No.:1990457-77-6+TX、CAS No.:1990457-85-6+TX、CAS No.:2032403-97-5+TX、CAS No.:2044701-44-0+TX、CAS No.:2095470-94-1+TX、CAS No.:2128706-04-5+TX、CAS No.:2128706-05-6+TX、CAS No.:2133042-31-4+TX、CAS No.:2133042-44-9+TX、CAS No.:2171099-09-3+TX、CAS No.:2220132-55-6+TX、CAS No.: 2396747-83-2+TX, CAS No.: 2408220-91-5+TX, CAS No.: 2408220-94-8+TX, CAS No.: 2415706-16-8+TX, CAS No.: 2615135-05-0+TX, CAS No.: 2719848-60-7+TX, CAS No.: RNA (recombinant double-stranded interference GS2 specific to potato beetles)+TX, chlorantraniliprole+TX, chlordane+TX, chlorfenapyr+TX, chlorpromazine+TX, chlorpropamide+TX, chlorfenapyr+TX, chlorfenapyr+TX, chlorfenapyr+TX, chlorfenapyr+TX, clenpyrine+TX, cloethocarb+TX, clothianidin+TX, 2-chlorophenyl N-methylaminoformamide Acid ester (CPMC) + TX, benzonitrile + TX, bromocyanamide + TX, cyclobromocyanamide + TX, cyclobutrifluram + TX, pyrethroid + TX, cycloxanil + TX, cytoxanil + TX, cyetpyrafen (or etpyrafen) + TX, cyflumetofen + TX, cyhalodiamide + TX, trihalothrin + TX, cypermethrin + TX, cyproflanilide + TX, cyromazine + TX, deltamethrin + TX, cyfluthrin + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, cyproflanilide + TX, cyromazine + TX, deltamethrin + TX, chlorfenapyr + TX, Phosphate + TX, dibrom + TX, dicloromezotiaz + TX, fluazifop + TX, diflubenzuron + TX, dimpropyridaz + TX, dimethoate + TX, dinotefuran + TX, vesiculophos + TX, emamectin (or emamectin benzoate) + TX, d-epsilon + TX, epsilon-momfluorothrin + TX, epsilon-metofluthrin + TX, esfenvalerate + TX, ethion + TX, ethiprole + TX, ethofenprox + TX, etoxazole + TX, fenamiphos + TX, fenazaquin + TX, pentothrin Ester + TX, fenmezoditiaz + TX, fenitrothion + TX, fenbucarb + TX, fenthiocarb + TX, fenoxycarb + TX, cypermethrin + TX, fenpyroximate + TX, fenthion + TX, fenthion + TX, yeselin + TX, cypermethrin + TX, fipronil + TX, flometoquin + TX, flonicamid + TX, pyrimidifen + TX, fluazaindolizine + TX, flupyrimid + TX, flufenoxam + TX, fluchlordiniliprole + TX,Flucitrinate + TX, flufenoxuron + TX, flucythrin + TX, fluthiazolin + TX, flumethrin + TX, flumethrin + TX, flubendiamide + TX, flufenoxamide + TX, flupyroxystrobin + TX, flupyrimin + TX, fluralaner + TX, fluvalinate + TX, fluxametamide + TX, thiazolin + TX, γ-cyhalothrin + TX, pyramid + TX, chlorfenapyr + TX, benzyl methoxysulf + TX, heptafluthrin + TX, hexathiazolin + TX, hydrazone + TX, imicyafos + TX, imidacloprid + TX, imiprodinil + TX, indazapyroxamet + TX, indoxacarb + TX, iodomethane + TX, iprodione + TX, isocycloseram + TX, isoflualanam (CAS No.: 2892524-05-7) + TX, isosulfanthate + TX, ivermectin + TX, κ-bifenthrin + TX, κ-tefluthrin + TX, λ-cyhalothrin + TX, ledprona + TX, lepidomycin + TX, lotilaner + TX, chlorfenuron + TX, metaflumizone + TX, metaldehyde + TX, methamphetamine + TX, methomyl + TX, methoxyfenozide + TX, metofluthrin + TX, methicillin + TX, cypermethrin + TX, cypermethrin + TX, momfluorothrin + TX, cypermethrin + TX, nicofluprole + TX; nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosulfyl + TX, Parathion-ethyl + TX, permethrin + TX, phenothrin + TX, phosphamidon + TX, thiocyclam + TX, piperonyl butoxide + TX, polyflubenzuron + TX, pirimiphos-ethyl + TX, pirimiphos-methyl + TX, polyhedrosis virus + TX, prallethrin + TX, profenofos + TX, profluthrin + TX, propargyl + TX, amitriptyline + TX, propoxur + TX, prothiophos + TX, protrifenbute + TX, pyflubumide + TX, pymetrozine + TX, pyrafluprole + TX,Pyridabenz + TX, pyridalyl + TX, pyrifluquinazon + TX, pyriminostrobin + TX, pyraclostrobin + TX, pyrimethoxam + TX, pyriproxyfen + TX, resmethrin + TX, sarolaner + TX, selamectin + TX, flutoxin + TX, spinosad + TX, spinosad + TX, spirobudifen + TX; spirodiclofen + TX, spiromesifen + TX, spiropidion + TX, spiroworm Ethyl ester + TX, spidoxamat + TX, sulfiflumin (CAS No.: 2377084-09-6) + TX, sulfenthrin + TX, tebufenoxam + TX, tebufenpyrad + TX, butyl pyrimidin (tebupirimiphos) + TX, tefluthrin + TX, tebufenoxam + TX, tetrachlorvinphos + TX, tetrachlorvinphos + TX, tetrachlorvinphos + TX, tetrachlorvinphos + TX, tetrachlorvinphos + TX, cypermethrin + TX, flucythrin + TX, cypermethrin + TX, flubendiamide + TX, θ-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, cypermethrin +TX, thiodicarb +TX, long-lasting carb +TX, methyl benzylphos +TX, sulfamyl propane +TX, tigolaner +TX, tiorantraniliprole +TX; tioxazafen +TX, tolfenpyrad +TX, toxaphene +TX, tralomethrin +TX, transfluthrin +TX, triazophos +TX, trichlorfon +TX, trichlorfon +TX, trifluenfuronate +TX, triflume TX, tyclopyrazoflor + TX, ζ-cypermethrin + TX, seaweed extract and fermentation products derived from sugar acyl + TX, seaweed extract and fermentation products derived from sugar acyl (containing urea + TX, amino acids + TX, potassium and molybdenum, and EDTA-chelated manganese) + TX, seaweed extract and fermented plant products + TX, seaweed extract and fermented plant products (containing plant hormones + TX, vitamins + TX, EDTA-chelated copper + TX, zinc + TX, and iron + TX), azadirachtin + TX, Bacillus ayuzawa aizawai) + TX, Bacillus chitinosporus AQ746 (NRRL Accession No. B-21 618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX,Bacillus pumilus (NRRL Accession No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus species AQ178 (ATCC Accession No. 53522) + TX, Bacillus species AQ175 (ATCC Accession No. 55608) + TX, Bacillus species AQ177 (ATCC Accession No. 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) + TX, Bacillus subtilis AQ30002 (NRRL Accession No. Accession No. B-50421) + TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455) + TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) + TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL Accession No. B-21530) + TX, Bacillus thuringiensis subspec. Kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Helicoverpa tatarinowii nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Helicoverpa australis nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodoralbus 620 (NRRL accession number 30547)+TX, Muscodor roseus A3-5 (NRRL accession number 30548)+TX, Neem-based products+TX, Paecilomyces fumosorum+TX, Paecilomyces lilacinus+TX, Pasteuria szabalensis+TX, Pasteuria penetrantis+TX, Pasteuria mycoides+TX, Pasteuria soreiroides thornei)+TX, Pasteurella+TX, p-cymene+TX, Plutella xylostella granulovirus+TX, Plutella xylostella nuclear polyhedrosis virus+TX, polyhedrosis virus+TX, pyrethrum+TX, QRD 420 (terpenoid blend)+TX, QRD 452 (terpenoid blend)+TX, QRD 460 (terpenoid blend)+TX, Quillaja saponaria+TX, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663)+TX, Spodoptera frugiperda nuclear polyhedrosis virus+TX, Streptomyces flavos (NRRL Accession No. 30232)+TX, Streptomyces sp. (NRRL Accession No. B-30145)+TX, terpenoid blend+TX, and Verticillium sp.+TX;

[0508] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) + TX, and triphenyltin hydroxide (IUPAC name) (347) + TX;

[0509] Anthelmintics selected from the group consisting of: avermectin (1) + TX, clofosinate (1011) + TX, cyclobutrifluram + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycinoxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX and thiophanate (1435) + TX;

[0510] Avicides selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) + TX and strychnine (745) + TX;

[0511] Bactericide selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercaptophenone ( Synonyms) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorpheniramine (766) + TX, and thimerosal (synonyms) [CCN] + TX;

[0512] A biological agent selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Agrobacterium radiobacterium (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, NPV of celery budworm (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, NPV of lucerne budworm (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus Neide)(scientific name)(49)+TX、Bacillus thuringiensis Berliner)(scientific name)(51)+TX、Bacillus thuringiensis subsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensis subsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensis subsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensis subsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Eretmocerus sibirica (scientific name) (293) + TX, Eretmocerus sibirica (alias) eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Spodoptera exigua NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var. anisopliae)(scientific name)(523)+TX, Neodiprion sertifer NPV and Neodiprion sertifer (Neodiprion sertifer) NPV.lecontei)NPV (alias) (575) + TX, Paecilomyces species (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimlis (alias) (644) + TX, Spodoptera exigua multicapsidnuclear polyhedrosis virus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema glaseri (alias) (742) + TX, Steinernema riobrave) (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema scapterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) + TX, and Verticillium lecanii (alias) (848) + TX;

[0513] Soil disinfectants selected from the group consisting of iodomethane (IUPAC name) (542) + TX and bromomethane (537) + TX;

[0514] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bisazir (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methicillin [CCN] + TX, methylthiothiazide ... hiotepa) [CCN] + TX, methylapholate [CCN] + TX, morzid [CCN] + TX, penfluron (other name) [CCN] + TX, tepa [CCN] + TX, thiohempa (other name) [CCN] + TX, thiohexamethylenetepa (other name) [CCN] + TX, trotamide (other name) [CCN] + TX, and urethaneimide (other name) [CCN] + TX;

[0515] An insect pheromone selected from the group consisting of (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadec-11-en- Aldehyde (IUPAC name) (436) + TX, (Z)-hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) + TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) + TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) + TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784 )+TX、(7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283)+TX、(9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780)+TX、(9Z,12E)-tetradec-9,12-dien-1-yl acetate (IUPAC name) (781)+TX、14-methyloctadec-1-ene (IUPAC name) (545)+TX、4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544)+TX、alpha-multistriat in)(alias)[CCN]+TX、brevicomin)(alias)[CCN]+TX、codlelure)(alias)[CCN]+TX、codlemone(alias)(167)+TX、cuelure(alias)(179)+TX、disparlure(277)+TX、1-dodecyl acetate(IUPAC name)(286)+TX、1-dodecyl acetate(IUPAC name)(287)+TX、12-dodecyl acetate10-dien-1-yl acetate (IUPAC name) (284) + TX, dominicalure (alias) [CCN] + TX, 4-methyloctanoic acid ethyl ester (IUPAC name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle aggregation pheromone (frontalin) (alias) [CCN] + TX, 1:1 mixture of (Z,E) and (Z,Z) isomers of (hexadec-7,11-dien-1-yl acetate) (420) + TX, grandlure (421) + TX, grandlure I (alternative name) (421) + TX, grandlure II (alternative name) (421) + TX, grandlure III (alternative name) (421) + TX, grandlure IV (alternative name) (421) + TX, hexalure [CCN] + TX, ipsdieno l)(alias) [CCN] + TX, ipsenol (alias) [CCN] + TX, japonilure (alias) (481) + TX, lineatin (alias) [CCN] + TX, litlure (alias) [CCN] + TX, looplure (alias) [CCN] + TX, medlure [CCN] + TX, megatomoic acid acid)(alias)[CCN]+TX、Muscalure(alias)(540)+TX、Muscalure(563)+TX、Octadec-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、Octadec-3,13-dien-1-yl acetate(IUPAC name)(589)+TX、Orfralure(alias)[CCN]+TX、Oryctalure(alias)(317)+TX、Ostromone(alias)[CCN]+TX、Siglu re)[CCN]+TX, banana bulb weevil attractant (sordidin) (alternative name) (736)+TX, sulcatol (alternative name) [CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (alternative name) (839)+TX, Mediterranean fruit fly attractant B1 (alternative name) (839)+TX, Mediterranean fruit fly attractant B2 (alternative name) (839)+TX, Mediterranean fruit fly attractant C (alternative name) (839) and trunc-call (alternative name) [CCN]+TX;

[0516] Insect repellents selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] + TX, and picaridin [CCN] + TX;

[0517] Molluscicide selected from the group consisting of: di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, chloranil (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-ethanolamine (576) + TX, pentachlorophenol (6 23)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347)+TX, triphenyltin hydroxide (IUPAC name) (347)+TX and pyriprole [394730-71-3]+TX;

[0518] A nematicide selected from the group consisting of: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ 60541 (compound code) + TX, benclothiaz[CCN] + TX, benomyl (62) + TX, butylpyridaben (alias) + TX, chlorpyrifos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbofuran (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, Xianwei (999) + TX, cyclobutaflutol + TX, cytokinin (alias) (210) + TX, dazomethane (216) + TX, DBCP (1045) + TX, DCIP (218) + TX, diamidafos (1044) + TX, dimethoate (1051) + TX, dicliphos (alias) + TX, dimethoate (262) + TX, doramectin (alias) [ CCN]+TX, emamectin (291)+TX, emamectin benzoate (291)+TX, eprinomectin (alias) [CCN]+TX, ethoprophos (312)+TX, dibromoethane (316)+TX, fenamiphos (326)+TX, fenpyrad (alias)+TX, fensulfuron (1158)+TX, thiazophos (408)+TX, butasulfophos (1196)+TX, furfural Aldehyde (alias) [CCN] + TX, GY-81 (research code) (423) + TX, cypermethrin [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidophos (1230) + TX, chlorfenapyr (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl azomethasone (1258) + TX,Metamex (519) + TX, Metamex potassium salt (alias) (519) + TX, Metamex sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, Milbemycin oxime (alias) [CCN] + TX, Moxidectin (alias) [CCN] + TX, Myrothecium verrucaria composition (alias) (565) + TX, NC-184 (compound code) + TX, Oxamyl (602) + TX, Phorate (636) + TX, Phosphamidon (639) + TX, Phosphamidon [CCN] + TX, Clendacarb (alias) + TX, Selamectin (alias) [CCN] N]+TX, spinosad (737)+TX, terbufos (alias)+TX, terbufos (773)+TX, tetrachlorothiophene (IUPAC / Chemical Abstracts name) (1422)+TX, thiafenox (alias)+TX, fenamiphos (1434)+TX, triazophos (820)+TX, triazuron (alias)+TX, dimethylol [CCN]+TX, YI-5302 (compound code)+TX and zeatin (alias) (210)+TX, fluensulfone [318290-98-1]+TX and fluopyram+TX;

