Pesticidally active azole-amide compounds

Abstract

To provide compounds that are used as insecticides.SOLUTION: Provided are compounds of formula (I) that can be used as insecticides, and agrochemically acceptable salts, stereoisomers, enantiomers, tautomers and N-oxides of the compounds.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to pesticidally active, in particular insecticidally active, azole-amide compounds, processes for their preparation, compositions containing these compounds and their use for controlling animal pests, including arthropods, in particular insects or representatives of the order Acarina. [Background technology]

[0002] WO2017192385 describes certain heteroaryl-1,2,4-triazole and heteroaryl-tetrazole compounds that are used to control ectoparasites in animals, such as mammals and non-mammalian animals.

[0003] Novel pesticidally active azole azine compounds have now been discovered. Summary of the Invention [Means for solving the problem]

[0004] Thus, in a first aspect, the present invention provides a compound of formula I [ka] (In the formula: R 1 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Cyanoalkyl, Aminocarbonyl C 1 ~C 6 Alkyl, Hydroxycarbonyl C 1 ~C 6 Alkyl, C 1 ~C 6 Nitroalkyl, trimethylsilane C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl;C 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl-(where C 3 ~C 4 Cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH 2 -; or halo or C 1 ~C 6 benzyl optionally substituted with haloalkyl; R 2 is phenyl, pyridine, pyrimidine, pyrazine, or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with 1 to 3 substituents, provided that no substituents are on any carbon adjacent to the carbon to which C=O is attached, and each substituent is selected from the group consisting of C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Thiohaloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, halogen, NO 2 ,SCIENCE FICTION 5 , C.N., C.O.N. 2 , COOH and C(S)NH 2 are independently selected from; R 3 is C 1 ~C 3 Alkyl or C 1 ~C 3 is haloalkyl; R 4 is pyridine, pyrimidine, pyrazine or pyridazine, where pyridine, pyrimidine, pyrazine or pyridazine is C 1 ~C 3 Alkyl, C 1~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 optionally substituted with 1 substituent selected from cycloalkyl, halogen, or hydroxy; Z 1 are halogens, CN, NH 2 C(O), amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, (C 1 ~C 3 Alkyl)C(O), HC(O), diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 or a stereoisomer, enantiomer, tautomer and N-oxide of a compound of formula I, or an agrochemically acceptable salt thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] Compounds of formula I having at least one basic centre can be, for example, acid addition salts, for example with strong inorganic acids, for example mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids, strong organic carboxylic acids, for example C carboxylic acids, which are unsubstituted or substituted, for example, by halogens. 1 ~C 4 Alkane carboxylic acids, such as acetic acid, for example saturated or unsaturated dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid or phthalic acid, for example hydroxycarboxylic acids, such as ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or acid addition salts, for example, with benzoic acid, or organic sulfonic acids, such as C which are unsubstituted or substituted, for example, by halogen. 1 ~C 4 It is possible to form acid addition salts with alkane- or arylsulfonic acids, such as methane- or p-toluenesulfonic acid. Compounds of formula I having at least one acidic group can, for example, form salts with bases, such as inorganic salts, such as alkali metal salts or alkaline earth metal salts, such as sodium salts, potassium salts or magnesium salts, or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, such as ethyl-, diethyl-, triethyl- or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, such as mono-, di- or triethanolamine.

[0006] In each case, the compounds of formula I according to the invention may be in free form, in oxidized form as N-oxide or in salt form, for example in an agronomically acceptable salt form.

[0007] N-oxides are the oxidized forms of tertiary amines or nitrogen-containing aromatic heterocyclic compounds. They are described, for example, in the book "Heterocyclic N-oxides", A. Albini and S. Pietra, CRC Press, Boca Raton 1991.

[0008] The compounds of formula I according to the present invention also include the hydrates which may be formed during salt formation.

[0009] As used herein, "C 1 ~C n The term "alkyl" refers to a saturated straight or branched hydrocarbon radical having 1 to n carbon atoms bonded via any of the carbon atoms, such as any one of the radicals 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.

[0010] As used herein, "C 1 ~C nThe term "haloalkyl" refers to a straight or branched saturated alkyl radical having 1 to n carbon atoms bonded via any of the carbon atoms (as defined above), in which some or all of the hydrogen atoms in these radicals may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, 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, Any one of 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. 1 ~C 2 The term "fluoroalkyl" refers to a C alkyl group having 1, 2, 3, 4 or 5 fluorine atoms. 1 ~C 2 It refers to an alkyl radical and may be, for example, any one of difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, or pentafluoroethyl.

[0011] As used herein, "C 1 ~C nThe term "alkoxy" refers to a straight or branched saturated alkyl radical having 1 to n carbon atoms (as defined above) attached through an oxygen atom, i.e., any one of, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, or 1,1-dimethylethoxy radicals. As used herein, "haloC 1 ~C n The term "alkoxy" refers to a C alkyl group in which one or more hydrogen atoms on an alkyl radical are replaced by the same or different halo atoms. 1 ~C n It refers to an alkoxy radical (examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy).

[0012] As used herein, "C 1 ~C n The term "cyanoalkyl" refers to a linear or branched saturated C alkyl group having 1 to n carbon atoms. 1 ~C n It refers to alkyl radicals (as described above) in which one of the hydrogen atoms in these radicals has been replaced by a cyano group, such as cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0013] As used herein, "C 3 ~C n The term "cycloalkyl" refers to a 3 to n-membered cycloalkyl group, such as cyclopropane, cyclobutane, cyclopropane, cyclopentane, and cyclohexane.

[0014] As used herein, "C 3 ~C 4 Cycloalkyl-C 1 ~C 2The term "alkyl-" refers to a 3- or 4-membered cycloalkyl group having a methylene or ethylene group attached to the remainder of the molecule. For example, C 3 ~C 4 Cycloalkyl-C 1 ~C 2 The alkyl-groups are substituted, the substituents being located on the cycloalkyl group.

[0015] As used herein, "aminocarbonyl C 1 ~C n The term "alkyl" refers to an alkyl radical, where one of the hydrogen atoms in the radical is replaced by a CONH2 group.

[0016] As used herein, "hydroxycarbonyl C 1 ~C n The term "alkyl" refers to an alkyl radical in which one of the hydrogen atoms in the radical has been replaced by a COOH group.

[0017] As used herein, "C 1 ~C n The term "nitroalkyl" refers to an alkyl radical in which one of the hydrogen atoms in the radical is replaced by a NO2 group.

[0018] As used herein, "C 1 ~C n The term "haloalkylthio" refers to a C bonded through a sulfur atom. 1 ~C 3 Refers to a haloalkyl moiety.

[0019] As used herein, "trimethylsilane C 1 ~C n The term "alkyl" refers to an alkyl radical, where one of the hydrogen atoms in the radical is replaced by -Si(CH 3 ) 3 is substituted by a group.

[0020] As used herein, "C 2 ~C n The term "alkenyl" refers to a straight or branched alkenyl chain having 2 to n carbon atoms and 1 or 2 double bonds, for example, ethenyl, prop-1-enyl, but-2-enyl.

[0021] As used herein, "C 2 ~C n The term "haloalkenyl" refers to a C substituted with one or more halo atoms, which may be the same or different. 2 ~C n Refers to the alkenyl moiety.

[0022] As used herein, "C 2 ~C n The term "alkynyl" refers to a straight or branched alkynyl chain having 2 to n carbon atoms and one triple bond, for example, ethynyl, prop-2-ynyl, but-3-ynyl.

[0023] As used herein, "C 2 ~C n The term "haloalkynyl" refers to a C alkynyl group substituted with one or more halo atoms, which may be the same or different. 2 ~C n Refers to the alkynyl moiety.

[0024] Halogen is generally fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0025] As used herein, "(C 1 ~C n The term "S(O) alkyl)sulfonylamino" refers to 2 C bonded to sulfur atom of part 1 ~C n refers to an alkyl group whose sulfur is also bonded to the nitrogen atom of an amino (i.e., NH) moiety, where the nitrogen atom of the amino moiety is CH 3 S(O)2 It is attached to the rest of the molecule as NH-.

[0026] As used herein, "(C 1 ~C n Alkyl)sulfonyl(C 1 ~C n The term "(C alkyl)amino" means 1 ~C n (alkyl)sulfonylamino group, where the hydrogen atom of the amino group is 3 S(O) 2 N(CH 3 )- and other C 1 ~C n It is substituted with an alkyl group.

[0027] As used herein, "(C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 The term "alkyl)N" refers to a C(=O) moiety bonded to the carbon atom of the C(=O) moiety. 1 ~C n It refers to an alkyl group, the carbon of which is also bonded to a nitrogen atom, which is C 1 ~C 3 It is also bonded to an alkyl group, and this nitrogen atom is CH 3 C(O)N(CH 3 )- and is attached to the rest of the molecule.

[0028] Examples of 5-membered aromatic heterocycles include pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; pyrazolyl is preferred.

[0029] R 2 and R 4 The pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstituted or substituted) of the formula are each bonded to the remainder of the compound via a carbon atom in their respective rings.

[0030] As used herein, the term "control" refers to reducing the number of pests such that damage to plants or plant-derived products is reduced, eradicating the pests, and / or preventing further pest damage.

[0031] As used herein, for example, Y 1 ; and R 4 The wavy line at -1 represents the point of attachment / connection to the remainder of the compound.

[0032] As used herein, the term "pest" refers to insects and mollusks found in agriculture, horticulture, forestry, storage of plant-derived products (such as fruit, grain, and lumber); and pests associated with damage to man-made structures. The term pest encompasses all stages in the life cycle of a pest.

[0033] As used herein, the term "effective amount" refers to that amount of a compound or a salt thereof that produces a desired effect in single or multiple applications.

[0034] Effective amounts are readily determined by those skilled in the art by the use of known techniques and by observing results obtained under analogous circumstances. Determining an effective amount takes into account a number of factors, including, but not limited to, the type of plant or plant-derived product to which it is applied; the pest to be controlled and its life cycle; the particular compound to be applied; the type of application; and other relevant circumstances.

[0035] As one of ordinary skill in the art will appreciate, the compounds of formula I contain stereogenic centers, as indicated in the structures below with an asterisk. [ka] In the formula, R 1 , R 2 , R 3 , R 4 , and Z 1 is as defined in the first aspect.

[0036] The present invention contemplates both the racemate and the individual enantiomers. Compounds with preferred stereochemistry are shown below.

[0037] Particularly preferred compounds of the invention have formula I'a: [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , and Z 1 is as defined in the first aspect) and the stereoisomers, enantiomers, tautomers and N-oxides, and agrochemically acceptable salts, of the compounds of formula (I'a).

[0038] As used herein, the term "optionally substituted" means that the referenced group is unsubstituted or substituted with the specified substituents, e.g., "C 3 ~C 4 "Cycloalkyl is optionally substituted with 1 or 2 halo atoms" means 3 ~C 4 Cycloalkyl, C substituted with 1 halo atom 3 ~C 4 Cycloalkyl and C substituted with 2 halo atoms 3 ~C 4 It means cycloalkyl.

[0039] An embodiment of the present invention is provided as follows.

[0040] In one embodiment of each aspect of the invention, R 1 teeth, A. Hydrogen; CN, CONH 2 , COOH, NO 2 and -Si(CH 3 ) 3 C optionally substituted with one substituent selected from 1 ~C6 Alkyl;C 1 ~C 6 Haloalkyl;C 2 ~C 6 Alkenyl; C 2 ~C 6 Alkynyl; C 2 ~C 6 Haloalkynyl;C 3 ~C 4 Cycloalkyl-C 1 ~C 2 Alkyl-(where C 3 ~C 4 Cycloalkyl- is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH 2 -; or halo or C 1 ~C 3 benzyl optionally substituted with haloalkyl; or B. Hydrogen; C 1 ~C 6 Haloalkyl; CN or Si(CH 3 ) 3 C optionally replaced by 1 ~C 6 Alkyl;C 3 ~C 6 Alkynyl; C 3 ~C 4 Cycloalkyl-C 1 ~C 2 Alkyl (where C 3 ~C 4 Cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH 2 -; or benzyl optionally substituted with halo; or C. Hydrogen, C 1 ~C 6 Alkyl, C 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl-(where C 3 ~C 4 Cycloalkyl is optionally substituted with 1 or 2 halo atoms) or oxetan-3-yl-CH 2 -or- D. Hydrogen, C 1 ~C 6 Alkyl or C 3 ~C 4 Cycloalkyl C 1 ~C 2 is alkyl; or E. Hydrogen; C 1 ~C 6 Haloalkyl; CN or Si(CH 3 ) 3 C optionally replaced by 1 ~C 6 Alkyl;C 3 ~C 6 Alkynyl; or C 3 ~C 4 Cycloalkyl-C 1 ~C 2 Alkyl (where C 3 ~C 4 cycloalkyl is optionally substituted with 1 or 2 halo atoms; or F. Hydrogen; C 1 ~C 6 Haloalkyl;C 1 ~C 6 Alkyl;C 3 ~C 6 Alkynyl; or C 3 ~C 4 Cycloalkyl-C 1 ~C 2 Alkyl (where C 3 ~C 4 cycloalkyl is optionally substituted with 1 or 2 halo atoms; or G. Cyclopropyl-CH 2 -, n-propyl, CH≡CCH 2 -, CF 3 CH 2 CH 2 -, F.C.H. 2 CH 2 -, F.C.H. 2 CH 2 CH 2 -,2,2-Difluorocyclopropyl-CH 2 -,2,2-Dichlorocyclopropyl-CH 2 -, hydrogen, CH 3, (CH 3 ) 3 SiCH 2 -, CH 3 CH 2 - or CNCH 2 -or- H. Cyclopropyl-CH 2 -, n-propyl, CH≡CCH 2 -, CF 3 CH 2 CH 2 -, F.C.H. 2 CH 2 -, F.C.H. 2 CH 2 CH 2 -,2,2-Difluorocyclopropyl-CH 2 - or 2,2-dichlorocyclopropyl-CH 2 -or- I. Cyclopropyl-CH 2 -, n-propyl, CH≡CCH 2 -, CF 3 CH 2 CH 2 -, F.C.H. 2 CH 2 -, F.C.H. 2 CH 2 CH 2 -,2,2-Difluorocyclopropyl-CH 2 -, hydrogen, CH 3 , (CH 3 ) 3 SiCH 2 - or CH 3 CH 2 -or- J.Cyclopropyl-CH 2 -, n-propyl, CH≡CCH 2 -, CF 3 CH 2 CH 2 -, F.C.H. 2 CH 2 -, F.C.H. 2 CH 2 CH 2 -, or 2,2-difluorocyclopropyl-CH 2 -or- K. Cyclopropyl-CH 2-, n-propyl, CH≡CCH 2 -, CF 3 CH 2 CH 2 -, F.C.H. 2 CH 2 - or FCH 2 CH 2 CH 2 -or- L.Cyclopropyl-CH 2 -, CH≡CCH 2 -, hydrogen or CH 3 or M.CH≡CCH 2 - or cyclopropyl-CH 2 -or- N-Cyclopropyl-CH 2 -or- O.Cyclopropyl-CH 2 -, hydrogen or CH 3 or P. Hydrogen.