[0519] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] + TX and nitrapyrin (580) + TX;

[0520] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) + TX, and Reynoutria sachalinensis extract (alias) (720) + TX;

[0521] Rodenticides consisting of the following substance groups: 2-isovalerylindan-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoquinol (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisulfamethoxazole (912) + TX, brodifacoum (89) + TX, bromadiolone (including α-Bromadiolone) + TX, Bromodiolamine (92) + TX, Calcium Cyanide (444) + TX, Chloralose (127) + TX, Chlorodiolone (140) + TX, Cholecalciferol (alias) (850) + TX, Chlorodiol (1004) + TX, Cholecalciferol (1005) + TX, Cytodextrin (175) + TX, Cytodextrin (1009) + TX, Cytodextrin (246) + TX, Cytodextrin (249) + TX, Cytodextrin (273) + TX, Calcifedol (301) + TX, Fluorodiol TX, fluoroacetamide (379) + TX, fluridine (1183) + TX, fluridine hydrochloride (1183) + TX, γ-HCH (430) + TX, HCH (430) + TX, hydrogen cyanide (444) + TX, iodomethane (IUPAC name) (542) + TX, lindane (430) + TX, magnesium phosphide (IUPAC name) (640) + TX, methyl bromide (537) + TX, thiamethoxam (1318) + TX, thiamethoxam (1336) + TX )+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, warfarin (1341)+TX, potassium arsenite [CCN]+TX, warfarin (1371)+TX, scilla glycoside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851)+TX, and zinc phosphide (640)+TX;

[0522] Synergist, which is selected from the group consisting of: 2-(2-butoxyethoxy)-ethyl piperonyl ester (IUPAC name) (934) + TX; 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX; farnesol with nerolidol (alias) (324) + TX; MB-599 (research code) (498) + TX; MGK 264 (research code) (296) + TX; piperonyl butoxide (649) + TX; piprotal (1343) + TX; propyl ester (1343) + TX isomer)(1358)+TX; S421(research code)(724)+TX; sesamex(1393)+TX; sesasmolin(1394)+TX and sulfoxide(1406)+TX;

[0523] Animal repellents, which are selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salamine (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] + TX, and ziram (856) + TX;

[0524] Virucidal agents selected from the group consisting of: imipenem (alias) [CCN] + TX and ribavirin (alias) [CCN] + TX;

[0525] A wound protection agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) + TX and thiophanate-methyl (802) + TX;