[0041] In one embodiment according to each aspect of the present invention, R 2 teeth A. Phenyl, pyridine, pyrimidine, pyrazine, or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with 1 to 3 substituents, provided that no substituents are located on any of the carbons adjacent to the carbon bonded to the -C(O)- group, each of which is selected from the group consisting of: 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Thiohaloalkyl, C 1 ~C 3 Alkoxy, C 1 -C 3 Haloalkoxy, Halo, NO 2 ,SCIENCE FICTION 5 , C.N., C.O.N. 2 , COOH and C(S)NH 2 are independently selected from; or B. Phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with 1-2 substituents, provided that the substituents are also not located on any carbon adjacent to the carbon to which the C=O is attached, and each substituent is selected from the group consisting of: 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 independently selected from haloalkoxy, halogen, or CN; or CC 1 ~C 3 Haloalkyl, C 1 ~C 3 Haloalkoxy, halo, CN or C(S)NH 2 phenyl, 3-pyridine or 4-pyridine substituted with 1 or 2 substituents independently selected from: DC 1 ~C 3 Haloalkyl, C 1 ~C 3 phenyl, 3-pyridine or 4-pyridine substituted with 1 or 2 substituents independently selected from haloalkoxy, halo or CN, provided that no substituent is located on any carbon adjacent to the carbon bonded to the -C(O)- group; or EC 1 ~C 3 Haloalkyl, C 1 ~C 3 a phenyl or 3-pyridine substituted with 1 or 2 substituents independently selected from haloalkoxy, halo, or CN, provided that no substituent is located on any carbon adjacent to the carbon bonded to the -C(O)- group; or F. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl, 3-bromo-5-trifluoromethylphenyl, 3-cyano-5-trifluoromethylphenyl or 2,6-bis(trifluoromethyl)pyridin-4-yl; or G. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyrid-3-yl, 3-bromo-5-trifluoromethylphenyl or 3-cyano-5-trifluoromethyl-phenyl; or H. 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, or 5-trifluoromethylpyridin-3-yl; or I. 3,5-bis(trifluoromethyl)phenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl 3-chloro-5-trifluoromethoxyphenyl, 5-trifluoromethylpyridin-3-yl or 3-cyano-5-trifluoromethylphenyl; or J. 3,5-bis(trifluoromethyl)phenyl, 3-chloro-5-trifluoromethylphenyl, 3-chloro-5-trifluoromethoxyphenyl or 5-trifluorometapyridin-3-yl; or K. 3,5-bis(trifluoromethyl)phenyl; or LY 1 ~Y 21 [ka] or M.Y. 1 , Y2 , Y 3 , Y 4 , Y 5 , Y 6 , Y 7 , Y 11 , Y 13 , or Y 15 or New York 1 , Y 2 , Y 5 , Y 6 , Y 11 , Y 13 , or Y 15 or OY 1 , Y 3 , or Y 11 or PY 1 , Y 5 , Y 6 , Y 11 , Y 13 , Y 15 , Y 19 , or Y 20 or QY 1 , Y 6 , Y 11 , Y 15 , Y 19 , or Y 20 or RY 1 , Y 15 , or Y 20 or S.Y. 1 It is.

[0042] In one embodiment according to each aspect of the present invention, R 3 teeth AC 1 ~C 3 Alkyl or C 1 ~C 3 haloalkyl; or B.C. 1 ~C 3 is alkyl; or C. Methyl.

[0043] In an embodiment of each aspect of the invention, R 4 teeth A. Pyridine or pyrimidine, where pyridine or pyrimidine has one C 1 ~C 3 optionally substituted with alkoxy or halogen; or B. 2-pyridine, 2-pyrimidine, 2-pyrazine or 2-pyridazine, each of which is C 1 ~C 3 optionally substituted with alkoxy or halo; or C. pyridine or pyrimidine, wherein the pyridine, pyrimidine is optionally substituted with one halogen; D. 2-pyridine or 2-pyrimidine, each of which is C 1 ~C 3 optionally substituted with alkoxy or halo; or E.J. 1 ~J 8 or [ka] FJ 1 , J 2 , J 3 , J 4 , J 6 , J 7 and J 8 or Good. 2 , J 3 , J 4 and J 7 or HJ 3 Or J 7 or IJ 2 Or J 4 or J. 2-pyridine (i.e., J 1 ) or 2-pyrimidine (i.e., J 3 ) or K. 2-pyrimidine.

[0044] In an embodiment of each aspect of the present invention, Z1 teeth A. Halogens, CN, NH 2 C(O), amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, (C 1 ~C 3 Alkyl)C(O), HC(O), diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle selected from pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl and tetrazolyl, wherein phenyl or a 5-membered aromatic heterocycle is selected from C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxy; B. Halogens, CN, NH 2 C(O), amino, (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 Haloalkoxy, (C 1 ~C 3 alkyl)C(O), HC(O) or diphenylmethanimine; or C. Halogen, CN, Amino, Di(C1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkyl sulfonyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3haloalkoxy or diphenylmethanimine; or D. Halogen, CN, Amino, Di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 haloalkoxy or diphenylmethanimine; or E. Halogen, CN, Amino, Di(C1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C1-C3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 haloalkoxy or diphenylmethanimine; or F. Halogen, CN, Amino, Di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C1 ~C 4 Haloalkylsulfonyl, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C1-C3 cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 haloalkoxy or diphenylmethanimine; or G. Halogen, CN, Amino, Di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 haloalkoxy or diphenylmethanimine; or H. Halogen, CN, Amino, Di(C 1 ~C3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 1 ~C 3 Haloalkoxy or C 3 ~C 4 is cyanocycloalkyl; or I. Halogen, CN, Amino, C 3 ~C 4 Halocycloalkyl, C 1 ~C 3 Haloalkoxy or C 3 ~C 4 is cyanocycloalkyl; or J. Halogen, Amino, C 3 ~C 4 Halocycloalkyl, C 1 ~C 3 Haloalkoxy or C 3 ~C 4 is cyanocycloalkyl; or K. Halogen, amino or C 1 ~C 3 haloalkoxy; or L. trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, fluoro, amino, 2,2,2-trifluoroethoxy, bromo or iodo; or M is trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino; or N is bromo, chloro, iodo, difluoromethoxy, trifluoromethoxy, or amino; or O. bromo, chloro, iodo, difluoromethoxy or trifluoromethoxy; or P. Bromo, chloro or iodo.

[0045] The present invention therefore relates to a compound represented by the formula: 1 , R 2 , R 3 , R 4 and Z 1In one embodiment, compounds of formula I are available having all combinations / permutations of R 1 In embodiment D (i.e., hydrogen, C 1 ~C 6 Alkyl or C 3 ~C 4 Cycloalkyl C 1 ~C 2 alkyl-) and R 2 is embodiment H (i.e., 3,5-bis(trifluoromethyl)phenyl, 3,5-dichlorophenyl, 3-trifluoromethoxyphenyl, 3-chloro-5-trifluoromethylphenyl, 3-cyanophenyl, 3-chloro-5-trifluoromethoxyphenyl, or 5-trifluoromethylpyridin-3-yl); R 3 is embodiment C (i.e., methyl); R 4 is embodiment A (i.e., pyridine or pyrimidine, wherein the pyridine, pyrimidine has one C 1 ~C 3 and Z is optionally substituted with alkoxy or halogen; 1 In embodiment E (i.e., halogen, CN, amino, di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C1-C3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 Compounds of formula I which are haloalkoxy or diphenylmethanimine) are available.

[0046] In an embodiment of each aspect of the invention, the compound of formula I is 1 As hydrogen, C 1 ~C 6 Alkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkynyl, C 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl-(where C 3 ~C 4 cycloalkyl is optionally substituted with 1 or 2 halo atoms) or oxetan-3-yl-CH 2 - has; R 2 as phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with 1 to 2 substituents, provided that no substituents are on either carbon adjacent to the carbon to which C=O is attached, and each substituent is selected from the group consisting of C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3haloalkoxy, halogen, or CN; R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0047] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl, allyl, proparyl or cyclopropmethyl; 2 as phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with 1 to 2 substituents, provided that no substituents are on either carbon adjacent to the carbon to which C=O is attached, and each substituent is selected from the group consisting of C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C1 ~C 3 haloalkoxy, halogen, or CN; R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0048] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0049] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 5 , Y 6 , Y 11 , Y 13 , Y 15 , Y 19 and Y 20 R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0050] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 5 , Y 6 , Y 11 , Y 13 , Y 15 , Y 19 Or Y 20 R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0051] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0052] In an embodiment of each aspect of the invention, the compound of formula I is 1R has hydrogen, methyl or cyclopropmethyl; 2 As Y 1 R 3 As, C 1 ~C 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3 optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0053] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As the aryl group, pyridine or pyrimidine is preferably used, and the pyridine or pyrimidine is preferably used, and more preferably has one C 1 ~C 3optionally substituted with alkoxy or halogen; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0054] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As the alkyl group, 2-pyridine or 2-pyrimidine is preferably C 1 ~C 3 optionally substituted with alkoxy or halo; and Z 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0055] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 1 ~J 8 and Z. 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0056] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 1 ~J 8 and Z. 1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0057] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 1 Or J 3 and Z.1 As halogen, CN, amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), (C 1 ~C 3 Cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl)(C 1 ~C 3alkyl)NC(O), (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein phenyl or a 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 which may be optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxyl.

[0058] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 1 ~J 8 and Z. 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0059] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J1 ~J 8 and Z. 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0060] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 1 ~J 8 and Z. 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0061] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 1 ~J 8 and Z. 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0062] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R3 R 4 As J 1 ~J 8 and Z. 1 As such, the aryl group has trifluoromethoxy, difluoromethoxy, chloro, bromo, iodo or amino.

[0063] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 2 , J 3 , J 4 and J 7 and Z. 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0064] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 2 , J 3 , J 4 and J 7 and Z. 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0065] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl;2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 2 , J 3 , J 4 and J 7 and Z. 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0066] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 2 , J 3 , J 4 and J 7 and Z. 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0067] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 2 , J 3 , J 4 and J 7 and Z. 1As such, the aryl group has trifluoromethoxy, difluoromethoxy, chloro, bromo, iodo or amino.

[0068] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 1 Or J 3 and Z 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0069] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J 1 Or J 3 and Z 1 as halogen, amino or C 1 ~C 3 Contains haloalkoxy.

[0070] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 , Y 6 , Y 11 , Y 15 , Y 19 Or Y 20 R 3 R 4 As J1 Or J 3 and Z 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0071] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 1 Or J 3 and Z 1 As such, the aryl group may have trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino.

[0072] In an embodiment of each aspect of the invention, the compound of formula I is 1 R has hydrogen, methyl or cyclopropmethyl; 2 As, Y 1 ~Y 21 R 3 R 4 As J 1 Or J 3 and Z 1 As such, the aryl group has trifluoromethoxy, difluoromethoxy, chloro, bromo, iodo or amino.

[0073] In a second aspect, the present invention makes available a composition comprising a compound of formula I as defined in the first aspect, one or more adjuvants and diluents and optionally one or more other active ingredients.

[0074] In a third aspect, the present invention makes available a method for combating and controlling insects, acarids, nematodes or molluscs, which comprises the step of applying to the pest, the pest's habitat or to plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect.

[0075] In a fourth aspect, the present invention makes available a method for the protection of plant propagation material from attack by insects, acarids, nematodes or mollusks, which comprises the step of treating the propagation material or the locus in which 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.

[0076] In a fifth aspect, the present invention makes available plant propagation material, such as seeds, which comprises, is treated with or has attached thereto a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0077] In a further aspect, the present invention provides a method of controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound of formula I as defined in the first aspect.The present invention further provides a method of controlling ectoparasites on an animal in need thereof comprising administering an effective amount of a compound of the first aspect.The present invention further provides a method of preventing and / or treating diseases transmitted by ectoparasites comprising administering to an animal in need thereof an effective amount of a compound of formula I as defined in the first aspect.

[0078] Compounds of formula I can be prepared by those skilled in the art by following known methods. More specifically, compounds and intermediates of formula I and I'a can be prepared as described below in the schemes and examples. The specific stereogenic centers are left unspecified for the sake of brevity and are not intended to limit the teaching of the schemes in any way.

[0079] The processes for preparing the compounds of formula I according to the invention are carried out by methods known to those skilled in the art. [ka] Amines of Formula II [ka] (In the formula, R 1 , R 3 , R 4 , Z 1 is as described in formula I) and a carboxylic acid derivative of formula III [ka] (In the formula, R 2 is as described in Formula I). ​​The chemistry is described in more detail in Scheme 1.

[0080] Scheme 1: [ka] In Scheme 1, a compound of formula III, where R 2 is as defined in formula I) is activated to a compound of formula IIIa by methods known to those skilled in the art and described, for example, in Tetrahedron, 61(46), 10827-10852, 2005. For example, X 0Compounds in which R is a halogen are formed, for example, by treatment of compounds of formula III with oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as methylene dichloride or THF at temperatures between 20° C. and 100° C., preferably 25° C. Compounds of formula II, in which R 1 , R 3 , R 4 and Z 1 Treatment of IIIa with X, optionally in the presence of a base such as triethylamine or pyridine, provides compounds of formula I. Alternatively, compounds of formula I can be prepared by catalyzing the reaction of an activated species IIIa (where X 0 are X 01 , X 02 and X 03 ), which is obtained by dicyclohexylcarbodiimide (DCC), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC) or (1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), for example in pyridine, DMF, acetonitrile, CH 2 Cl 2 or THF, optionally in the presence of a base, for example triethylamine, at temperatures between 30 and 180° C. Finally, acids of formula III can be prepared by the treatment of compounds of formula IIIa, where X is a carboxylic acid, as described, for example, in Synthesis 2013, 45, 1569. 0 X 04 Further reaction with an amine of formula II provides a compound of formula I.

[0081] A compound of formula II, where R 1 , R 3 , R 4 and Z 1(wherein x is as defined above) are generally known or can be readily prepared by one skilled in the art. A typical example of such a synthesis is shown in Scheme 2.

[0082] Scheme 2. [ka] For example, a compound of formula II can be prepared by reacting a compound of formula VI, where R 3 , R 4 and Z 1 is as defined in formula I) and a compound of formula VIII, 1 is as defined in formula I) with

[0083] A compound of formula VI, where R 3 , R 4 and Z 1 is as defined above) in a suitable solvent which may comprise, for example, a mixture of acetic acid and 1,4-dioxane, typically under heating at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, to obtain a compound of formula IVa, where R 3 and Z 1 is as defined in formula I) and a compound of formula VII, 4 is as defined in formula I). ​​Such a process has already been described, for example, in Tetrahedron 2017, 73, 750.

[0084] A compound of formula IVa, where R 3 and Z 1is as defined above) can be reacted with a compound of formula IV, where R is as defined above, in a suitable solvent which may comprise, for example, DMF, in the presence of a suitable base, such as DIPEA, under heating at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture. 3 is as defined in formula I) and a compound of formula V, 1 is as defined in formula I). ​​Such a process has already been described, for example, in Journal of Organic Chemistry, 2011, 76, 1177.

[0085] Alternatively, a compound of formula I, wherein R 1 , R 2 , R 3 , R 4 and Z 1 wherein is as defined above) can also be prepared by the process shown in Scheme 3.

[0086] Scheme 3. [ka] For example, a compound of formula I, where R 1 , R 2 , R 3 , R 4 and Z 1 is as defined above) in a suitable solvent which may comprise, for example, a mixture of acetic acid and 1,4-dioxane, typically at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, under heating, optionally under microwave heating conditions, a compound of formula XIII, where R 1 , R 2 , R 3 and Z 1 is as defined above) and a compound of formula VII, 4 is as defined in formula I). ​​Such a process has already been described, for example, in Tetrahedron 2017, 73, 750.

[0087] A compound of formula XIII, where R 1 , R 2 , R 3 and Z 1 is as defined above), in a suitable solvent which may comprise, for example, DMF, in the presence of a suitable base, such as DIPEA, under heating at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, a compound of formula XII, where R 1 , R 2 and R 3 is as defined above) and a compound of formula V, 1 is as defined in formula I). ​​Such a process has already been described, for example, in J. Org. Chem., 2011, 76, 1177.

[0088] A compound of formula XII, where R 1 , R 2 and R 3 is as defined above) in THF / H 2 In a suitable solvent, which may contain a mixture of 1,2-dichlorophenyl ether, ... and 1,2-dichlorophenyl ether, typically at room temperature to 200° C., under heating, a compound of formula XI, where R 1 , R 2 and R 3 wherein R is as defined above) with a base such as lithium hydroxide or sodium hydroxide.

[0089] A compound of formula XI, where R 1 , R 2 and R 3 is as defined above) can be used in, for example, pyridine, DMF, acetonitrile, CH 2 Cl 2 or THF, optionally in the presence of a base, for example triethylamine or pyridine, and typically with heating at temperatures between room temperature and 200° C. 2 and Xo are as defined above) with a compound of formula X, where R 1and R 3 can be prepared by reaction with

[0090] A compound of formula X, where R 1 and R 3 is as defined above) in a suitable solvent which may comprise, for example, acetonitrile or dioxane, in the presence of a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate), typically under heating at temperatures between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, to obtain a compound of formula IX, where R 3 is as defined in formula I) and a compound of formula VIII, 1 is as defined in formula I) with

[0091] Alternatively, a compound of formula I, wherein R 1 , R 2 , R 3 , R 4 and Z 1 wherein is as defined above) can also be prepared by the process shown in Scheme 4.