[0526] Biologically active substances selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenylsulfone+TX, acetofenapyr+TX, aldisulfonyl+TX, sagofos+TX, fomanphos+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxaphos+TX, benzyl benzoate+TX, bixafenthion+TX, bromethrin+TX, bromothiophene+TX, bromophos+TX X, bromocriptine + TX, buprofezin + TX, butanone carbendazim + TX, butanone sulfonate + TX, butylpyridaben + TX, calcium polysulfide + TX, octachlorocamphene + TX, chlormethoxam + TX, trithion + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, cypermethrin + TX, chlordimeform + TX, chlordimeform hydrochloride + TX, chlorfenapyr + TX, chlorfenapyr + TX, chlorfenapyr + TX, ethyl chlorfenapyr + TX, chlorfenapyr + TX, propyl chlorfenapyr + TX, chlorfenapyr + TX, cypermethrin I + TX, chlordimeform II + TX, chlordimeform + TX, closantel + TX, coumaphos + TX, crotamiton + TX, baclofos + TX, thiophanate+TX, fruit insect phosphorus+TX, DCPM+TX, DDT+TX, tianlephos+TX, tianlephos-O+TX, tianlephos-S+TX, demeton-methyl+TX, demeton-O+TX, demeton-O-methyl+TX, demeton-S+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, demeton-S-methyl+TX, bacteriostatic+TX, dichlorvos+TX, dicliphos+TX, dichlorvos+TX, dimethoate+TX, dimethoate+TX, dimethoate+TX, dinex+TX, dinex-diclexine+TX, Diclofenac-4+TX, Diclofenac-6+TX, Orthodiclofenac+TX, Nitropentyl+TX, Nitrooctyl+TX, Nitrobutyl+TX, Dimethoate+TX, Sulfondiphenyl+TX, Disulfiram+TX, DNOC+TX, Fenoxyfen+TX, Doramectin+TX, Indoxophos+TX, Eprinomectin+TX, Ethiophos+TX, Ethiophos+TX, Antifox+TX, Fenbutatin+TX, Fenthiocarb+TX, Fenpyrad+TX, Fenpyrad+TX, Fenpyraclostrobin ... 1137+TX, fenvalerate+TX, fenvalerate hydrochloride+TX, carbendazim+TX, γ-HCH+TX, chlorpyrifos+TX, benzyl methoxyfen+TX, hexadecyl cyclopropane carboxylate+TX, isocarbophos+TX, jasmonate I+TX, jasmonate II+TX, iodonium sulfate+TX, lindane+TX, propanil+TX,Mefenacet + TX, dithiophos + TX, methylthiophene + TX, acarb + TX, methyl bromide + TX, methicillin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, dibromophos + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + TX, pentocyanamide + TX, pentocyanamide 1:1 zinc chloride complex + TX, omethoate + TX, isothiocarb + TX, sulfamethoxam + TX, pp'-DDT + TX, parathion + TX, permethrin + TX, fenthion + TX, phosalone + TX, thiophanate + TX, phosphamidon + TX, phosphamidon + TX, chlorinated turpentine + TX, acaricide + TX, proclonol + TX, cypermethrin + TX, propoxur + TX, ethidium + TX, pyrethrin + TX, pyrethrin I + TX, pyrethrin II + TX, pyrethrin + TX, pyrimethoxam + TX, pyrimithiophos + TX, quinalphos + TX, quintiofos + TX, R-1492 + TX, glyphosate + TX, rotenone + TX, octamidine + TX, clomar + TX, selamectin + TX, thiothion + TX, SSI-121 + TX, sulfluramid + TX, sulfotep + TX, sulfur + TX, fluazifop + TX, τ-fluvalinate + TX, TEPP + T X, terbucarb + TX, tetrachlorobenzene + TX, acarbicide + TX, thiafenox + TX, pyrimidine + TX, long-lasting chlorpyrifos + TX, methyl benzylphos + TX, chlorpyrifos + TX, thiamethoxam + TX, thiamethoxam + TX, triazophos + TX, chlorpyrifos + TX, triclosan + TX, triamcinol + TX, aphidoxam + TX, methyl fipronil + TX, pyrimidine + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, chlorpyrifos + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenylhydrazine Tin oxide + TX, folate + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX, 8-hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dipyrithione + TX, dodixan + TX, sodium disulfide + TX, formaldehyde + TX, mercury + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhiothione + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX,Thiabendazole+TX, Streptomycin+TX, Streptomycin sesquisulfate+TX, Chlorophyll+TX, Thimerosal+TX, GV of the cotton brown-banded tormentor+TX, Agrobacterium radiobacterium+TX, Amblyseius species+TX, Spodoptera exigua NPV+TX, Procera ceranae+TX, Aphididae short-spurred wasp+TX, Cotton aphid parasitoid wasp+TX, Aphid midge+TX, Spodoptera lucerne NPV+TX, Bacillus sphaericus+TX, Beauveria bassiana+TX, Common lacewing+TX, Cryptochilus mandshurica+TX, GV of the codling moth+TX, Siberian sibirica+TX, Pea leafminer+TX, Aphididae ensifolia+TX , Aphididae + TX, Bacteriotrophic Heterorhabditis elegans and Heterorhabditis elegans + TX, Spotted Long-legged Ladybird + TX, Scale Parasitoid Wasp + TX, Misty Bug + TX, Cabbage Lobelia NPV + TX, Yellow-stalked Jumping Lobelia + TX, Yellow-green Metarhizium + TX, Metarhizium anisopliae Microspore Var. + TX, New European Pine Sawfly NPV and New Red-headed Pine Sawfly NPV + TX, Small Flower Bug Species + TX, Fumosomolus Roseus + TX, Chilean Small Plant Mite + TX, Hairy Mosquito Nematode + TX, Small Rolled Moth Nematode + TX, Noctuid Moth Nematode + TX, Grill's Nematode + TX, Steinernema sharpiena + TX, Steinernema riobravis+TX, Steinernema nematode+TX, Steinernema species+TX, Trichogramma species+TX, Western Typhlostomus+TX, Verticillium lecanii+TX, zophosphine+TX, bis(aziridine)methylaminophosphonium sulfide (bisazir)+TX, busulfan+TX, dimetifoxine+TX, hexamethylmelamine+TX, hexamethylphosphonium+TX, methyl tibazine+TX, methylthiotibazine+TX, methylzophosphine+TX, infertile+TX, fenfluramide+TX, tibazine+TX, hexamethylphosphonium thioate+TX, thiotibazine+TX, trothamide+TX, urethaneimide+TX, (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol+TX, (E)-tridec-4-en-1-yl acetate+TX, (E)-6-methylhept-2-en-4-ol+TX, (E,Z) -Tetradec-4,10-dien-1-yl acetate + TX, (Z)-dodec-7-en-1-yl acetate + TX, (Z)-hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7 -ene-1-al+TX, (Z)-tetradec-9-en-1-ol+TX, (Z)-tetradec-9-en-1-yl acetate+TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate+TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate+TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate+TX,14-Methyloctadec-1-ene+TX, 4-methylnon-5-ol and 4-methylnon-5-one+TX, α-polystyrene+TX, western pine beetle gathering pheromone+TX, dodecadienol+TX, caldmon+TX, tardigrade+TX, epoxynonadecane+TX, dodec-8-en-1-yl acetate+TX, dodec-9-en-1-yl acetate+TX, dodec-8,10-dien-1-yl acetate+TX, dominicalure+TX, 4- Ethyl methyloctanoate + TX, eugenol + TX, southern pine beetle gathering pheromone + TX, trapene mixture + TX, trapene mixture I + TX, trapene mixture II + TX, trapene mixture III + TX, trapene mixture IV + TX, hexane attractant + TX, tooth beetle dienol + TX, eugenol + TX, scarab sex attractant + TX, trimethyldioxytricyclononane + TX, litlure + TX, cabbage looper sex attractant + TX, trapene ester + TX, megatomoic acid+TX, entophore+TX, entophore+TX, octadec-2,13-dien-1-yl acetate+TX, octadec-3,13-dien-1-yl acetate+TX, Hekangbi+TX, coconut rhinoceros beetle aggregation pheromone+TX, Feilekang+TX, entophore ring+TX, sordidin+TX, fungivorous methyl entol+TX, tetradec-11-en-1-yl acetate+TX, Mediterranean fruit fly attractant+TX, Mediterranean fruit fly attractant A +TX, Mediterranean fruit fly attractant B1+TX, Mediterranean fruit fly attractant B2+TX, Mediterranean fruit fly attractant C+TX, trunc-call+TX, 2-(octylthio)ethanol+TX, dimethoate+TX, butoxy (polypropylene glycol)+TX, dibutyl adipate+TX, dibutyl phthalate+TX, dibutyl succinate+TX, DEET+TX, mosquito repellent+TX, dimethyl phthalate+TX, ethyl hexanediol+TX, hexyl urea+ TX, mequindine + TX, methyl neodecylamide + TX, oxamate + TX, picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methylphosphonate Ester + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyl diethyl phosphate + TX, 2-imidazolidinone + TX, 2-isovaleryl indan-1,3-dione + TX,2-Methyl (prop-2-ynyl) aminophenyl methylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazol-5-yl dimethylcarbamate + TX, 4-methyl (prop-2-ynyl) amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyl dimethylcarbamate + T X, acethion + TX, acrylonitrile + TX, aldrin + TX, aloamicin + TX, chlorpyrifos + TX, α-decadin + TX, aluminum phosphide + TX, chlorpyrifos + TX, neonicotinoids + TX, ethyl methidathion + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + T X, β-cyfluthrin + TX, β-cypermethrin + TX, pentocyclam + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromophenazone + TX, bromo-DDT + TX, cypermethrin + TX, cyfluthrin + TX, temirphos + TX, butylphos + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cypermethrin hydrochloride + TX, servadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chloranisole + TX, chlorpyrifos + TX, cis-resmethrin + TX, cismethrin + TX, cypermethrin + TX, copper acetylarensite + TX, copper arsenate + TX, copper oleate + TX, cypermethrin + TX, cryolite + TX, CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-cypermethrin+TX, DAEP+TX, dazomethon+TX, demethylcarbofuran+TX, chloranil+TX, isochlorvinphos+TX, chloranil+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, thiophene+TX, tetrafluthrin+TX, demacarb+TX, pyrethrin+TX, methylchlorfenapyr+TX, difenocarb+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpropathrin+TX, vegetable phosphorus+TX, thiopyraphos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, ethiobencarb+TX, fenitrothion+TX, pyrimidine+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, chlorpyrifos+TX, butylfenthion+TX, phosphamidon+TX,Butylthion + TX, Fusalcarb + TX, Pyrethroid + TX, Biguanidine salt + TX, Biguanidine acetate + TX, Sodium tetrathiocarbonate + TX, Benzofen + TX, HCH + TX, HEOD + TX, Heptachlor + TX, Methiothion + TX, HHDN + TX, Hydrogen cyanide + TX, Quinoline + TX, IPSP + TX, Cyclofos + TX, Carbochlorin + TX, Isoaldrin + TX, Isothiophos + TX, Transplanting agent + TX, Blasticide + T X, oxazophos + TX, juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenophos + TX, pyralidon + TX, thiazophos + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphorus azide + TX, methyl azoxyphos + TX, thiamethoxam + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamifene + TX, metamifene potassium salt +TX, sodium salt of Metamex +TX, methylsulfonyl fluoride +TX, butenamidophos +TX, methoprene +TX, methylthiothrin +TX, methoxychlor +TX, methyl isothiocyanate +TX, methyl chloroform +TX, dichloromethane +TX, oxadiazine +TX, mirex +TX, napeptide +TX, naphthalene +TX, NC-170 +TX, nicotine +TX, nicotine sulfate +TX, nithiazine +TX, pronicotine +TX, O-5-dichloro-4-iodo Phenyl O-ethyl ethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-yl phosphonothioate + TX, O,O-diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphonothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious phosphine I+TX, precocious phosphine II+TX, precocious phosphine III+TX, amidothrin+TX, fluthrin+TX, fenvalerate+TX, prothiophos+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, quinalphos+TX , iodosamide + TX, resmethrin + TX, rotenone + TX, thiamethoxam + TX, ryanodine + TX, sabaveratrol + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiapronil + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulfofenol + TX, sulfofenol sodium salt + TX, sulfuryl fluoride + TX, sulfaprophos + TX, tar + TX, thiabendazole + TX,TDE+TX, butylpyrimidophos+TX, dimethophos+TX, cyclopentylthrin+TX, tetrachloroethane+TX, thiochlorvos+TX, cyclohexane+TX, cyclohexane oxalate+TX, cypermethrin+TX, cypermethrin monosodium+TX, tralomethrin+TX, permethrin+TX, triazolam+TX, isothiocarb-3+TX, chlorpyrifos+TX, cyclohexanil+TX, trifloxycarb+TX, chlorpyrifos-butyl+TX, methoprene+TX, veratridine+TX, veratridine+TX, XMC+TX, zetamethrin+TX, zinc phosphide+TX, tolfenphos+TX, chlorfluanid+TX Ethofenprox + TX, tetrafluthrin + TX, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyrimorph + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, anisiflupurin + TX, Benzylchlorothiazide + TX, cytokinin + TX, DCIP + TX, furfural + TX, isoamidophos + TX, kinetin + TX, verrucous myristic fungus composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethyl xanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, giant knotweed extract + TX, α-chlorohydrin + TX, anto + TX, barium carbonate + TX, bifenthionine + TX, brodifacoum + TX, bromadiolone + TX, brofenalidone + TX, chlorfenapyrone + TX, cholecalciferol + TX, chlorfenapyr + TX, rodenticide + TX, rodenticide naphthalene + TX, Warfarin + TX, Warfarin + TX, Thiazide + TX, Diphacin + TX, Calciferol + TX, Fludioxaline + TX, Fluacetamide + TX, Fludioxaline + TX, Fludioxaline hydrochloride + TX, Fentil + TX, Fentil + TX, Fentilphos + TX, Phosphorus + TX, Fentiloxone ... 264+TX, piperonyl butoxide+TX, synergistic aldehyde+TX, propyl isomer+TX, S421+TX, synergistic powder+TX, sesame linolenic acid+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, ceram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, chloroinconazide+TX, mercuric oxide+TX,Thiophanate methyl + TX, azaconazole + TX, bifenthiazolin + TX, oxadiazol + TX, cyproconazole + TX, difenoconazole + TX, diniconazole + TX, epoxiconazole + TX, fenbuconazole + TX, fluquinconazole + TX, flusilazole + TX, flutriafol + TX, furazolidone + TX, hexaconazole + TX, imazalil + TX, imidazole + TX, picronil + TX, metconazole + TX, myclobutrazol + TX, paclobutrazol + TX, blastifungin + TX, penconazole + TX, prothioconazole + TX, pyraclostrobin + TX, prochloraz + TX, propiconazole + TX, pyraclostrobin + TX, silyfenazole + TX, tebuconazole + TX, fluconazole + TX, triadimefon + TX, triadimenol + TX, triflumizole + TX, triticonazole + TX, pyrimidine Alcohol + TX, chlorfenapyr + TX, flufenapyr + TX, pyrimidine sulfonate + TX, mefenamic acid + TX, mefenamic acid + TX, dodecacyclic morpholine + TX, fenpropidin + TX, fenpropimorph + TX, spiroxafil + TX, tridemorph + TX, cyprodinil + TX, myclobutanil + TX, myclobutanil + TX, fenpiclonil + TX, fludioxonil + TX, bensulfuron + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX, furamide + TX, oxadixyl + TX, carbendazim + TX, imidacloprid + TX, maisinin- + TX, thiabendazole + TX, mefenamic acid + TX, sclerotinol + TX, mefenamic acid + TX, procymidone + TX, vinclozolin + TX, boscalid + TX, carboxin + TX, Furoxamide + TX, Flutolanil + TX, Methiocarb + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifuroxamide + TX, Dodine + TX, Biguanide + TX, Azoxystrobin + TX, Dioxastrobin + TX, Enstrobin + TX, Enstrobin + TX, Fluoxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Dioxastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyraclostrobin + TX, Pyraclostrobin + TX, Ferram + TX, Mancozeb + TX, Maneb + TX, Maneb + TX, Metiram + TX, Methionb + TX, Maneb + TX, Maneb + TX, Captafol + TX, Captan + TX, Fulbotox + TX, Folpet + TX, Tolylfluanid + TX X, Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalocyanine + TX, kewensan + TX, isoprene + TX, chlorpyrifos + TX, tolclofos-methyl + TX, difop-butyl + TX, benzathiapiprolin + TX, blasticidin-S + TX, chlorpyrifos + TX, chlorothalonil + TX, cyfluanid + TX, cymoxanil + TX, cyclobutrifluram + TX, dichlorocyanamide + TX, pyraclostrobin + TX, chloranil + TX, diethofencarb + TX, dimethomorph + TX, flumorph + TX, dithianon + TX, ethidiumb + TX, oxadone + TX, famoxadone + TX, fenamidone + TX, blastamide + TX, pyrimidine + TX, fluazinam + TX,flumetylsulforim+TX, fluopyram+TX, fluoxytioconazole+TX, sulfaquinoxaline+TX, flupyrosinone+TX, fenhexamid+TX, fosetyl-aluminum+TX, oxamexazole+TX, propineb+TX, saizoline+TX, sulfaquinoxaline+TX, mefenacet+TX, pencycuron+TX, phthalide+TX, polyoxin+TX, propamocarb+TX, pyraclostrobin+TX, iodoquinoxaline+TX, pyraclostrobin+TX, fenpyrad+TX, quinoxyfen+TX, pentachloronitrobenzene+TX, thiazolinone+TX, imidazolin+TX, tricyclazole+TX, triamcinol+TX, validamycin+TX, valosin+TX, zoxamide+TX , dimethomorph + TX, flubeneteram + TX, pyraclostrobin + TX, flutoxafen + TX, benzovinflumizone + TX, flutoxafen + TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, isoflurane + TX, isothianid + TX, dipymetitrone + TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithiino[1,2-c]isothiazole-3-carbonitrile + TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide +TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+Tx, Jiaxiangjunzhi+TX, lvbenmixianan+TX, dich lobentiazox+TX, Mandespin+TX, 3-(4,4-difluoro-3,4-dihydro-3,3-dimethylisoquinolin-1-yl)quinolone+TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolinyl)oxy]phenyl]propan-2-ol+TX, thiophene+TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tert-butyl ester+TX, pyraziflumid+TX, inpyrfluxam+TX, trolprocarb+TX, chlorfluanidazole+TX, ipfentrifluconazole+TX,2-(Difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4-(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazole oxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridachlometyl + TX, 3-(difluoromethyl)-1-methyl-N -[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX, aminopyrifen+TX, pyraclostrobin+TX, indazolesulfamyl+TX, fluopicolide+TX, (Z,2E)-5-[1-(4 -chlorophenyl) pyrazol-3-yl] oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX, florylpicoxamid + TX, benzylpicoxamid + TX, metarylpicoxamid + TX, isobutylethoxyquinoline + TX, ipflufenoquin + TX, quinofumelin + TX, isopropylthiopyrad + TX, 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolane-2-yl] methoxy] phenyl] methyl] pyrazole-3-carboxylic acid ethyl ester + TX (can be made from WO 2020 / 056090), 1-[[4-[(Z)-2-ethoxy-3,3,3-trifluoro-prop-1-enyloxy]phenyl]methyl]pyrazole-3-carboxylic acid ethyl ester + TX (can be prepared by the method described in WO 2020 / 056090), N-[[4-[1-(4-cyclopropyl-2,6-difluoro-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamic acid methyl ester + TX (can be prepared by the method described in WO 2020 / 097012),Methyl N-[[4-[1-(2,6-difluoro-4-isopropyl-phenyl)pyrazol-4-yl]-2-methyl-phenyl]methyl]carbamate + TX (can be prepared by the method described in WO 2020 / 097012), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(2,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide + TX (can be prepared by the method described in WO 2020 / 109391), 6-chloro-N-[2-(2-chloro-4-methyl-phenyl)-2,2-difluoro-ethyl]-3-(3-cyclopropyl-2-fluoro-phenoxy)-5-methyl-pyridazine-4-carboxamide + TX (can be prepared by the method described in WO 2020 / 109391), 6-chloro-3-(3-cyclopropyl-2-fluoro-phenoxy)-N-[2-(3,4-dimethylphenyl)-2,2-difluoro-ethyl]-5-methyl-pyridazine-4-carboxamide+TX (can be prepared by the method described in WO 2020 / 109391), N-[2-[2,4-dichloro-phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, N-[2-[2-chloro-4-(trifluoromethyl)phenoxy]phenyl]-3-(difluoromethyl)-1-methyl-pyrazole-4-carboxamide+TX, thiocyanatoxin+TX, cyproconazole+TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt ( 2:1)+TX, fluopyram+TX, flufenoxadiazam+TX, fluthiazolinone+TX, fluopyram+TX, pyrapropoyne+TX, piperacodazole+TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide+TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3- Formamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, metyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'- (Trifluoromethoxy) [1,1'-diphenyl] -4-yl] -5-pyrimidinemethanol + TX, fluoxapiprolin + TX, enoxastrobin + TX, (Z) -3-methoxy-2- [2-methyl-5- [4- (trifluoromethyl) triazol-2-yl] phenoxy] prop-2-enoic acid methyl ester + TX, (Z) -3-methoxy-2- [2-methyl-5- (4-propyltriazol-2-yl) phenoxy] prop-2-enoic acid methyl ester + TX,(Z)-2-[5-(3-isopropylpyrazol-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazol-1-yl)phenoxy]prop-2-enoic acid methyl ester + TX, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazol-1-yl]phenoxy]prop-2-enoic acid methyl ester + TX (these compounds can be prepared by the method described in WO 2020 / 079111), (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester + TX, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester + TX (these compounds can be prepared by the method described in WO 2020 / 193387), 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-1,2,4- 1-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringostaryl + TX, zhongshengmycin + TX, thiophanate-methyl + TX, thiazole zinc + TX, amectotractin + TX, iprodione + TX, seboctylamine + TX; N'-[5-bromo-2-methyl-6-[(1S)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-[(1R)-1-methyl-2-propoxy-ethoxy]-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX, N'-[5-chloro-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX,N'-[5-bromo-2-methyl-6-(1-methyl-2-propoxy-ethoxy)-3-pyridinyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO2015 / 155075); N'-[5-bromo-2-methyl-6-(2-propoxypropoxy)-3-pyridinyl]-N-ethyl-N-methyl-formamidine + TX (this compound can be prepared by the method described in IPCOM000249876D); N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenyl-ethyl)phenyl]-N-methyl N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N'-[4-(1-cyclopropyl-2,2,2-trifluoro-1-hydroxy-ethyl)-5-methoxy-2-methyl-phenyl]-N-isopropyl-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO2018 / 228896); N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine + TX, N-ethyl-N'-[5-methoxy-2-methyl-4-[(2-trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine + TX (these compounds can be prepared by the method described in WO 2019 / 110427); N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, N-[(1S)-1 -benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide + TX, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide + TX, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide + TX, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX,N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide + TX (these compounds can be prepared by the method described in WO 2017 / 153380); 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline + TX, 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4,6-trifluoro-3,3-dimethyl-isoquinoline + TX, 4,4-difluoro-3,3-dimethyl -1-(6-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 4,4-difluoro-3,3-dimethyl-1-(7-methylpyrazolo[1,5-a]pyridin-3-yl)isoquinoline+TX, 1-(6-chloro-7-methyl-pyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX (these compounds can be prepared by WO 2017 / 025510); 1-(4,5-dimethylbenzimidazol-1-yl)-4,4,5-trifluoro-3,3-dimethyl-isoquinoline+TX, 1-(4,5-dimethylbenzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-isoquinoline+TX, 6-chloro-4,4-difluoro-3,3-dimethyl-1-(4-methylbenzimidazol-1-yl)isoquinoline+TX, 4,4-difluoro-1-(5-fluoro-4-methyl-benzimidazol-1-yl)-3,3-dimethyl-isoquinoline+TX, 3-(4,4-difluoro-3,3-dimethyl-1-isoquinolyl)-7,8-dihydro-6H-cyclopenta[e]benzimidazole+TX (these compounds can be prepared by WO 2016 / 156085); N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 1-methoxy-3-methyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX,4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylic acid ethyl ester+TX, N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX. The compounds in this paragraph can be prepared by WO 2017 / 055473, WO 2017 / 055469,Prepared by the method described in WO 2017 / 093348 and WO 2017 / 118689; 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2017 / 029179); 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol+TX (this compound can be prepared by the method described in WO 2017 / 029179); 3-[2-(1-chlorocyclopropyl)-3-(2-fluorophenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile+TX (this compound can be prepared by the method described in WO 2016 / 156290); 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (this compound can be prepared by the method described in WO 2016 / 156290); 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (this compound can be prepared by the method described in WO2014 / 006945); 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone + TX (this compound can be prepared by the method described in WO 2011 / 138281); N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX; (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide+TX (this compound can be prepared by the method described in WO 2018 / 153707); N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine+TX; N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine+TX (this compound can be prepared by the method described in WO 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (this compound can be prepared by the method described in WO 2014 / 095675); (5-methyl-2-pyridyl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX,(3-methylisoxazol-5-yl)-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methanone + TX (these compounds can be prepared by the method described in WO 2017 / 220485); 2-oxo-N-propyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide + TX (this compound can be prepared by the method described in WO 2018 / 065414); 1-[[5-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-2-thienyl]methyl]pyrazole-4-carboxylic acid ethyl ester + TX (this compound can be prepared by the method described in WO 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide+TX, N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-[N-methoxy-C-methyl-carbonimino]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX (these compounds can be prepared by the method described in WO 2018 / 202428);