[0092] Scheme 4. [ka] For example, a compound of formula I, where R 1 , R 2 , R 3 , R 4 and Z 1 is as defined above), optionally in the presence of a copper catalyst, for example CuI, in the presence of a suitable solvent, such as DMF or NMP, in the presence of a suitable base, such as sodium hydrogen carbonate, potassium carbonate or cesium carbonate, typically under heating at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, to give a compound of formula XV, where R 1 , R2 , R 3 and Z 1 is as defined above) and a compound of formula XVI, 4 is as defined in formula I, and Hal is a halogen, such as chlorine, bromine or iodine. Such processes have been described, for example, in Chem.Asian J.2014,9,166; and also in WO2013161904 and WO2009131173.

[0093] A compound of formula XV, where R 1 , R 2 , R 3 and Z 1 is as defined above), can be reacted with a compound of formula XIV, where R 1 , R 2 and R 3 is as defined above) and a compound of formula V, 1 is as defined above).

[0094] A compound of formula XIV, where R 1 , R 2 and R 3 is as defined above), can be reacted with a compound of formula XII, where R 1 , R 2 and R 3 (wherein R is as defined above) with ethyl chloroformate and hydrazine. Such a process has already been described, for example, in WO2008055013.

[0095] Compounds of formula Ia, where R 1 , R2 , R 3 and R 4 wherein Xa is as defined above and Xa is a halogen, such as chlorine, bromine or iodine, can be prepared by the process shown in Scheme 5.

[0096] Scheme 5. [ka] For example, a compound of formula Ia, where R 1 , R 2 , R 3 and R 4 is as defined above and Xa is a halogen such as chlorine, bromine or iodine, optionally in the presence of a copper catalyst, for example CuI, in the presence of a suitable solvent, for example DMF or NMP, in the presence of a suitable base, for example sodium hydrogen carbonate, potassium carbonate or cesium carbonate, under heating, typically at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, to give a compound of formula XVa, where R 1 , R 2 and R 3 is as defined above and Xa is a halogen, such as chlorine, bromine or iodine, with a compound of formula XVI, where R 4 is as defined above and Hal is a halogen, such as chlorine, bromine or iodine. Such processes have been described, for example, in Chem.Asian J.2014,9,166; and also in WO2013161904 and WO2009131173.

[0097] A compound of formula XVa, where R 1 , R 2 , R 3 and Xa are as defined above) can be, for example, CH 2 Cl 2in the presence of a suitable base such as sodium hydroxide, potassium hydroxide or lithium hydroxide, typically at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, in a suitable solvent which may contain 1 , R 2 and R 3 (wherein R is as defined above) can be prepared by halogenation with a halogenating agent such as benzyltrimethylammonium tribromide, N-iodosuccinimide, etc. Such a process has already been described, for example, in US Patent Application Publication No. 2014206700 (see pages 37-38).

[0098] A compound of formula XVIII, where R 1 , R 2 and R 3 is as defined above), in a suitable solvent which may comprise, for example, acetic acid, a mixture of acetic acid and 1,4-dioxane or a mixture of acetic acid and toluene, typically at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, under heating, optionally under microwave heating conditions, a compound of formula XVII, where R 1 , R 2 and R 3 (wherein R is as defined above) with hydrazine. Such a process has already been described, for example, in J. Heterocyclic Chem. 2008, 45, 887; Bioorg. Med. Chem. Lett. 2015, 25, 5121.

[0099] An intermediate of formula XVII, where R 1 , R 2 and R 3 where x is as defined above) can be prepared by the process shown in Scheme 6.

[0100] Scheme 6. [ka] A compound of formula XVII, where R 1 , R 2 and R 3 is as defined above) can be reacted with a compound of formula XXI, where R 1 , R 2 and R 3 (wherein is as defined above) with N,N-dimethylformamide dimethyl acetal (DMF-DMA). Such a process has already been described, for example, in Tetrahedron 2017, 73, 750 and US Patent Publication No. 2016296501, Preparation 7, page 29.

[0101] A compound of formula XXI, where R 1 , R 2 and R 3 is as defined above) can be used in, for example, pyridine, DMF, acetonitrile, CH 2 Cl 2 or THF, optionally in the presence of a base, for example triethylamine or pyridine, and typically with heating at temperatures between room temperature and 200° C. 1 and R 3 is as defined above) and a compound of formula IIIa, 2 and Xo can be prepared by reaction with (as defined in Scheme 1).

[0102] A compound of formula XX, where R 1 and R 3is as defined above) in a suitable solvent which may comprise, for example, acetonitrile or dioxane, in the presence of a suitable base such as sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate), typically under heating at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions, to obtain a compound of formula XIX, where R 3 is as defined in formula I) and a compound of formula VIII, 1 is as defined in formula I) with

[0103] Alternatively, a compound of formula I, wherein R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1a is diphenylmethanimine, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkoxyalkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 haloalkynyl, phenyl or a 5-membered aromatic heterocycle, where phenyl or a 5-membered aromatic heterocycle is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 wherein R 1 is an integer from 1 to 3, and R 2 is an integer from 1 to 3, and R 3 ...

[0104] Scheme 7. [ka] A compound of formula I, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1a is diphenylmethanimine, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Alkoxyalkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 haloalkynyl, phenyl or a 5-membered aromatic heterocycle, where phenyl or a 5-membered aromatic heterocycle is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 R 1 is optionally substituted with 1 to 3 substituents selected from cycloalkyl, halogen, CN, or hydroxy, as depicted in Scheme 7, can be reacted with a compound of formula Ia, where R 1 , R 2 , R 3 , R 4 and X a is as previously described) and a compound of formula XXII, 1a is as above, and W 0 can be prepared by reaction with a boronic acid or boronic ester or a tin compound or hydrogen. This reaction can be carried out, for example, with Pd(PPh 3 ) 4In the presence of a palladium catalyst such as , in the presence of a suitable solvent such as dioxane or toluene, in the presence of a suitable base such as potassium carbonate or cesium carbonate, under heating at a temperature usually between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture, optionally under microwave heating conditions. Such processes have already been described, for example, in WO2016006523 or in J.Med.Chem.,2014,57,3687-3706.

[0105] Compounds of formula Ic, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1b is amino, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N or (C 1 ~C 3 Alkyl)C(O)NH) can be prepared by the process shown in Scheme 8.

[0106] Scheme 8. [ka] Compounds of formula Ic, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1b is (C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C3 alkyl)amino, (C 1 ~C 3 Alkyl)C(O)(C 1 ~C 3 Alkyl)N or (C 1 ~C 3 The compound Ib" (where R 1 , R 2 , R 3 , R 4 is as defined above) and compound XXIII (wherein X 0 is shown in Scheme 1, and X shown in Scheme 1 01 , X 02 , X 03 and X 04 and Z 2 is (C 1 ~C 3 Alkyl), (C 1 ~C 3 alkyl)sulfonyl or (C 1 ~C 3 The compound obtained can be optionally alkylated in a second step by treating the latter with compound XXIV (wherein LG is a leaving group such as chlorine, mesyloxy or tosyloxy) in a suitable solvent such as THF or DMF, in the presence of a suitable base such as trimethylamine or pyridine, under heating at a temperature usually between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture. Such transformations are easily performed by those skilled in the art or are cautioned as described in WO 2010010186 or Eur. J. Med. Chem, 2013, 67, 243-251.

[0107] Compounds of formula Ib" (wherein R 1 , R 2 , R 3 , R4 is as defined above) can be prepared by reacting compound Ib′ (where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1aa is diphenylmethanimine). This reaction is carried out in a suitable solvent such as THF, in the presence of an acid such as hydrogen chloride or citric acid, usually at a temperature between room temperature and 200° C., preferably at 20° C. to the boiling point of the reaction mixture. Such processes have already been described, for example, in WO 2018067432 or Eur. J. Med. Chem, 2018, 144, 151-163.

[0108] Compounds of formula Id, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1c is a halogen such as chlorine, bromine or iodine, CN, (C 1 ~C 3 Alkyl)amino, C 2 ~C 6 Alkenyl or C 1 ~C 4 Scheme 9 is a process for preparing alkylsulfanyl compounds, which may be prepared by the process shown in Scheme 9.

[0109] Scheme 9. [ka] Compounds of formula Id, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1c is a halogen such as chlorine, bromine or iodine, CN, (C 1 ~C 3 Alkyl)amino, C 2 ~C 6 Alkenyl or C 1 ~C 4alkylsulfanyl) can be prepared by reacting a compound of formula Ib′, where R 1 , R 2 , R 3 and R 4 is as previously described) and a compound of formula XXV (wherein Z 1c is as above, and W 1 is hydrogen, an alkali metal or copper). This reaction is carried out by treating a compound of formula Ib' with a suitable nitrosating agent such as sodium nitrite, t-butyl nitrite or isoamyl nitrite in the presence of a suitable acid such as hydrochloric acid, sulfuric acid or tetrafluoroboric acid in a suitable solvent such as acetonitrile or water at a temperature usually between 0° and room temperature. This diazonium intermediate can be converted to a compound of formula XXV (wherein Z is hydrogen, an alkali metal or copper) by heating, usually at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture. 1c and W 1 (wherein R is as described above). Such processes have already been described, for example, in WO 2010141796 or in J. Med. Chem. 1990, 33, 1230-41.

[0110] Compounds of formula Ie, where R 1 , R 2 , R 3 , R 4 is as defined above, and Z 1d is hydroxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl or C 1 ~C 3 haloalkoxy) can be prepared by the process shown in Scheme 10.

[0111] Scheme 10. [ka] Compounds of formula Ie, where R 1 , R 2 , R 3 , R 4is as defined above, and Z 1d is hydroxy, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl or C 1 ~C 3 haloalkoxy) can be used in the compounds of formula Ic" where R 1 , R 2 , R 3 and R 4 is as previously described) and a compound of formula XXVI, 1d is as above and LG is a leaving group such as chlorine, triflate, mesyloxy or tosyloxy, or alternatively, by reaction of compound Ic″ above with 2-chloro-2,2-difluoro-acetic acid. The reaction is carried out in a suitable solvent such as acetonitrile or DMF, in the presence of a suitable base such as triethylamine or potassium carbonate, and under heating, usually at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture.

[0112] Compounds of formula Ic" can be prepared by heating in a suitable solvent such as acetic acid or water, usually at a temperature between room temperature and 200°C, preferably at a temperature between 20°C and the boiling point of the reaction mixture, to give compounds of formula Ic', where R 1 , R 2 , R 3 and R 4 (as described above) with a suitable acid, such as hydrobromic acid or hydrochloric acid. Such processes have been described, for example, in US Patent Publication No. 20090291967 or in Bioorganic & Medicinal Chemistry 2018, 26, 3321-3344.

[0113] Formula III 1 (where R 2 is Y 1 , Y 3 , Y 5 Or Y 11 ) is commercially available and was not prepared by the inventors themselves.

[0114] Formula III 2 (where R 2 is Y 6 ) can be prepared by the process shown in Scheme 11.

[0115] Scheme 11. [ka] Formula III 2 (where R 2 is Y 6 (which is a fluoride-containing amine) can be prepared by converting compound XXVIII by treatment with 1,3-dibromo-5,5-dimethylhydantoin and hydrogen fluoride in a suitable solvent, which may include, for example, dichloromethane, at low temperatures, usually between −78° C. and 0° C. The resulting compound can then be reacted under classical conditions known to those skilled in the art (sodium or lithium hydroxide, MeOH / THF / H 2 O) to the corresponding carboxylic acid.

[0116] Compounds of formula XXVIII can be prepared by reaction of compound XXVII with carbon disulfide in a suitable solvent, which may include, for example, DMF, in the presence of a suitable base, such as sodium hydride, and under heating, usually at temperatures between room temperature and 200° C., followed by a methylation step with methyl iodide as a methylating agent. Such a process has been described, for example, in Bioorg.Med.Chem. 2007,17,4308, and other conditions can be found, for example, in J.Fluorine Chem. 2015,179,48 or Chem.Soc.Jp. 2000,73,471.

[0117] Formula III 3 (where R 2 is Y 13 ) can be prepared by the process shown in Scheme 12.

[0118] Scheme 12. [ka] Formula III 3 (where R 2 is Y 13 is MeOH, THF, H 2 XXX can be prepared by reaction of compound XXX with a suitable base, such as sodium hydroxide or lithium hydroxide, in a suitable solvent, such as 0 or a mixture of these three, usually under heating at temperatures between room temperature and reflux.

[0119] Compounds of formula XXX can be prepared by reaction of compound XXIX with a suitable copper trifluoromethylthiolate reagent, such as (bpy)CuSCF3, in a suitable solvent, which may comprise, for example, acetonitrile, under heating, usually at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture. Such a process has already been described, for example, in Angew. Chem. Int. Ed. 2013, 52, 1548-1552.

[0120] Formula III 4 (where R 2 is Y 15 ) can be prepared by the process shown in Scheme 13.

[0121] Scheme 13. [ka] Formula III 4 (where R 2 is Y 15 (wherein X is an integer from 1 to 3) can be prepared by reaction of compound XXXI with compound XXXII in a suitable solvent, which may include, for example, chloroform, in the presence of a suitable base, such as sodium hydroxide, under heating, usually at temperatures between room temperature and reflux. Such a process has already been described, for example, in WO2002044145.

[0122] Depending on the method 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, alkylamides, alkylenediamides, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples which 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).

[0123] The reactants can be reacted with each other as is, i.e. without the addition of a solvent or diluent. In most cases, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. When the reaction is carried out in the presence of a base, the base used in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also serve as the solvent or diluent.

[0124] The reaction is advantageously carried out at a temperature in the range of about -80°C to about +140°C, preferably about -30°C to about +100°C, and in many cases in the range of ambient temperature to about +80°C.

[0125] Depending on the respective suitable reaction conditions and the choice of starting materials, it is possible, for example, to simply replace one substituent with another substituent according to the invention in one reaction step, or multiple substituents can be replaced with other substituents according to the invention in the same reaction step.

[0126] Salts of compounds of formula I can be prepared in a manner known per se: thus, for example, acid addition salts of compounds of formula I can be obtained by treatment with a suitable acid or with a suitable ion exchange reagent, and base salts can be obtained by treatment with a suitable base or with a suitable ion exchange reagent.

[0127] The salts of the compounds of formula I can be converted in a customary manner, for example into acid-addition salts of the free compounds I by treatment with suitable basic compounds or with suitable ion exchange reagents, and into base salts, for example by treatment with a suitable acid or with a suitable ion exchange reagent.

[0128] Salts of compounds of formula I may be converted into other salts, such as acid addition salts, of compounds of formula I in a manner known per se, for example by treating the inorganic acid salt, such as the hydrochloride, with a suitable metal salt, such as the sodium, barium or silver salt of the acid, for example silver acetate, in a suitable solvent in which the inorganic salt that forms silver chloride is insoluble and therefore precipitates from the reaction mixture.

[0129] Depending on the procedure or reaction conditions, compounds of formula I having salt-forming properties may be obtained in free form or in salt form.

[0130] The compounds of formula I and, where appropriate, their tautomers, can exist in the form of pure isomers, such as, for example, enantiomers and / or diastereomers, or as isomeric mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures, depending on the number, the absolute and relative configuration of asymmetric carbon atoms occurring in the molecule and / or depending on the configuration of non-aromatic double bonds occurring in the molecule, respectively in free or salt form; the invention relates to the pure isomers and also to all possible isomeric mixtures, and is to be understood in this sense above and below, respectively, even if the respective stereochemical details are not specifically stated.