[0527] Microorganisms, including: Acinetobacter lwoffii + TX, Acremonium alternifolium + TX + TX, Acremonium cephalosporium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, and AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria interspersed +TX, Alternaria cassiae +TX, Alternaria destruens +TX, Powdery mildew +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Aureobasidium +TX, Azospirillum spp. ( TAZO )+TX, nitrogen-fixing bacteria+TX, Azotobacter chroocuccum +TX, nitrogen-fixing bacteria cysts (Bionatural Blooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (e.g. Biostart TM , the previous )+TX, Bacillus licheniformis strain 3086 ( Green )+TX, Bacillus circulans+TX, Bacillus firmus +TX, Bacillus firmus strain I-1582 +TX, Bacillus macerans +TX, Bacillus marismortui +TX, Bacillus megaterium +TX, Bacillus mycoides strain AQ726 +TX, Milky Spore )+TX, Bacillus pumilus species+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( Ballad )+TX, Bacillus spahericus +TX, Bacillus sp. +TX, Bacillus sp. strain AQ175 +TX, Bacillus sp. strain AQ177 +TX, Bacillus sp. strain AQ178 +TX, Bacillus subtilis strain QST 713 +TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant strain FZB24 +TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis aizawai GC 91 +TX, Bacillus thuringiensis israelensis +TX, Bacillus thuringiensis kurstaki ( Scutella Turilav Dipel )+TX, Bacillus thuringiensis kurstaki BMP 123 +TX, Bacillus thuringiensis subsp. Kurstaki HD-1 +TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var. aizawai +TX, bacterial species +TX, bacteriophage of Clavipacter michiganensis +TX, +TX, Beauveria bassiana ( Brocaril )+TX, Beauveria bassiana GHA (Mycotrol Mycotrol )+TX, Beauveria brongniartii ( Schweizer )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia ( Blue )+TX, Burkholderia gladii+TX, Burkholderia gladioli+TX, Burkholderia species+TX, Canadian thistle fungus (CBH Canadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana +TX, Candida sake +TX, Candida species +TX, Candida tenius +TX, Cedecea dravisae +TX, Cellulomonas flavigena +TX, Chaetomium cochliodes +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides +TX, Cladosporium oxysporum +TX, Cladosporium chlorocephalum +TX, Cladosporium spp. +TX, Cladosporium tenuissimum +TX, Clonostachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis +TX, Cydia pomonella granulovirus +TX, Cydia pomonella granulovirus ( Max, Carpovirusine )+TX、Cylindrobasidium laeve +TX, Cylindrocladium +TX, Debaryomyces hansenii +TX, Drechslera hawaiinensis +TX, Enterobacter cloacae +TX, Enterobacteriaceae +TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum spp. +TX, Filobasidium floriforme +TX, Fusarium umaminasium +TX, Fusarium chlamydosporum +TX, Fusarium oxysporum ( Biofox )+TX, Fusarium proliferatum+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum +TX, Gliocladium roseum +TX, Gliocladium spp. +TX, Gliocladium virens +TX, Granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas spp. +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hanseniaspora uvarum +TX, Helicoverpa armigera nucleopolyhedrovirus +TX, Helicoverpa zea nuclear polyhedrosis virus +TX, Isoflavone-formononetin +TX, Kloeckera apiculata +TX, Kloeckera spp. +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria Dispar nucleopolyhedrosisvirus +TX, Marinococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima+TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. ( Root )+TX, Myrothecium verrucaria strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosoroseus +TX, Paecilomyces linacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea spp.+TX, Pasteuria spp. +TX, Pasteuria nishizawae +TX, Penicillium aurantiogriseum +TX, Penicillium billai +TX, Penicillium brevicompactum +TX, Penicillium frequentans +TX, Penicillium griseofulvum +TX, Penicillium purpurogenum +TX, Penicillium spp. +TX, Penicillium viridicatum +TX, Phlebiopsis gigantean +TX, phosphate solubilizing bacteria +TX, Phytophthora cryptogea +TX, Phytophthora palmivora +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaefaciens +TX, Pichia onychis +TX, Pichia stipites +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas spp.+TX, Pseudomonas syringae +TX, Pseudomonas viridiflava +TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Pucciniathlaspeos(Wood )+TX, Pythium paroecandrum+TX, Pythium oligandrum +TX, Pythium periplocum +TX, Rhanella aquatilis +TX, Rhanella spp. +TX, Rhizobia +TX, Rhizoctonia +TX, Rhodococcus globerulus strain AQ719 +TX, Rhodosporidium diobovatum +TX, Rhodosporidium toruloides +TX, Rhodotorula spp. +TX, Rhodotorula glutinis +TX, Rhodotorula graminis +TX, Rhodotorula mucilagnosa +TX, Rhodotorula rubra +TX, Saccharomyces cerevisiae +TX, Salinococcus roseus +TX, Sclerotinia minor +TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosis virus +TX, Serratia marcescens +TX, Serratia plymuthica +TX, Serratia spp. +TX, Sordaria fimicola +TX, Spodopteralittoralis nucleopolyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma magamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 ( PlantShield )+TX, Trichoderma harzianum T-39 +TX, Trichoderma inhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum (Binab )+TX, Trichoderma taxi+TX, Trichoderma virens+TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon pullulans +TX, Trichosporon spp. +TX, Trichothecium spp. +TX, Trichothecium roseum +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium atrum +TX, Ulocladium oudemansii +TX, Ustilago maydis +TX, various bacteria and supplementary nutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii +TX、Vip3Aa20 +TX, Virgibaclillus marismortui +TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii+TX, Xenorhabdus nematophila+TX;

[0528] Plant extracts including: pine oil +TX, Azadirachtin (Plasma Neem ), Plant IGR +TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extracts (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, neem oil +TX, catnip (Nepeta cataria) (catnip oil) +TX, Nepeta catarina +TX, nicotine +TX, oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Giant knotweed +TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, Melaleuca alternifolia extract (also known as tea tree oil) (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and peppermint extract mixture (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae +TX;

[0529] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, Codling moth pheromone (Paramount dispenser-(CM) / Isomate )+TX, Grape Leaf Roller Pheromone (3M MEC-GBM Sprayable )+TX, leaf roller pheromone (3M MEC-LR Sprayable )+TX, Muscamone (Snip7 Fly Starbar Premium Fly )+TX, Pear fruit moth pheromone (3Moriental fruit moth sprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm Pheromone (3M Sprayable )+TX, Entostat powder (from palm tree extract) (Exosex )+TX、(3E,8Z,11Z)-3,8,11-tetradecatriene acetate+TX、(7Z,11Z,13E)-7,11,13-hexadecatrienal+TX、(E,Z)-7,9-dodecadien-1-yl acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX, +TX, Lavandulylsenecioate+TX;

[0530] Macrobial agents (Macrobial), including: short-spurred aphid wasp + TX, Alphid wasp +TX, Acerophagus papaya+TX, Coccinella bispot +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, cocoon jumping wasp+TX, nest moth polyembryonic jumping wasp+TX, Anderson's blunt mite +TX, Amblyseius californicus +TX, Amblyseius cucumber mite ( Bugline )+TX, Pseudo-Amblyseius +TX, Bugline )+TX, Amblyseius osbornei +TX, whitefly wasp+TX, original cherry-winged wasp+TX, dark-bellied long-line jumping wasp+TX, Kama long-line jumping wasp+TX, Anagyrusloecki+TX, mealybug long-line jumping wasp +TX, Red wax scale flat-horned jumping wasp +TX, Golden wasp +TX, Woodland flower bug +TX, short-spurred aphid wasp +TX, short-winged aphid wasp+TX, cotton aphid parasitic wasp +TX, Alphididae +TX, tobacco aphid wasp+TX, peach red aphid wasp +TX, aphid-eating gall midge +TX, aphid-eating gall midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Ha's long-tailed biting wasp +TX, ant-shaped winged beetle +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European bumblebee +TX, Cephalonomia stephanoderis+TX, Black-backed ladybug+TX, Common lacewing +TX, Common Lacewing +TX, Red Lacewing+TX, Cirrospilus ingenuus+TX, Four-banded Scirgid Wasp+TX, White-starred Orange Wasp+TX, Closteroceruschamaeleon+TX, Closterocerus species+TX, Coccidoxenoides perminutus +TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Aphididae spp.+TX, Cryptochilus spp. +TX, Japanese square-headed beetle+TX, Siberian gnathostome +TX, Siberian gnathostome +TX, Pea leafminer +TX, Little Black Ladybug +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Diaparsis jucunda+TX, Ali louse-eating wasp+TX, Pea leafminer wasp+TX, Pea leafminer wasp +TX, Siberian Braconidia +TX, Encarsia species+TX, Encarsia longita +TX, Encarsia spp. )+TX, Psammocera spp. +TX, Goden's aphid wasp+TX, Haidian's aphid wasp+TX, thin flat hoverfly +TX, Eretmoceris siphonini+TX, California scyphoceras+TX, scyphoceras ( Eretline )+TX, Psammocera spp. +TX, Heinrich's aphid wasp+TX, Monterey's aphid wasp ( Eretline )+TX, Eretmocerus siphonini+TX, Four-spotted light-edged ladybug+TX, Mite-eating gall midge +TX, Acarina +TX, Alishan fly miner +TX, Fopiusceratitivorus +TX, Wirless )+TX, thrips slender waist +TX, Western Stachybotrys +TX, Scleroderma hornbeak +TX, Lycosa axyridis +TX, Harmonia axyridis +TX, Heterorhabditis species (Lawn )+TX, Heterorhabditis elegans (NemaShield )+TX, Nemasys BioNem Exhibitline )+TX, spotted long-legged ladybug+TX, pointed narrow shield mite +TX, Hypoline )+TX, Black Branch Gall Wasp+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, Tricolor Jumping Wasp+TX, Citrus Flour Scale Parasitic Wasp +TX, Longhorn Jumping Wasp+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Green Fly +TX, tea-footed aphid wasp+TX, blind bug ( Macroline )+TX, Mesoseiulus longipes+TX, Yellow broad-handled jumping wasp+TX, Metaphycuslounsburyi+TX, Corner vein brown lacewing +TX, yellow flower-winged jumping wasp +TX, Muscidifuraxraptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, Neodryinus californicus+TX, Neodryinus typhlocybae cucumber +TX, Neoseiulus fallacis +TX, Nesideocoris tenuis +TX, Bronze Blackfly +TX, Cunning Flower Bug ( Oriline )+TX, Hairless Flower Bug ( Oriline )+TX, Oriline )+TX, small black flower stink bug +TX, Pauesiajuniperorum+TX, Phasmarhabditis hermaphrodita+TX +TX, Phymastichus coffea+TX, Phytoseiidae coarse hair mite+TX, Phytoseiidae Chileanus ( Phytoline )+TX, Cypripedium scaly-bellied +TX, parasitic flea fly curvatus+TX, parasitic flea fly obtusus+TX, parasitic flea fly tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, hairy psyllid jumping wasp+TX, short-backed braconid wasp (complex)+TX, species of the genus Myxomyssinus+TX, Rhyzobius lophanthae+TX, Australian ladybird+TX, Ruminadecollate+TX, Semielacher petiolatus+TX, wheat aphid +TX, Steinernema carinii (Nematac BioNem )+TX, Steinernema carinata ( Nemasys BioNem Exhibitline )+TX, Nemasys BioNem Exhibitline )+TX, Steinernia rapis +TX, Nematacornae )+TX, Steinernema species+TX, Steinernema species (Guardian )+TX, Deep-point mite-feeding ladybug +TX, bright-bellied enameled wasp+TX, Tetrastichus setifer+TX, Thropobius semiluteus+TX, Chinese long-tailed wasp+TX, Tricholine )+TX, Trichogrammatid wasp +TX, Trichogramma spleniformis +TX, Trichogramma microstomata +TX, Trichogramma ostriniae +TX, Trichogramma broad-veined +TX, Trichogramma short-tubed +TX, Trichogramma striata +TX;

[0531] Other biological agents, these other biological agents include: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Colletotrichum spondyloticum +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( Ni-HIBIT Gold )+TX, fatty acids derived from natural by-products of extra virgin olive oil +TX, ferric phosphate +TX, Funneltrap (Trapline )+TX、 +TX, Grower's +TX, Homo-brassonolide +TX, Ferric Phosphate (Lilly Miller Worry Free Ferramol Slug & Snail )+TX、MCP Hailtrap (Trapline )+TX, parasitic insect Microctonus hyperodae+TX, Mycoleptodiscus terrestris +TX, +TX, +TX, +TX, Pheromone Net (Thripline )+TX, potassium bicarbonate +TX, potassium salt of fatty acids +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, spider venom +TX, locust microsporidia (Semaspore Organic Grasshopper )+TX, Trapline Rebell )+TX and capture (Takitrapline )+TX;

[0532] (1) An antibacterial agent selected from the group consisting of:

[0533] (1.1) Bacteria, examples of which are Bacillus mojavensis strain R3B (accession number NCAIM (P) B001389) (WO 2013 / 034938), from Certis USA LLC +TX; Bacillus pumilus, in particular strain BU F-33, with NRRL accession number 50185 (from BASF); EPA registration number 71840-19) + TX; Bacillus subtilis, in particular strain QST713 / AQ713 (SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, with NRRL registration number B21661, U.S. Patent No. 6,060,051) + TX; Bacillus subtilis strain BU1814 (from BASF SE PLUS, FLEX and EXTRA) + TX; Bacillus subtilis variant amyloliquefaciens strain FZB24, with registration number DSM 10271 (available as or ECO (EPA registration number 70127-5) obtained from Novozymes) + TX; Bacillus subtilis CX-9060 + TX from Certis USA LLC; Bacillus species, specifically strain D747 (available as DOUBLE obtained from Kumiai Chemical Industry Co., Ltd.) with accession number FERM BP-8234, U.S. Patent No. 7,094,592+TX; Paenibacillus sp. strains with accession number NRRL B-50972 or accession number NRRL B-67129, WO 2016 / 154297+TX; Paenibacillus polymyxa, particularly strain AC-1 (e.g., from Green Biotech Company Ltd.) ) + TX; Pantoea agglomerans, in particular strain E325 (accession number NRRL B-21856) (available as BLOOMTIME BIOLOGICAL TM FD BIOPESTICIDE (from Northwest Agri Products) + TX; Pseudomonas proradix (e.g., from Sourcon Padena) )+TX; and

[0534] (1.2) Fungi, examples of which are Aureobasidium pullulans, in particular blastospores of strain DSM 14940, blastospores of strain DSM 14941 or a mixture of blastospores of strains DSM 14940 and DSM 14941 (e.g., blastospores from bio-ferm, Switzerland). and BLOSSOM )+TX; Pseudozyma aphidis (as disclosed in WO 2011 / 151819 by Yissum Research Development Company of the Hebrew University of Jerusalem)+TX; Saccharomyces cerevisiae, in particular strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938 or CNCM No. 1-3939 (as disclosed in WO 2010 / 086790, from Lesaffre et Compagnie, France)+TX;

[0535] (2) Biofungicides selected from the group consisting of:

[0536] (2.1) Bacteria, an example of which is Agrobacterium radiobacterium strain K84 (e.g., from AgBioChem, California) )+TX; radiobacterium strain K1026 (e.g., NOGALL from BASF TM )+TX; Bacillus subtilis variant amyloliquefaciens strain FZB24, with accession number DSM10271 (available as or ECO (EPA registration number 70127-5) obtained from Novozymes) + TX; Bacillus amyloliquefaciens, specifically strain D747 (available as Double Nickel TM obtained from Kumihiko Chemical Industries, Ltd., with accession number FERM BP-8234, U.S. Patent No. 7,094,592) + TX; Bacillus amyloliquefaciens strain F727 (also known as strain MBI110) (NRRL accession number B-50768, WO 2014 / 028521) (from Marrone Bio Innovations )+TX; Bacillus amyloliquefaciens strain FZB42, registration number DSM 23117, (can be used as from ABiTEP, Germany) + TX; Bacillus amyloliquefaciens isolate B246 (e.g., AVOGREEN from the University of Pretoria); TM )+TX; Bacillus licheniformis, in particular strain SB3086, having accession number ATCC 55406, WO 2003 / 000051 (available as Biofungicides and Green Release TM Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (from FMC Corporation) (WG) and (WP)) + TX; Bacillus methylotrophicus strain BAC-9912 (from the Institute of Applied Ecology, Chinese Academy of Sciences) + TX; Bacillus mojavensis strain R3B (accession number NCAIM(P)B001389) (WO 2013 / 034938), from Certis USA LLC + TX; Bacillus mycoides isolate with accession number B-30890 (available as BMJ or WG and LifeGardTM obtained from Surtice USA) + TX; Bacillus pumilus, specifically strain QST2808 (available as obtained from Bayer CropScience, USA, with registration number NRRL B-30087 and described in US Pat. No. 6,245,551) + TX; Bacillus pumilus, in particular strain GB34 (available as Yield pumilus, in particular strain BUF-33, having NRRL accession number 50185 (available as part of the CARTISSA product from BASF, EPA accession number 71840-19) + TX; Bacillus subtilis, in particular strain QST713 / AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience in the United States, having NRRL accession number B21661, and described in U.S. Patent No. 6,060,051) + TX; Bacillus subtilis Y1336 (available as WP was obtained from Bion-Tech, Taiwan, China, and registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Bacillus subtilis strain MBI 600 (available as SUBTILEX from BASF, with registration number NRRL B-50595, U.S. Patent No. 5,061,495) + TX; Bacillus subtilis strain GB03 (available as obtained from Bayer AG, Germany) + TX; Bacillus subtilis strain BU1814, (available as PLUS, FLEX and EXTRA obtained from BASF) + TX; Bacillus subtilis CX-9060, obtained from Sertis America, a subsidiary of Mitsui & Co., Ltd. + TX; Bacillus subtilis KTSB strain (obtained from Donaghys )+TX; Bacillus subtilis IAB / BS03 (AVIV from STK Bio-Ag Technologies) TM , from IdaiNature )+TX; Bacillus subtilis strain Y1336 (can be used as WP was obtained from Biotech, Taiwan, China, and registered as a biofungicide in Taiwan under registration numbers 4764, 5454, 5096, and 5277) + TX; Paenibacillus epiphyticus (WO 2016 / 020371) from BASF + TX; Paenibacillus polymyxa plantarum species (WO 2016 / 020371) from BASF + TX; Paenibacillus species strains with registration number NRRL B-50972 or registration number NRRL B-67129, WO 2016 / 154297 + TX; Pseudomonas chlororaphis strain AFS009 with registration number NRRL B-50897, WO 2017 / 019448 (e.g., HOWLER from AgBiome Innovations, USA). TM and ) + TX; Pseudomonas chlororaphis strains, in particular strain MA342 (e.g., from Bioagri and Koppert); and )+TX; Pseudomonas fluorescens strain A506 (e.g., from NuFarm A506) + TX; Pseudomonas proradix (e.g., from Soconpadna) ) + TX; Streptomyces griseoviridis strain K61 (also known as Streptomyces luteus strain K61) (accession number DSM7206) (from Verdera BioWorks See Crop Protection 2006, 25, 468-475) + TX; Streptomyces lydicus strain WYEC108 (also known as Streptomyces lydicus strain WYCD108US) (from Novozymes and )+TX; and

[0537] (2.2) Fungi, an example of which is Pseudomonas aeruginosa, in particular strain AQ 10 (e.g. AQ from IntrachemBio Italia) )+TX; Pseudomonas graminearum strain AQ10, with accession number CNCM 1-807 (e.g., AQ from Intrachem Biologia Italia S.A. )+TX; Aspergillus flavus strain NRRL21882 (as a and known products) + TX; budding mold, especially the spores of strain DSM14940 + TX; budding mold, especially the spores of strain DSM 14941 + TX; budding mold, especially the mixture of spores of strains DSM14940 and DSM 14941 (for example, from Bio-Philippe Co., Ltd., Switzerland )+TX; Chaetomium cupreum (accession number CABI 353812) (e.g., BIOKUPRUM from AgriLife TM )+TX; Chaetomium globosum (can be used as from Rivale) + TX; Cladosporium cladosporioides, strain H39, with accession number CBS122244, US2010 / 0291039 (from Wageningen Research Foundation (Stichting Dienst Landbouwkundig Onderzoek)) + TX; Coniothyrium minitans, in particular strain CON / M / 91-8 (accession number DSM9660, e.g., from Bayer CropScience Biologics GmbH) + TX; )+TX; Cryptococcus flavescens, strain 3C (NRRL Y-50378), (B2.2.99)+TX; Dactylaria candida+TX; Dilophosphora alopecuri (can be used as TWIST Obtain) + TX; Fusarium oxysporum, strain Fo47 (can be used as obtained from Natural Plant Protection) + TX; Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate) strain J1446 (e.g., from Lallemand) )+TX; Glioma rosea (also known as Glioma pink), in particular strain 321U from Adjuvants Plus, strain ACM941 as disclosed in Xue AG (Efficacy of Clonostachys rosea strain ACM941 and fungicide seed treatments for controlling the root tot complex of field pea, Can. J. Plant Sci. 2003, 83(3):519-524), or strain IK726 (Jensen DF et al. Development of a biocontrol agent for plant disease control with special emphasis on thenear commercial fungal antagonist Clonostachys rosea). strain 'IK726' [with particular emphasis on the development of a biocontrol agent for plant disease control using the near-commercial fungal antagonist Gliocladium roseum strain 'IK726'], Australasian Plant Pathol. 2007, 36(2), 95-101) + TX; conidia of Lecanicillium lecanii (formerly Verticillium lecanii) strain KV01 (e.g., from Corbett / Arysta )+TX; Metschnikowia fructicola, in particular strain NRRL Y-30752, (B2.2.3)+TX; Microsphaeropsis ochracea+TX; Muscodor roseus, in particular strain A3-5 (accession number NRRL 30548)+TX; Penicillium steckii (DSM 27859, WO 2015 / 067800) from BASF+TX; Penicillium vermiculatum+TX; Phlebiopsis gigantea strain VRA 1992 (from Danstar Ferment) C) + TX; Pichia anomala, strain WRL-076 (NRRL Y-30842), U.S. Patent No. 7,579,183 + TX; Pseudozyma flocculosa, strain PF-A22 UL (can be used as L obtained from Plant Products Co., California) + TX; Saccharomyces cerevisiae, specifically strain LASO2 (from Agro-Levures et Dérivés), strain LAS117 cell wall (from Lesaffre From BASF ), strains CNCM No. 1-3936, CNCM No. 1-3937, CNCM No. 1-3938, CNCM No. 1-3939 (WO 2010 / 086790) + TX from Lesaffre, France; Simplicillium lanosoniveum + TX; Talaromyces flavus, strain V117b + TX; Trichoderma asperelloides JM41R (registration number NRRL B-50759) (from TRICHO )+TX; Trichoderma asperellum, in particular strain kd (e.g., T-Gro from Andermatt Biocontrol)+TX; Trichoderma asperellum, in particular strain SKT-1, with accession number FERM P-16510 (e.g., ), strain T34 (e.g., T34 from Biocontrol Technologies SL, Spain) or strain ICC 012+TX from Isagro; Trichoderma aureoviride, in particular strain SC1 (accession number CBS122089, WO 2009 / 116106 and U.S. Patent No. 8,431,120 (from Bi-PA), strain 77B (T77 from Andermat Biocontrol) or strain LU132 (e.g., Sentinel from Agrimm Technologies Ltd.)+TX; Trichoderma aureoviride, strain CNCM 1-1237 (e.g., Sentinel from Agrauxine, France); WP) + TX; Trichoderma viride, strain No. V08 / 002387 + TX; Trichoderma viride, strain NMI No. V08 / 002388 + TX; Trichoderma viride, strain NMI No. V08 / 002389 + TX; Trichoderma viride, strain NMI No. V08 / 002390 + TX; Trichoderma viride, strain LC52 (e.g., Tenet from Agri-Mount Technology Co., Ltd.) + TX; Trichoderma viride, strain ATCC 20476 (IMI 206040) + TX; Trichoderma viride, strain T11 (IMI352941 / CECT20498) + TX; Trichoderma viride, strain SKT-1 (FERM P-16510), Japanese Patent Publication (Kokai) 11-253151A + TX; Trichoderma viride, strain SKT-2 (FERM P-16511), Japanese Patent Publication (Kokai) 11-253151A+TX; Dark green Trichoderma, strain SKT-3 (FERM P-17021), Japanese Patent Publication (Kokai) 11-253151A+TX; Trichoderma fertile (for example, the product TrichoPlus from BASF) + TX; Trichoderma gamsii (original green Trichoderma), strain ICC080 (IMICC 392151CABI, for example, BioDerma from AGROBIOSOL DE MEXICO, SADE CV) + TX; Trichoderma gamsii (original green Trichoderma), strain ICC 080 (IMICC 392151CABI) (can be used as obtained from Agribelso Mexico) + TX; Trichoderma harmatum + TX; Trichoderma harmatum, with accession number ATCC 28012 + TX; Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Kobert) or strain CepaSimbT5 (from Simbiose Agro) + TX; Trichoderma harzianum + TX; Trichoderma harzianum slant (rifai) T39 (e.g., from Makhteshim, USA) )+TX; Trichoderma harzianum, strain ITEM 908 (e.g., Trianum-P from Kobert)+TX; Trichoderma harzianum, strain TH35 (e.g., Root-Pro from Mycontrol)+TX; Trichoderma harzianum, strain DB 103 (can be used as 7456 from Dagutat Biolab) + TX; Trichoderma polysporum, strain IMI 206039 (e.g., Binab TF WP from BINAB Bio-Innovation AB, Sweden) + TX; Trichoderma stromaticum, with accession number Ts3550 (e.g., Tricovab from CEPLAC, Brazil) + TX; Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (e.g., SoilGard from Certis, USA) + TX; Trichoderma virens strain G-41, formerly known as Gliocladium virens (accession number ATCC 20906) (e.g., from Biovox, USA) + TX; PLUS WP and PLUS WP) + TX; Trichoderma viride, strain TV1 (e.g., Trianum-P from Kobert) + TX; Trichoderma viride, in particular strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie [Science of the Agricultural University of Szczecin] 161: 125-137) + TX; a mixture of Trichoderma asperellum strain ICC 012 (also known as Trichoderma harzianum ICC 012) (with the accession number CABI CC IMI 392716) and Trichoderma gamsii (formerly known as Trichoderma viride) strain ICC 080 (with the accession number IMI 392151) (e.g., BIO-TAM from Esig USA, Inc. TM and from Agriberso Mexico )+TX; Ulocladium oudemansii strain U3, having accession number NM 99 / 06216 (e.g., from Botry-Zen Ltd, New Zealand) and from Byworth )+TX; Verticillium albo-atrum (formerly V. dahliae), strain WCS850, having accession number WCS850, deposited with the Central Bureau for FungiCultures (e.g., by Tree Care Innovations, DUTCH )+TX; Verticillium chlamydosporium+TX;

[0538] (3) Biological control agents having the effect of improving plant growth and / or plant health selected from the following group:

[0539] (3.1) Bacteria, an example of which is Azospirillum brasilense (e.g., from KALO, Inc.) )+TX; Azospirillum lipoferum (e.g., VERTEX-IF from TerraMax, Inc.) TM)+TX; Azorhizobiumcaulinodans, in particular strain ZB-SK-5+TX; Azotobacter chroococcum, in particular strain H23+TX; Azotobacter vinelandii, in particular strain ATCC 12837+TX; a mixture of Azotobacter vinelandii and Clostridium pasteurianum (which can be used as from Agrinos) + TX; Bacillus amyloliquefaciens pm414 (from Biofilm Crop Protection) )+TX; Bacillus amyloliquefaciens SB3281 (ATCC#PTA-7542, WO 2017 / 205258)+TX; Bacillus amyloliquefaciens TJ1000 (can be used as Bacillus amyloliquefaciens, in particular strain IN937a+TX; Bacillus amyloliquefaciens, in particular strain FZB42 (e.g., from Abbott, Germany). ) + TX; Bacillus amyloliquefaciens BS27 (accession number NRRL B-5015) + TX; EE128 (NRRL No. B-50917) + TX; EE349 (NRRL No. B-50928) + TX; Bacillus cereus, in particular strain BP01 (ATCC 55675, for example, from Arysta Lifescience, USA ) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g., from BASF )+TX; Bacillus mycoides BT155 (NRRL No. B-50921)+TX; Bacillus mycoides EE118 (NRRL No. B-50918)+TX; Bacillus mycoides EE141 (NRRL No. B-50916)+TX; Bacillus mycoides BT46-3 (NRRL No. B-50922)+TX; Bacillus pumilus, in particular strain QST2808 (accession number NRRL No. B-30087)+TX; Bacillus pumilus, in particular strain GB34 (e.g., YIELD® from Bayer CropScience, Germany) )+TX; Bacillus siamensis, particularly strain KCTC 13613T+TX; Bacillus subtilis, particularly strain QST713 / AQ713 (having NRRL accession number B-21661 and described in U.S. Patent No. 6,060,051, can be used as OPTI or ASO was obtained from Bayer CropScience in the United States) + TX; Bacillus subtilis, in particular strain AQ30002 (accession number NRRL B-50421 and described in U.S. patent application number 13 / 330,576) + TX; Bacillus subtilis, in particular strain AQ30004 (and NRRL number B-50455 and described in U.S. patent application number 13 / 330,576) + TX; Bacillus subtilis strain BU1814 (available as from BASF), Bacillus subtilis rm303 (from Biofilm Crop Protection ) + TX; Bacillus thuringiensis BT013A (NRRL No. B-50924), also known as Bacillus thuringiensis 4Q7 + TX; a mixture of Bacillus licheniformis FMCH001 and Bacillus subtilis FMCH002 (can be used as (WG), (WP) obtained from FMC Corporation) + TX; Bacillus subtilis, in particular strain MBI 600 (e.g., from BASF )+TX; Bacillus tequilensis, in particular strain NII-0943+TX; Bradyrhizobium japonicum (e.g., from Novozymes )+TX; Delftia acidovorans, in particular strain RAY209 (e.g., from Brett Young Seeds )+TX; Mesorhizobium cicer (e.g., NODULATOR from BASF)+TX; Lactobacillus species (e.g., Lactobacillus from Latpafi) ) + TX; Rhizobium leguminosarium biovar viciae (e.g., NODULATOR from BASF) + TX; Pseudomonas proradix (e.g., ) + TX; Pseudomonas aeruginosa, in particular strain PN1 + TX; Rhizobium leguminosarum, in particular Rhizobium villus (bv. viceae) strain Z25 (accession number CECT 4585) + TX; Bacillus polymyxa, in particular strain AC-1 (e.g., from Green Biotechnology Co., Ltd. ) + TX; Serratia marcescens, in particular strain SRM (accession number MTCC 8708) + TX; Sinorhizobium meliloti strain NRG-185-1 (from Bayer CropScience GOLD) + TX; Thiobacillus sp. (e.g., from Cropaid Ltd, UK) )+TX; and

[0540] (3.2) Fungi, examples of which are Purpureocillium lilacinum (formerly Paecilomyces lilacinus) strain 251 (AGAL 89 / 030550, e.g., BioAct from Bayer CropScience Bio) +TX; Penicillium bilaii, strain ATCC 22348 (e.g., from Acceleron BioAg); ), yellow basket fungus (Talaromyces flavus), strain V117b + TX; dark green Trichoderma strain CNCM 1-1237 (for example, from Aglaocosin, France) WP), viride, e.g., strain B35 (Pietr et al., 1993, Zesz. Nauk. AR w Szczecinie [Science of the Agricultural University of Szczecin] 161: 125-137) + TX; Trichoderma atroviride strain LC52 (also known as Trichoderma atroviride strain LU132, e.g., from Agri-Mountain Technologies Ltd. )+TX; dark green Trichoderma strain SC1 (described in WO 2009 / 116106)+TX; Trichoderma asperellum strain kd (e.g., T-Gro from Andermatt Biocontrol)+TX; Trichoderma asperellum strain (Eco-T from Plant Health Products of New Zealand)+TX, Trichoderma harzianum strain T-22 (e.g., Trianum-P from Andermatt Biocontrol or Cobert)+TX; Myroderma verrucosum strain AARC-0255 (e.g., DiTera from Valent Biosciences) TM )+TX; Penicillium bilaii strain ATCC ATCC20851+TX; Pythium oligandrum strain M1 (ATCC 38472, for example, Polyversum from Bioprepraty, Czech Republic)+TX; Trichoderma virens strain GL-21 (for example, from Sertis, USA) )+TX; Verticillium albo-atrum (formerly V. dahliae) strain WCS850 (CBS276.92, e.g., Dutch Trig from Tree Care Innovations)+TX; Trichoderma aureum, particularly strain No. V08 / 002387, strain No. NMI No. V08 / 002388, strain No. NMI No. V08 / 002389, strain No. NMI No. V08 / 002390+TX; Trichoderma harzianum strain ITEM 908, Trichoderma harzianum strain TSTh20+TX; Trichoderma harzianum strain 1295-22+TX; Pythium oligandrum strain DV74+TX; Rhizopogon amylopogon (e.g., from Agri-Enterprise, LLC, formerly known as Helena Chemical Company Chem. Company) + TX; Rhizopogon fulvigleba (e.g., Myco-Sol from Agri-Enterprise, LLC, formerly known as Helena Chemical Company) + TX; Trichoderma virens strain GI-3 + TX;

[0541] (4) Insecticidal biological control agents selected from the following

[0542] (4.1) Bacteria, examples of which are Agrobacterium radiobacterium strain K84 (Galltrol from Egger Biochemicals) + TX; Bacillus amyloliquefaciens, in particular strain PTS-4838 (e.g., AVEO from Hualun Biosciences, USA) + TX; Bacillus firmus, in particular strain CNMC 1-1582 (e.g., from BASF ) + TX; Bacillus mycoides, isolate J. (e.g., BmJ from Certis USA ALLC) + TX; Bacillus sphaericus, particularly serotype H5a5b strain 2362 (strain ABTS-1743) (e.g., from Hualun Biosciences, Inc., USA ) + TX; Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372, e.g., from Hualun Biosciences ) + TX; Bacillus thuringiensis subsp. aizawai, particularly serotype H-7 (e.g., from Hualun Biosciences, USA WG) + TX; Bacillus thuringiensis israelensis strain BMP 144 (e.g., from Becker Microbial Products, Inc., Illinois); ) + TX; Bacillus thuringiensis subsp. israelensis (serotype H-14) strain AM65-52 (accession number ATCC 1276) (e.g., from Hualun Biosciences, USA )+TX; Bacillus thuringiensis subsp. aizawai strain GC-91+TX; Bacillus thuringiensis var. Colmeri (e.g., TIANBAOBTC from Changzhou Jianghai Chemical Factory)+TX; Bacillus thuringiensis Japonica strain Buibui+TX; Bacillus thuringiensis subsp. Kurstaki strain BMP 123 (from Becker Microbial Products, Illinois)+TX; Bacillus thuringiensis subsp. Kurstaki strain BMP 123 (from Becker Microbial Products, Illinois), e.g., BARITONE+TX from Bayer CropScience; Bacillus thuringiensis subsp. Kurstaki strain HD-1 (e.g., from Hualun Biosciences, USA). ES) + TX; Bacillus thuringiensis variant Kurstaki strain EVB-113-19 (e.g., from AEF Global )+TX; Bacillus thuringiensis subsp. Kurstaki strain ABTS 351+TX; Bacillus thuringiensis subsp. Kurstaki strain PB 54+TX; Bacillus thuringiensis subsp. Kurstaki strain SA 11 (from Sertis, USA) )+TX; Bacillus thuringiensis subsp. Kurstaki strain SA12 (THURICIDE from the United States, Sertis)+TX; Bacillus thuringiensis subsp. Kurstaki strain EG2348 (from the United States, Sertis )+TX; Bacillus thuringiensis subsp. Kurstaki strain EG 7841 (from Sertis, USA ) + TX; Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428, e.g., BioFa, Germany) FC) + TX; Brevibacillus laterosporus (from Ecolibrium Biologicals Ltd.) )+TX; Burkholderia species, in particular Burkholderia rinojensis strain A396 (also known as Burkholderia rinojensis strain MBI 305) (Accession No. NRRL B-50319; WO 2011 / 106491 and WO 2013 / 032693; e.g., MBI206 TGAI and from Maroni BioInnovations )+TX; Chromobacterium subtsugae, particularly strain PRAA4-1T (e.g., MBI-203; e.g., from Maroni Bioinnovations )+TX; Lecanicillium muscarium Ve6 (MYCOTAL from Kobert)+TX; Paenibacillus popilliae (formerly known as Bacillus popilliae); for example, MILKY SPORE POWDER from St. Gabriel Laboratories TMor Milky Spore Granular TM ) + TX; Pasteurella pseudoszavara strain Pn1 (CLARIVA from Syngenta / China Chemical Corporation) + TX; Serratia entomophila (e.g., Wrightson Seeds) )+TX; Serratia marcescens, in particular strain SRM (accession number MTCC 8708)+TX; Trichoderma asperellum (TRICHODERMAX from Novozymes)+TX; Wolbachia pipientis ZAP strain (e.g., ZAP from MosquitoMate) )+TX; and

[0543] (4.2) Fungi, an example of which is Beauveria bassiana strain ATCC 74040 (e.g. from Intrachem Bio, Italy). ) + TX; Beauveria bassiana strain GHA (accession number ATCC74250, e.g., from Laverlam Int. Corp. ES and )+TX; Beauveria bassiana strain ATP02 (accession number DSM 24665)+TX; Isaria fumosorosea (formerly known as Paecilomyces fumosoroseus), strain Apopka97, e.g., from SePRO )+TX; Metarhizium anisopliae 3213-1 (deposited under NRRL accession number 67074, disclosed in WO 2017 / 066094; Pioneer Hi-Bred International)+TX; Metarhizium robertsii 15013-1 (deposited under NRRL accession number 67073)+TX; Metarhizium robertsii 23013-3 (deposited under NRRL accession number 67075)+TX; Paecilomyces lilacinus strain 251 (from Sertis, USA )+TX; Zoophtora radicans+TX;

[0544] (5) A virus selected from the group consisting of: summer fruit tortrix granulovirus (GV) + TX; Cydia pomonella (codling moth) granulovirus (GV) + TX; Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV) + TX; Spodoptera exigua (beet armyworm) mNPV + TX; Spodoptera frugiperda (fall armyworm) mNPV + TX; Spodoptera littoralis (African cotton moth) NPV + TX;

[0545] (6) Bacteria and fungi selected from the group consisting of Agrobacterium spp. + TX; Azorhizobium caulinodans + TX; Azospirillum spp. + TX; Azotobacter spp. + TX; Bradyrhizobium spp. + TX; Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia) + TX; Gigaspora spp. or Gigaspora monosporum + TX; Glomus spp. + TX; Laccaria spp. + TX; Lactobacillus buchneri + TX; Paraglomus spp. spp.) + TX; Pisolithus tinctorus + TX; Pseudomonas species + TX; Rhizobium species, especially Rhizobium trifolii + TX; Rhizopogon species + TX; Scleroderma species + TX; Suillus species + TX; Streptomyces species + TX;

[0546] (7) Plant extracts and products formed by microorganisms (including proteins and secondary metabolites) that can be used as biocontrol agents, selected from garlic (Allium sativum) (NEMGUARD from Eco-Spray; BRALIC from ADAMA) + TX; Armour-Zen + TX; Artemisia absinthium + TX; azadirachtin (e.g., AZATIN XL from Sertis, USA) + TX; Biokeeper WP + TX; extracts from the Brassicaceae family, in particular rapeseed meal or mustard meal + TX; Cassia nigricans + TX; Celastrus angulatus + TX; Chenopodium anthelminticum + TX; chitin + TX; Dryopteris filix-mas + TX; Equisetum arvense + TX; arvense)+TX; Fortune Aza+TX; Fungastop+TX; Quinoa saponin extract from quinoa seeds (e.g., HeadsUp plant protectants from Canada) (quinoa saponins) + TX; naturally occurring Blad peptide extracted from lupin seeds (from Certis EU ) + TX; naturally occurring Blad polypeptide extracted from lupin seeds (from FMC )+TX; Pyrethrum / Pyrethrins+TX; Quassia amara+TX; Quercus+TX; Quillaja extract (QL AGRI 35 from BASF)+TX; Giant knotweed extract (from MarroneBio) MAXX)+TX; "Requiem TM "Insecticide" + TX; Rotenone + TX; Ryania / ryanodine + TX; Symphytum officinale + TX; Artemisia selengensis + TX; Thymol + TX; Thymol mixed with Geraniol (CEDROZ from Eden Research) + TX; Thymol mixed with Geraniol and Eugenol (CEDROZ from Eden Research) + TX )+TX; Triact 70+TX; TriCon+TX; Tropaeulum majus+TX; Melaleuca alternifolia extract (TIMOREX from Stockton Corporation (STK) )+TX; Urtica dioica+TX; Veratrin+TX; and Viscum album+TX; and

[0547] Safeners such as fenoxacorb+TX, cloquintocet-mexyl (including cloquintocet-mexyl)+TX, cyclopropylsulfonamide+TX, dichloropropane+TX, fenoxac (including fenoxac-ethyl)+TX, fenoxac+TX, fluazifop+TX, fenoxac+TX, isoxadiazole+TX, isoxadiazole (including isoxadiazole-ethyl)+TX, mefenpyr (including mefenpyr-diethyl)+TX, metcamifen+TX and fenoxaconitrile+TX.

[0548] References in brackets after the active ingredient, e.g. [3878-19-1] refer to Chemical Abstracts Registry Numbers. The mixed partners described above are known. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; Editor: CDSTomLin; The British Crop Protection Council]], they are described therein by the entry number given above in parentheses for the specific compound; e.g. the compound "avermectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of Pesticide Common Names , 1995-2004]; for example, the compound "acetoprolin" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html middle.

[0549] Most of the active ingredients described above are referred to by what are referred to as "common names" above, with the corresponding "ISO common name" or another "common name" being used in different cases. If a name is not a "common name," the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name," "Traditional Name," "Compound Name," or "Research Code" is used, or if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0550] A trade name in parentheses following an active ingredient refers to one or more commercially available products containing that active ingredient.

[0551] Active ingredient mixtures of a compound of formula (I) selected from compounds of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or the compounds listed in Table P (below) and the active ingredients described above contain a compound selected from a compound of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or the compounds listed in Table P (below) and the active ingredients as described above, preferably in a mixing ratio of from 100:1 to 1:6000, in particular in a mixing ratio of from 50:1 to 1:50, more particularly in a ratio of from 20:1 to 1:20, even more particularly from 10:1 to 1:1 0, very especially in a ratio of from 5:1 and 1:5, particularly preferably in a ratio of from 2:1 to 1:2, and likewise preferably in a ratio of from 4:1 to 2:1, especially in a ratio of 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 2:5, or 3:5, or 4:5, or 1:4, or 2:4, Or a ratio of 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0552] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0553] Mixtures comprising a compound of formula (I) selected from a compound of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or a compound listed in Table P (below) and one or more active ingredients as described above can be applied, for example, in a single "ready-to-use" form, as a combined spray mixture consisting of separate formulations of the individual active ingredient components, such as a "tank mix", and when applied in a sequential manner, for example, one after another within a reasonably short period of time (such as a few hours or days), in combination with a single active ingredient. The order in which the compound of formula (I) and the active ingredients as described above are applied is not critical for the practice of the present invention.

[0554] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example, non-epoxidized or epoxidized vegetable oils (for example, epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example, silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, for example, bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0555] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound I for preparing these compositions are also subject matter of the present invention.

[0556] Methods of applying these compositions, i.e., methods for controlling the aforementioned types of pests, such as spraying, atomizing, dusting, brushing, coating, broadcasting, or pouring—selected to suit the intended purpose in the prevailing situation—and the use of these compositions for controlling the aforementioned types of pests are further subjects of the present invention. Typical concentration ratios are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of the active ingredient. The application rate per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g / ha, preferably 10 to 600 g / ha.

[0557] In the field of crop protection, the preferred method of application is application to the leaves of the plants (foliar application), it being possible to select the frequency and rate of application to suit the risk of infestation by the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by saturating the locus of the plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants (e.g. into the soil, for example in the form of granules (soil application)). In the case of rice crops, such granules can be metered into flooded rice fields.

[0558] The compound with formula (I) of the present invention and composition thereof will also be suitable for the protection of plant propagation materials (such as seeds, such as fruit, tuber or grain, or nursery plants), to resist the harmful organism of above-mentioned type.Can be used before planting, this propagation material is processed, for example, can be processed before sowing, seed.Alternately, can be by being immersed in liquid composition by seed or by applying solid composition layer, this compound is applied to seed grain (coating).Also may be when this propagation material is planted in application site, use these compositions, for example, during drilling, these compositions are applied to seed furrow.These treatment methods for plant propagation materials and the plant propagation materials so processed are other themes of the present invention.Typical treatment ratio will depend on plant to be controlled and harmful organism / fungus, and usually between 1 gram to 200 grams of every 100kg seed, preferably between 5 grams to 150 grams of every 100kg seed, as between 10 grams to 100 grams of every 100kg seed.

[0559] The term "seed" encompasses all kinds of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings, etc. and in preferred embodiments means true seeds.