[0131] Diastereomeric or racemic mixtures of compounds of formula I, in free or salt form, obtained depending on which starting materials and procedures are selected, may be separated in known manner into pure diastereomers or racemates on the basis of the physical chemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0132] Enantiomeric mixtures, such as racemates, obtained in a similar manner can be resolved into their optical antipodes by known methods, for example by recrystallization from optically active solvents, by chromatography on chiral adsorbents, for example by high performance liquid chromatography (HPLC) on acetylcellulose using suitable microorganisms, by cleavage with specific immobilized enzymes via the formation of inclusion compounds, for example with chiral crown ethers, whereby 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, such as 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 thus obtained, for example by fractional crystallization based on different solubilities, to obtain diastereomers from which the desired enantiomer can be released, by the action of a suitable substance, for example a basic substance.

[0133] Pure diastereomers or enantiomers can be obtained according to the invention not only by separating the appropriate isomeric mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, e.g. by carrying out the process according to the invention using stereochemically specific starting materials.

[0134] The N-oxide can be prepared by reacting a compound of formula I with a suitable oxidizing agent, e.g., H in the presence of an acid anhydride, e.g., trifluoroacetic anhydride. 2 O 2 / urea adduct. Such oxidations are known from the literature, for example from J. Med. Chem., 32(12), 2561-73, 1989 or WO 2000 / 15615.

[0135] When the individual components have different biological activities, it may be advantageous to isolate or synthesize the respective more biologically effective isomer, e.g., enantiomer or diastereomer, or mixture of isomers, e.g., mixture of enantiomers or diastereomers.

[0136] The compounds of formula I and, where appropriate, their tautomers, may also be obtained in free or salt form, optionally in the form of hydrates, and / or contain other solvents, for example solvents that may have been used for the crystallization of compounds present in solid form.

[0137] In a further aspect, the present invention provides a compound of formula XV [ka] (In the formula, R 1 , R 2 , R 3 and Z 1 is as defined in the first aspect according to formula (I), or the stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I, or an agrochemically acceptable salt thereof. 1 , R 2 , R 3 and Z 1The embodiments described for also apply to formula (XV).

[0138] In a preferred embodiment, the compound of formula XV is R 2 As embodiments L and R 1 As embodiments L and R 3 As embodiments C and Z 1 As an embodiment, it has one of the embodiments A to M.

[0139] In a further aspect, the present invention provides a compound of formula II [ka] (In the formula, R 1 , R 3 , R 4 and Z 1 is as defined for the first aspect according to formula (I) or the stereoisomers, enantiomers, tautomers and N-oxides of the compounds of formula I, or an agrochemically acceptable salt thereof. 1 , R 2 , R 3 and Z 1 The embodiments described for also apply to formula (II).

[0140] In a preferred embodiment, the compound of formula II is R 1 As embodiments L and R 3 As embodiments C and R 4 As embodiments G and Z 1 As an embodiment, it has one of the embodiments A to P.

[0141] The compounds of formula I according to the following Tables A-1 to A-92 can be prepared according to the above-mentioned methods. The following examples are intended to illustrate the present invention and to present preferred compounds of formula I in the form of compounds of formula Ia. [ka]

[0142] Table A-1 provides 45 compounds of formula Iaa, A-1.001 to A-1.045, where R 1 is H and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z. For example, A-1.009 is [ka] It is.

[0143] [Table 1-1] [Table 1-2]

[0144] Table A-2 provides 45 compounds of formula Iaa, A-2.001 to A-2.045, where R 1 is H and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0145] Table A-3 provides 45 compounds of formula Iaa, A-3.001 to A-3.045, where R 1 is H and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0146] Table A-4 provides 45 compounds of formula Iaa, A-4.001 to A-4.045, where R 1 is H and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0147] Table A-5 provides 45 compounds of formula Iaa, A-5.001 to A-5.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0148] Table A-6 provides 45 compounds of formula Iaa, A-6.001 to A-6.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0149] Table A-7 provides 45 compounds of formula Iaa, A-7.001 to A-7.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0150] Table A-8 provides 45 compounds of formula Iaa, A-8.001 to A-8.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0151] Table A-9 provides 45 compounds of formula Iaa, A-9.001 to A-9.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0152] Table A-10 provides 45 compounds of formula Iaa, A-10.001 to A-10.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0153] Table A-11 provides 45 compounds of formula Iaa, A-11.001 to A-11.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0154] Table A-12 provides 45 compounds of formula Iaa, A-12.001 to A-12.045, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0155] Table A-13 provides 45 compounds of formula Iaa, A-13.001 to A-13.045, where R 1 is H and R 2is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0156] Table A-14 provides 45 compounds of formula Iaa, A-14.001 to A-14.045, where R 1 is H and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0157] Table A-15 provides 45 compounds of formula Iaa, A-15.001 to A-15.045, where R 1 is H and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0158] Table A-16 provides 45 compounds of formula Iaa, A-16.001 to A-16.045, where R 1 is H and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0159] Table A-17 provides 45 compounds of formula Iaa, A-17.001 to A-17.045, where R 1 is H and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1is as defined in Table Z.

[0160] Table A-18 provides 45 compounds of formula Iaa, A-18.001 to A-18.045, where R 1 is H and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0161] Table A-19 provides 45 compounds of formula Iaa, A-19.001 to A-19.045, where R 1 is H and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0162] Table A-20 provides 45 compounds of formula Iaa, A-20.001 to A-20.045, where R 1 is H and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0163] Table A-21 provides 45 compounds of formula Iaa, A-21.001 to A-21.045, where R 1 is H and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0164] Table A-22 provides 45 compounds of formula Iaa, A-22.001 to A-22.045, where R 1 is H and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0165] Table A-23 provides 45 compounds of formula Iaa, A-23.001 to A-23.045, where R 1 is H and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0166] Table A-24 provides 45 compounds of formula Iaa, A-24.001 to A-24.045, where R 1 is H and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0167] Table A-25 provides 45 compounds of formula Iaa, A-25.001 to A-25.045, where R 1 is H and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0168] Table A-26 provides 45 compounds of formula Iaa, A-26.001 to A-26.045, where R1 is H and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0169] Table A-27 provides 45 compounds of formula Iaa, A-27.001 to A-27.045, where R 1 is H and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0170] Table A-28 provides 45 compounds of formula Iaa, A-28.001 to A-28.045, where R 1 is H and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0171] Table A-29 provides 45 compounds of formula Iaa, A-29.001 to A-29.045, where R 1 CH 3 and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0172] Table A-30 provides 45 compounds of formula Iaa, A-30.001 to A-30.045, where R 1 CH 3 and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0173] Table A-31 provides 45 compounds of formula Iaa, A-31.001 to A-31.045, where R 1 CH 3 and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0174] Table A-32 provides 45 compounds of formula Iaa, A-32.001 to A-32.045, where R 1 CH 3 and R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0175] Table A-33 provides 45 compounds of formula Iaa, A-33.001 to A-33.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0176] Table A-34 provides 45 compounds of formula Iaa, A-34.001 to A-34.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1is as defined in Table Z.