[0560] The present invention also includes seeds coated or treated with a compound of formula (I) or seeds containing a compound of formula (I). Although more or less parts of the ingredients depending on the method of application can penetrate into the seed material, the term "coated or treated with ... and / or containing" generally means that when applied, in most cases, the active ingredient is on the surface of the seed. When (re)planting the seed product, it can absorb the active ingredient. In an embodiment, the present invention makes it possible to obtain plant propagation materials having a compound of formula (I) adhered thereto. In addition, thus making it possible to obtain a composition comprising plant propagation materials treated with a compound of formula (I).

[0561] Seed treatment includes all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with a compound of formula (I) can be applied by any known method, such as spraying or dusting the seeds before sowing or during sowing / planting.

[0562] The compounds of the present invention can be distinguished from other similar compounds by greater efficacy and / or different pest control at low application rates, which can be determined by those skilled in the art using experimental procedures, using lower concentrations (if necessary), for example, 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or lower application rates, such as per m 2 Greater efficacy may be observed through increased safety (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties or increased biodegradability).

[0563] In each aspect and embodiment of the present invention, "consisting essentially of and variations thereof are preferred embodiments of "comprising" and variations thereof, and "consisting of and variations thereof are preferred embodiments of "consisting essentially of and variations thereof.

[0564] The disclosure of this application enables every combination of the embodiments disclosed herein.

[0565] It should be noted that the disclosure herein regarding compounds of formula (I) applies equally to compounds of each of formula (I), (Ia), (Ib), (I-A1), (I-A2), or a compound selected from the group consisting of compounds as presented in Tables A1 to A2, or compounds listed in Table P (below),

[0566] The compounds according to the present invention can be used as pesticides in their unmodified form, but they are usually formulated into compositions in a variety of ways using formulation adjuvants such as carriers, solvents, and surfactants. The formulations can be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersants, oily dispersants, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (using water or water-miscible organic solvents as carriers), impregnated polymer films, or in other known forms, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, First Edition, Second Revision (2010). Such formulations can be used directly or can be diluted before use. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0567] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely divided solid, granules, solution, dispersant or emulsion. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants or combinations thereof.

[0568] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredient to be released (for example, slowly released) into the environment in a controlled amount. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredient they contain is about 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymers and starch xanthate or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredient is contained in a solid matrix of a base material in the form of finely dispersed particles, but these microcapsules themselves are not wrapped.

[0569] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers, water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glyceryl acetate, glyceryl diacetate, glyceryl triacetate, decaglycerol Hexadecane, Hexanediol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Lauramine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, Oleic Acid, Oleylamine, o-Xylene, Phenol, Polyethylene Glycol, Propionic Acid, Propyl Lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0570] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0571] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium laurylsulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammoniums, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and dialkyl phosphates; and further substances, such as are described, for example, in McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company. Corp., Ridgewood New Jersey (1981).

[0572] Additional adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0573] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil with an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or an oil of plant origin, for example, rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, for example, methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, for example, methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0574] These compositions according to the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound according to the invention and from 1% to 99.9% by weight of formulation adjuvants, which preferably include from 0 to 25% by weight of surface-active substances. Whereas commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0575] The rate of application varies within wide limits and depends on the nature of the soil, the method of application, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors dictated by the method of application, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 to 2000 l / ha, in particular from 10 to 1000 l / ha.

[0576] A preferred formulation may have the following composition (wt %):

[0577] Emulsifiable concentrates :

[0578] Active ingredient: 1% to 95%, preferably 60% to 90%

[0579] Surfactant: 1% to 30%, preferably 5% to 20%

[0580] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0581] powder :

[0582] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0583] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0584] Suspension concentrate:

[0585] Active ingredient: 5% to 75%, preferably 10% to 50%

[0586] Water: 94% to 24%, preferably 88% to 30%

[0587] Surfactant: 1% to 40%, preferably 2% to 30%

[0588] wettable powder :

[0589] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0590] Surfactants: 0.5% to 20%, preferably 1% to 15%

[0591] Solid carrier: 5% to 95%, preferably 15% to 90%

[0592] Granules:

[0593] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0594] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0595] Examples

[0596] The following examples further illustrate (but do not limit) the present invention.

[0597] Throughout this specification, temperatures are given in degrees Celsius (° C.) and “mp.” means melting point. LC / MS means liquid chromatography mass spectrometry and a description of the apparatus and methods follows.

[0598] LC-MS and GC-MS methods

[0599] Method A (LC-MS): Spectra were recorded on an ACQUITY mass spectrometer from Waters (SQD or SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative, capillary: 3.0 kV, cone: 30 V, extractor: 3.00 V, source temperature: 150°C, desolvation temperature: 400°C, cone gas flow: 60 L / hr, desolvation gas flow: 700 L / hr, mass range: 140 to 800 Da) and an ACQUITY UPLC from Waters with a solvent degasser, binary pump, heated column compartment, and diode array detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 400, solvent gradient: A = water / methanol 9:1 + 0.1% formic acid, B = acetonitrile + 0.1% formic acid, gradient: 0-100% B in 2.5 min; flow rate (ml / min) 0.75.

[0600] Method B (LC-MS):Spectra were recorded on a mass spectrometer from Waters (SQD2 or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary: 0.8-3.00 kV, cone range: 25 °C, source temperature: 120°C-150°C, desolvation temperature: 500°C-600°C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110 to 850 Da) and an Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 x 2.1 mm, temperature: 40°C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH: Gradient: 0 min 10% B; 0.min-0.2 min 10%-50% B; 0.2 min-0.6 min 50%-100% B; 0.6-1.3 min 100% B; 1.3 min-1.4 min 100%-10% B; 1.4 min-1.6 min 10% B; flow rate (mL / min) 0.6.

[0601] Method C (LC-MS): Spectra were recorded on a mass spectrometer from Agilent Technologies (6410 triple quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive or negative ion, MS2 scan, capillary voltage: 4.00 kV, fragmentor voltage: 100 V, desolvation temperature: 350°C, gas flow: 11 L / min, nebulizer gas: 45 psi, mass range: 110 to 1000 Da) and a 1200 series HPLC from Agilent: quaternary pump, heated column compartment and VWD detector. Column: KINETEX EVO C18, 2.6 μm, 50 x 4.6 mm, temperature: 40°C, detector VWD wavelength: 254 nm, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.1% HCOOH: gradient: 0 min 10% B, 90% A; 0.9-1.8 min 100% B; 1.8-2.2 min 100% -10% B; 2.2-2.5 min 10% B; flow rate (mL / min) 1.8.

[0602] Method D (LC-MS):Spectra were recorded on a mass spectrometer from Waters (SQD2 or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative switching, capillary: 0.8-3.00 kV, cone range: 25 °C, source temperature: 120°C-150°C, desolvation temperature: 500°C-600°C, cone gas flow: 50 L / h, desolvation gas flow: 1000 L / h, mass range: 110 to 850 Da) and an Acquity UPLC from Waters: quaternary solvent manager, heated column compartment, diode array detector. Column: Acquity UPLC HSS T3 C18, 1.8 μm, 30 x 2.1 mm, temperature: 40°C, DAD wavelength range (nm): 200 to 400, solvent gradient: A = water + 5% acetonitrile + 0.1% HCOOH, B = acetonitrile + 0.05% HCOOH: Gradient: 0 min 10% B; 0.0-0.5 min 10% B; 0.5-2 min 100% B; 2-3 min 100% B; 3-3.5 min 10% B; 3.5-4 min 10% B; flow rate (mL / min) 0.6.

[0603] Method E (LC-MS): Spectra were recorded on a mass spectrometer from Waters Corporation (SQD, SQDII or QDA single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative ions), capillary voltage: 0.8-3.00 kV, cone: 5-30 V, source temperature: 120°C-150°C, desolvation temperature: 350°C-600°C, cone gas flow: 50-150 l / h, desolvation gas flow: 650-1000 l / h, mass range: 110 to 950 Da and Acquity UPLC from Waters Corporation: binary pump, heated column compartment, diode array detector and ELSD. Column: Waters UPLCHSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60° C., DAD wavelength range (nm): 210 to 400, run time: 1.5 min; solvent: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; flow rate (ml / min) 0.85, gradient: 10% B isocratic for 0.2 min, then 10%-100% B in 1.0 min, 100% B isocratic for 0.2 min, 100%-10% B in 0.05 min, 10% B isocratic for 0.05 min.

[0604] Preparation Examples

[0605]

[0606] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0607]

[0608] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0609] Emulsifiable concentrates

[0610]

[0611] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0612]

[0613] Ready-to-use powders are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such powders can also be used for dry seed dressing.

[0614] Extruder granules

[0615]

[0616] The combination is mixed with the adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0617] Coated granules

[0618] Active ingredient 8%

[0619] Polyethylene glycol (molecular weight 200) 3%

[0620] Kaolin 89%

[0621] The finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0622] Suspension concentrates

[0623]

[0624] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0625] Flowable concentrate for seed treatment

[0626]

[0627] The finely ground combination is intimately mixed with adjuvants to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such a dilution, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0628] Extended-release capsule suspension

[0629] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is reached. To this emulsion, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until polymerization is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0630] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished drug substances (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible

[0631] abbreviation

[0632] CDCl3 deuterated chloroform

[0633] DCM dichloromethane (methylene chloride or methylene dichloride)

[0634] DMF dimethylformamide

[0635] DMSO dimethyl sulfoxide

[0636] DMSO-d6 deuterated dimethyl sulfoxide

[0637] EtOAc

[0638] HCl

[0639] h / hrs hours

[0640] LC-MS liquid chromatography-mass spectrometry

[0641] rt room temperature

[0642] Rt retention time

[0643] TBME tert-butyl methyl ester or tert-butyl methyl ester

[0644] THF Tetrahydrofuran

[0645] TMS Tetramethylsilane

[0646] Preparation Example

[0647] "Mp" means melting point in ° C. Free radical means a methyl group.

[0648] Recorded on a Bruker 400 MHz spectrometer 1 H NMR and 19 F NMR measurements, chemical shifts relative to TMS ( 1 H) or CFCl3( 19 F) Standards are given in ppm. Spectra were measured in deuterated solvents as indicated.

[0649] The compounds were characterized using any of the LC-MS methods. Characteristic LC-MS values obtained for each compound were the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + .

[0650] Example P1: N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonylamino)propoxy]-3-pyridinyl]methyl] Preparation of propionamide (Compound P-1, Table P)

[0651]

[0652] Step A: Preparation of [(2S)-2-(tert-butoxycarbonylamino)propyl]methanesulfonate

[0653]

[0654] At 0 ℃, to N-[(1S)-2-hydroxy-1-methyl-ethyl] carbamic acid tert-butyl ester (5.00g, 28.5mmol) in THF (100mL) solution, add triethylamine (5.97mL, 42.8mmol, 1.50 equivalents), add methanesulfonyl chloride (2.49mL, 31.4mmol, 1.10 equivalents) subsequently.Reactant mixture is stirred 2.5 hours under rt.Then it is diluted with EtOAc and quenched with saturated sodium bicarbonate solution.Water layer is extracted with additional EtOAc.The organic layer merged is dried over sodium sulfate, filtered and under reduced pressure concentrated, to obtain thick [(2S)-2-(tert-butoxycarbonylamino) propyl group] methanesulfonate, which is used in the next step as it is.

[0655] 1 H NMR(400MHz, CDCl3)δppm:4.58-4.74(m,1H)4.22(br s,1H)4.12-4.19(m,1H)3.98(br s,1H)3.04(s,3H)1.45(s,9H)1.24(d,3H)

[0656] Step B: tert-Butyl N-[(1S)-2-[(6-chloro-5-cyano-3-pyridinyl)oxy]-1-methyl-ethyl]carbamate Preparation of esters

[0657]

[0658] At rt under nitrogen atmosphere, cesium carbonate (23mmol, 2 equivalents) is added to the stirring solution of 2-chloro-5-hydroxy-pyridine-3-carbonitrile (1.8g, 12mmol, 1 equivalent) and [(2S)-2-(tert-butoxycarbonylamino) propyl group] methanesulfonate (15mmol, 1.3 equivalents) in N, N-DMF (20mL / g). The gained suspension is stirred at 60 DEG C and spent the night and then diluted with EtOAc. The solution is washed with water and the aqueous phase is extracted with EtOAc. The organic layer combined is dried over sodium sulfate, and is concentrated under reduced pressure. The desired product as a white solid is obtained by silica gel column chromatography (eluent: mixture cyclohexane / EtOAc) purification.

[0659] 1 H NMR (400MHz, CDCl3) δppm 1.31(d,3H)1.46(s,9H)3.94-4.26(m,3H)4.56-4.75(m,1H)7.53(d,1H)8.30(d,1H).

[0660] Step C: Preparation of [(1S)-2-(6-chloro-5-cyano-pyridin-1-ium-3-yl)oxy-1-methyl-ethyl]ammonium dichloride preparation

[0661]

[0662] At 0 DEG C, 4M solution of hydrochloric acid in EtOAc (66mmol, 14 equivalents) is added dropwise to a stirred solution of N-[(1S)-2-[(6-chloro-5-cyano-3-pyridyl)oxy]-1-methyl-ethyl] tert-butyl carbamate (1.5g, 4.8mmol, 1 equivalent) in EtOAc (4.1mL / g).Then the temperature is raised to rt and the reaction mixture is stirred overnight. The gained reaction mixture is concentrated under reduced pressure, washed with n-pentane and dried in a vacuum, to obtain the desired product as a white solid.

[0663] 1 H NMR(400MHz, DMSO-d6)δppm 1.29(d,3H)3.57-3.68(m,1H)4.14-4.22(m,1H)4.32(m,1H)8.26(d,1H)8.28-8.38(m,2H)8.48(d,1H).

[0664] Step D: N-[(1S)-2-[(6-chloro-5-cyano-3-pyridinyl)oxy]-1-methyl-ethyl]-1,1,1-trifluoro- Preparation of methanesulfonamide

[0665]

[0666] At 0 DEG C, triethylamine (6 equivalents, 21.1mmol) and trifluoromethanesulfonic anhydride (1.2 equivalents, 4.2mmol) are added dropwise to a solution of [(1S)-2-(6-chloro-5-cyano-pyridin-1-ium-3-yl)oxy-1-methyl-ethyl] ammonium dichloride (1g, 3.5mmol) in acetonitrile (20mL / g). The reaction mixture is allowed to reach rt and stirred overnight. The reaction mixture is diluted with EtOAc and citric acid aqueous solution. The two phases are separated, and the water layer is extracted with EtOAc. The combined organic layer is dried over sodium sulfate and concentrated under reduced pressure. The desired product as a white solid is obtained by silica gel column chromatography (eluent: a mixture of cyclohexane / EtOAc).

[0667] 1 H NMR (400MHz, CDCl3) δppm 1.49 (d, 3H) 4.02-4.17 (m, 3H) 5.51 (m, 1H) 7.52 (d, 1H) 8.30 (d, 1H).

[0668] Step E: N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonylamino)propoxy]-3-pyridinyl]methyl]propanoyl Preparation of amide (Compound P-1, Table P)

[0669] Under nitrogen atmosphere, propionic anhydride (3 equivalents, 0.44mmol) and sodium bicarbonate aqueous solution (4 equivalents, 0.58mmol, 28.5mL / g) are added to a stirred solution of N-[(1S)-2-[(6-chloro-5-cyano-3-pyridyl)oxy]-1-methyl-ethyl]-1,1,1-trifluoro-methanesulfonamide (50mg, 0.15mmol) in THF (60mL / g). Then Raney nickel (4.5 equivalents, 0.65mmol, 50% by mass) is added to the mixture. The reaction mixture is then placed under a hydrogen atmosphere and stirred for 5 hours. Next, the reaction mixture is filtered through diatomaceous earth, and the filter cake is fully washed with THF. The combined filtrate is concentrated under reduced pressure and diluted with EtOAc. The organic phase is washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The desired product is obtained by purification by silica gel column chromatography (eluent: a mixture of cyclohexane / EtOAc).

[0670] 1 H NMR (400 MHz, acetonitrile-d3) δ ppm 1.09 (t, 3H) 1.34 (d, 3H) 2.23 (q, 2H) 3.81-4.03 (m, 2H) 4.03-4.13 (m, 1H) 4.33 (d, 2H) 6.84 (br s, 1H) 6.94 (br s, 1H) 7.26 (d, 1H) 7.96 (d, 1H).

[0671] Example P2: N-[[2-Chloro-5-[(2S)-2-(trifluoromethylsulfonylamino)propoxy]phenyl]methyl]propionamide Preparation of (Compound P-4, Table P)

[0672]

[0673] Step A: Preparation of tert-butyl N-[(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl]carbamate

[0674]

[0675] Under rt, cesium carbonate (2 equivalents, 65.1mmol) and [(2S)-2-(tert-butoxycarbonylamino) propyl group] methanesulfonate (1.5 equivalents, 48.8mmol) are added to a stirred solution of 2-chloro-5-hydroxy-benzonitrile (5g, 32.6mmol) in N,N-DMF (20mL / g). Gained suspension is stirred overnight at 65 ℃. Next, the reaction mixture is diluted with EtOAc and water. The two layers are separated, and the water layer is extracted with EtOAc. The organic layer merged is dried over sodium sulfate and under reduced pressure concentrated. By silica gel column chromatography (eluent: mixture of hexanaphthene / EtOAc) purifying obtains desired N-[(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl] t-butyl carbamate.

[0676] 1H NMR (400MHz, CDCl3) δppm 1.29(d,J=6.75Hz,3H)1.45(s,9H)3.89-4.14(m,3H)4.78-4.91(m,1H)7.10(dd,J=8.88,3.00Hz,1H)7.15-7.17(m,1H)7.38(d,J=9.01Hz,1H)

[0677] Step B: Preparation of [(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl]ammonium chloride

[0678]

[0679] At 0 DEG C, 4M solution of hydrochloric acid in EtOAc (270mmol, 11.7 equivalents) is added dropwise to a stirred solution of N-[(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl] tert-butyl carbamate (7.4g, 23mmol, 1 equivalent) in EtOAc (4.1mL / g).Then the temperature is raised to rt and the reaction mixture is stirred overnight. The gained reaction mixture is concentrated under reduced pressure, washed with TBME and dried in a vacuum, to obtain the desired product as a white solid.

[0680] 1 H NMR(400MHz,DMSO-d6)δppm 1.26-1.32(m,3H)3.58(br s,1H)4.10(dd,J=10.39,7.21Hz,1H)4.23(dd,J=10.39,3.91Hz,1H)7.38(dd,J=9.05,3.06Hz,1H)7.64-7.70(m,2H)8.44(br s,3H)

[0681] Step C: N-[(1S)-2-(4-Chloro-3-cyano-phenoxy)-1-methyl-ethyl]-1,1,1-trifluoro-methanesulfonamide Preparation

[0682]

[0683] At 0 ℃, triethylamine (6 equivalents, 130mmol) and trifluoromethanesulfonic anhydride (1.05 equivalents, 23mmol) are added dropwise to a solution of [(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl] ammonium chloride (5.3g, 21mmol) in dichloromethane (10mL / g). The reaction mixture is then allowed to reach rt and stirred overnight. The reaction mixture is diluted with EtOAc and water. The two phases are separated, and the aqueous layer is extracted with EtOAc. The combined organic layer is dried over sodium sulfate and concentrated under reduced pressure. The desired product is obtained by purification by silica gel column chromatography (eluent: a mixture of cyclohexane / EtOAc).

[0684] 1 H NMR(400MHz, CDCl3)δppm 1.44-1.48(m,3H)3.93-3.99(m,1H)4.02-4.14(m,2H)5.70(s,1H)7.08-7.12(m,1H)7.14-7.16(m,1H)7.39-7.44(m,1H)

[0685] 19 F NMR (377MHz, CDCl3) δppm-77.76 (s, 1F)

[0686] Step D: N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonylamino)propoxy]phenyl]methyl]propionamide Preparation of (Compound P-4, Table P)

[0687] Under nitrogen atmosphere, propionic anhydride (3 equivalents, 2,6mmol) and sodium bicarbonate aqueous solution (4 equivalents, 3.5mmol, 18.5mL / g) are added to a stirred solution of N-[(1S)-2-(4-chloro-3-cyano-phenoxy)-1-methyl-ethyl]-1,1,1-trifluoro-methanesulfonamide (300mg, 0.87mmol) in THF (60mL / g). Then Raney nickel (4.5 equivalents, 3.94mmol, 50% by mass) is added to the mixture. The reaction mixture is then placed under a hydrogen atmosphere and stirred for 5h. Next, the reaction mixture is filtered through diatomaceous earth, and the filter cake is fully washed with THF. The combined filtrate is concentrated under reduced pressure and diluted with EtOAc. The organic phase is washed with water, dried over sodium sulfate, and concentrated under reduced pressure. The desired product is obtained by purification by silica gel column chromatography (eluent: a mixture of cyclohexane / EtOAc).

[0688] 1 H NMR (400MHz, CDCl3) δppm 1.17(t,J=7.58Hz,3H)1.43(d,J=6.72Hz,3H)2.22-2.29(m,3H)3.92-4.00(m,1H)4.01-4.03(m,2H)4.47(dd,J=6.05,4.46Hz,2H)6.02(br d,J=5.26Hz,1H)6.75(dd,J=8.80,2.93Hz,1H)6.96(d,J=2.93Hz,1H)7.25-7.30(m,1H)

[0689] 19 F NMR (377MHz, CDCl3) δppm-77.79 (s, 1F)

[0690] Example P3: N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino]propoxy]benzene Preparation of 1,2-dimethyl]propionamide (Compound P-3, Table P)

[0691]

[0692] Step A: N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino]propoxy]phenyl] Preparation of [methyl]propionamide (Compound P-3, Table P)

[0693] At 0 ℃, triethylamine (3 equivalents, 0.30mmol) and chloro(methoxy)methane (1.2 equivalents, 0.12mmol) are added dropwise to the stirred solution of N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonyl)amino] propoxy] phenyl] methyl] propionamide (40mg, 0.10mmol) in acetonitrile (20mL / g).Then the reaction is made to reach rt and stirred for 2 hours. Next, the reaction mixture is diluted with EtOAc and the 1N HCl aqueous solution. Each layer is separated, and the water layer is extracted with EtOAc. The organic layer merged is dried over sodium sulfate, and is under reduced pressure concentrated. By column chromatography (eluent mixture of hexanaphthene / EtOAc) purifying, desired N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino] propoxy] phenyl] methyl] propionamide is obtained.

[0694] 1 H NMR (400MHz, CDCl3) δppm 1.18(t,J=7.63Hz,3H)1.44(d,J=6.88Hz,3H)2.26(q,J=7.55Hz,2H)3.37(s,3H)3.92-4.05(m,1H)4.13(dd,J=9.88,8.00Hz,1H)4.39(br d,J=6.88Hz,1H)4.49(d,J=6.13Hz,2H)4.82(s,2H)5.95(br s,1H)6.76(dd,J=8.76,2.88Hz,1H)6.92(d,J=3.00Hz,1H)7.24-7.29(m,1H)

[0695] 19 F NMR(377MHz, CDCl3)δppm-77.03(s,1F)-75.88(s,1F)

[0696] Example P4: N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino]propoxy]-3- Preparation of pyridyl]methyl]propionamide (Compound P-5, Table P)

[0697]

[0698] Step A: N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino]propoxy]-3-pyrrolidone Preparation of [pyridyl]methyl]propionamide

[0699] At 0 ℃, triethylamine (3 equivalents, 0.19mmol) and chloro(methoxy)methane (1.2 equivalents, 0.08mmol) are added dropwise to a stirred solution of N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonyl)amino] propoxy]-3-pyridyl] methyl] propionamide (26mg, 0.064mmol) in acetonitrile (20ml / g).Then the reaction mixture is made to reach rt and stirred for 2 hours. Next, the reaction mixture is diluted with EtOAc and the 1N HCl aqueous solution. Each layer is separated, and the water layer is extracted with EtOAc. The organic layer merged is dried over sodium sulfate, and under reduced pressure concentrated. By column chromatography (eluent mixture of hexanaphthene / EtOAc) purifying, desired N-[[2-chloro-5-[(2S)-2-[methoxymethyl(trifluoromethylsulfonyl)amino] propoxy]-3-pyridyl] methyl] acrylamide is obtained.

[0700] 1 H NMR (400MHz, CDCl3) δppm 1.18 (t, J = 7.58Hz, 3H) 1.45 (d, J = 6.85Hz, 3H) 2.28 (q, J = 7.58Hz, 2H) 3.37 (s, 3H) 4.04 (br dd,J=9.66,5.99Hz,1H)4.19(dd,J=9.66,7.95Hz,1H)4.37-4.49(m,3H)4.75-4.86(m,2H)6.10(br s,1H)7.31(d,J=2.81Hz,1H)7.94-8.00(m,1H)

[0701] Example P5: N-[[2-chloro-5-[(2S)-2-(trifluoromethylsulfonylamino)propoxy]-3-pyridinyl]methyl] Preparation of cyclopropanecarboxamide (Compound P-9, Table P)

[0702]

[0703] Step A: N-[[2-chlor...

Claims

1. A compound of formula (I), or a salt or N-oxide in: X is CH or N; R 1 C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, cyano-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, cyano-C3-C6-cycloalkyl, C4-C8-bicycloalkyl, 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl, phenyl-C1-C4-alkyl or 5-membered or 6-membered heteroaryl-C1-C3-alkyl; wherein any of said 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl contains 1 or 2 heteroatoms or groups independently selected from N, O, S, S=O or SO2, with the proviso that not more than one is O, S, S=O or SO2 wherein any of the 5-membered or 6-membered heteroaryl-C1-C3-alkyl contains 1 or 2 heteroatoms independently selected from N, S and O, with the proviso that not more than one is O or S; wherein any of the C3-C6-cycloalkyl, C4-C8-bicycloalkyl and 3-membered, 4-membered, 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl, and wherein any of the phenyl or the 5-membered or 6-membered heteroaryl is unsubstituted or substituted with 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy; R 2 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, or C1-C4-alkoxycarbonyl; R 3 and R 4 are independently selected from hydrogen or C1-C3-alkyl; or R 3 and R 4 Together with the carbon to which they are attached, they represent C3-C5-cycloalkyl; R 5 and R 6 are independently selected from hydrogen or C1-C3-alkyl; or R 5 and R 6 Together with the carbon to which they are attached, they represent C3-C5-cycloalkyl; R 7 is selected from C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, phenyl, or 5-membered or 6-membered heteroaryl, wherein the cycloalkyl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl; wherein any of the 5-membered or 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, S and O, and wherein any of the phenyl and the 5-membered or 6-membered heteroaryl is unsubstituted or substituted by 1, 2 or 3 substituents independently selected from halogen, cyano, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkoxy; R 8 is selected from hydrogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkylcarbonyl, C3-C5-cycloalkylcarbonyl or C1-C4-alkoxycarbonyl; and R 9 is selected from halogen or C1-C3-alkyl.

2. The compound according to claim 1, wherein R 5 and R 6 are independently selected from hydrogen or methyl; or R 5 and R 6 Together with the carbon to which they are attached, cyclopropyl groups are represented.

3. The compound according to claim 1 or claim 2, wherein R 9 It's chlorine.

4. The compound according to any one of claims 1 to 3, wherein R 3 and R 4 are independently selected from hydrogen or methyl; or R 3 and R 4 Together with the carbon to which they are attached, cyclopropyl groups are represented.

5. The compound according to any one of claims 1 to 4, wherein R 5 is methyl and R 6 It's hydrogen.

6. The compound according to any one of claims 1 to 5, wherein R 8 It's hydrogen.

7. The compound according to any one of claims 1 to 6, wherein R 2 It's hydrogen.

8. The compound according to any one of claims 1 to 7, wherein R 7 It is dichloromethyl, difluoromethyl or trifluoromethyl.

9. The compound according to any one of claims 1 to 8, wherein R 1 is C1-C3-alkyl, C1-C3-haloalkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C3-alkyl, cyano-C3-C6-cycloalkyl, phenyl, or 5-membered or 6-membered heterocycloalkyl; wherein any of the 5-membered or 6-membered heterocycloalkyl contains 1 heteroatom selected from N, O, S, S=O or SO2; wherein any of the 5-membered or 6-membered heterocycloalkyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C3-C6 cycloalkyl; and wherein the phenyl is unsubstituted or substituted with 1 or 2 substituents independently selected from halogen, cyano, C1-C2 alkyl, C1-C2 haloalkyl or C1-C2 alkoxy.

10. The compound according to claim 9, wherein R 1 is C1-C3-alkyl, C1-C3-haloalkyl or C3-C6-cycloalkyl.

11. A composition comprising a compound as defined in any one of claims 1 to 10.

12. The composition according to claim 11, further comprising at least one additional active ingredient and / or an agrochemically acceptable diluent or carrier.

13. A method for combating and controlling insects, acarines or molluscs, which comprises applying an insecticidally, acaricidally or molluscicidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 10 or a composition as defined in claim 11 or 12 to the pest, the locus of the pest, or a plant susceptible to attack by the pest.

14. A method for protecting plant propagation material from attack by insects, mites or molluscs, comprising treating the propagation material or the site in which the propagation material is planted with an effective amount of a compound of formula (I) as defined in any one of claims 1 to 10 or a composition as defined in claim 11 or 12.

15. Plant propagation material, such as a seed, comprising, treated with or having attached thereto, a compound of formula (I) as defined in any one of claims 1 to 10.

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