[0177] Table A-35 provides 45 compounds of formula Iaa, A-35.001 to A-35.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0178] Table A-36 provides 45 compounds of formula Iaa, A-36.001 to A-36.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0179] Table A-37 provides 45 compounds of formula Iaa, A-37.001 to A-37.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0180] Table A-38 provides 45 compounds of formula Iaa, A-38.001 to A-38.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0181] Table A-39 provides 45 compounds of formula Iaa, A-39.001 to A-39.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0182] Table A-40 provides 45 compounds of formula Iaa, A-40.001 to A-40.045, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0183] Table A-41 provides 45 compounds of formula Iaa, A-41.001 to A-41.045, where R 1 CH 3 and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0184] Table A-42 provides 45 compounds of formula Iaa, A-42.001 to A-42.045, where R 1 CH 3 and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0185] Table A-43 provides 45 compounds of formula Iaa, A-43.001 to A-43.045, where R 1 CH 3 and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0186] Table A-44 provides 45 compounds of formula Iaa, A-44.001 to A-44.045, where R 1 CH 3 and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0187] Table A-45 provides 45 compounds of formula Iaa, A-45.001 to A-45.045, where R 1 CH 3 and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0188] Table A-46 provides 45 compounds of formula Iaa, A-46.001 to A-46.045, where R 1 CH 3 and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0189] Table A-47 provides 45 compounds of formula Iaa, A-47.001 to A-47.045, where R 1 CH 3 and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0190] Table A-48 provides 45 compounds of formula Iaa, A-48.001 to A-48.045, where R 1 CH 3 and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0191] Table A-49 provides 45 compounds of formula Iaa, A-49.001 to A-49.045, where R 1 CH 3 and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0192] Table A-50 provides 45 compounds of formula Iaa, A-50.001 to A-50.045, where R 1 CH 3 and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0193] Table A-51 provides 45 compounds of formula Iaa, A-51.001 to A-51.045, where R 1 CH 3 and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0194] Table A-52 provides 45 compounds of formula Iaa, A-52.001 to A-52.045, where R 1 CH 3 and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0195] Table A-53 provides 45 compounds of formula Iaa, A-53.001 to A-53.045, where R 1 CH 3 and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0196] Table A-54 provides 45 compounds of formula Iaa, A-54.001 to A-54.045, where R 1 CH 3 and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0197] Table A-55 provides 45 compounds of formula Iaa, A-55.001 to A-55.045, where R 1 CH 3 and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0198] Table A-56 provides 45 compounds of formula Iaa, A-56.001 to A-56.045, where R 1 CH 3 and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0199] Table A-57 provides 45 compounds of formula Iaa, A-57.001 to A-57.045, where R 1 is cyclopropylmethyl, R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0200] Table A-58 provides 45 compounds of formula Iaa, A-58.001 to A-58.045, where R 1 is cyclopropylmethyl, R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0201] Table A-59 provides 45 compounds of formula Iaa, A-59.001 to A-59.045, where R1 is cyclopropylmethyl, R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0202] Table A-60 provides 45 compounds of formula Iaa, A-60.001 to A-60.045, where R 1 is cyclopropylmethyl, R 2 is [3,5-bis(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0203] Table A-61 provides 45 compounds of formula Iaa, A-61.001 to A-61.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0204] Table A-62 provides 45 compounds of formula Iaa, A-62.001 to A-62.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0205] Table A-63 provides 45 compounds of formula Iaa, A-63.001 to A-63.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0206] Table A-64 provides 45 compounds of formula Iaa, A-64.001 to A-64.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0207] Table A-65 provides 45 compounds of formula Iaa, A-65.001 to A-65.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0208] Table A-66 provides 45 compounds of formula Iaa, A-66.001 to A-66.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0209] Table A-67 provides 45 compounds of formula Iaa, A-67.001 to A-67.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0210] Table A-68 provides 45 compounds of formula Iaa, A-68.001 to A-68.045, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0211] Table A-69 provides 45 compounds of formula Iaa, A-69.001 to A-69.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0212] Table A-70 provides 45 compounds of formula Iaa, A-70.001 to A-70.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0213] Table A-71 provides 45 compounds of formula Iaa, A-71.001 to A-71.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0214] Table A-72 provides 45 compounds of formula Iaa, A-72.001 to A-72.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0215] Table A-73 provides 45 compounds of formula Iaa, A-73.001 to A-73.045, where R 1 is cyclopropylmethyl, R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0216] Table A-74 provides 45 compounds of formula Iaa, A-74.001 to A-74.045, where R 1 is cyclopropylmethyl, R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0217] Table A-75 provides 45 compounds of formula Iaa, A-75.001 to A-75.045, where R 1 is cyclopropylmethyl, R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0218] Table A-76 provides 45 compounds of formula Iaa, A-76.001 to A-76.045, where R 1is cyclopropylmethyl, R 2 is [3-bromo-5-(trifluoromethyl)phenyl], R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0219] Table A-77 provides 45 compounds of formula Iaa, A-77.001 to A-77.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0220] Table A-78 provides 45 compounds of formula Iaa, A-78.001 to A-78.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0221] Table A-79 provides 45 compounds of formula Iaa, A-79.001 to A-79.045, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0222] Table A-80 provides 45 compounds of formula Iaa, A-80.001 to A-80.045, where R 1 is cyclopropylmethyl, R 2is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0223] Table A-81 provides 45 compounds of formula Iaa, A-81.001 to A-81.045, where R 1 is cyclopropylmethyl, R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0224] Table A-82 provides 45 compounds of formula Iaa, A-82.001 to A-82.045, where R 1 is cyclopropylmethyl, R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0225] Table A-83 provides 45 compounds of formula Iaa, A-83.001 to A-83.045, where R 1 is cyclopropylmethyl, R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0226] Table A-84 provides 45 compounds of formula Iaa, A-84.001 to A-84.045, where R 1 is cyclopropylmethyl, R 2is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0227] Table A-85 provides 45 compounds of formula Iaa, A-85.001 to A-85.045, where R 1 is H and R 2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0228] Table A-86 provides 45 compounds of formula Iaa, A-86.001 to A-86.045, where R 1 is H and R 2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0229] Table A-87 provides 45 compounds of formula Iaa, A-87.001 to A-87.045, where R 1 is H and R 2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0230] Table A-88 provides 45 compounds of formula Iaa, A-88.001 to A-88.045, where R 1 is H and R 2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4is (5-bromopyrimidin-2-yl), and Z 1 is as defined in Table Z.

[0231] Table A-89 provides 45 compounds of formula Iaa, A-89.001 to A-89.045, where R 1 is H and R 2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is 2-pyridyl, and Z 1 is as defined in Table Z.

[0232] Table A-90 provides 45 compounds of formula Iaa, A-90.001 to A-90.045, where R 1 is H and R 2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromo-2-pyridyl), and Z 1 is as defined in Table Z.

[0233] Table A-91 provides 45 compounds of formula Iaa, A-91.001 to A-91.045, where R 1 is H and R 2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is pyrimidin-2-yl, and Z 1 is as defined in Table Z.

[0234] Table A-92 provides 45 compounds of formula Iaa, A-92.001 to A-92.045, where R 1 is H and R 2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], and R 4 is (5-bromopyrimidin-2-yl), and Z 1is as defined in Table Z.

[0235] Certain intermediate compounds of formula XV are also made available. The following Tables B-1 to B-21 illustrate certain compounds of formula XVaa. [ka]

[0236] Table B-1 provides four compounds of formula XVaa, B-1.001 to B-1.004, where R 1 is H and R 2 is [3,5-bis(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0237] [Table 2]

[0238] Table B-2 provides four compounds of formula XVaa, B-2.001 to B-2.004, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0239] Table B-3 provides four compounds of formula XVaa, B-3.001 to B-3.004, where R 1 is H and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and Z 1 is as defined in Table W.

[0240] Table B-4 provides four compounds of formula XVaa, B-4.001 to B-4.004, where R 1 is H and R 2is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0241] Table B-5 provides four compounds of formula XVaa, B-5.001 to B-5.004, where R 1 is H and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0242] Table B-6 provides four compounds of formula XVaa, B-6.001 to B-6.004, where R 1 is H and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and Z 1 is as defined in Table W.

[0243] Table B-7 provides four compounds of formula XVaa, B-7.001 to B-7.004, where R 1 is H and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0244] Table B-8 provides four compounds of formula XVaa, B-8.001 to B-8.004, where R 1 CH 3 and R 2 is [3,5-bis(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0245] Table B-9 provides four compounds of formula XVaa, B-9.001 to B-9.004, where R 1 CH 3 and R2 is [3-chloro-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0246] Table B-10 provides four compounds of formula XVaa, B-10.001 to B-10.004, where R 1 CH 3 and R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and Z 1 is as defined in Table W.

[0247] Table B-11 provides four compounds of formula XVaa, B-11.001 to B-11.004, where R 1 CH 3 and R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0248] Table B-12 provides four compounds of formula XVaa, B-12.001 to B-12.004, where R 1 CH 3 and R 2 is [3-bromo-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0249] Table B-13 provides four compounds of formula XVaa, B-13.001 to B-13.004, where R 1 CH 3 and R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and Z 1 is as defined in Table W.

[0250] Table B-14 provides four compounds of formula XVaa, B-14.001 to B-14.004, where R 1 CH 3 and R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0251] Table B-15 provides four compounds of formula XVaa, B-15.001 to B-15.004, where R 1 is cyclopropylmethyl, R 2 is [3,5-bis(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0252] Table B-16 provides four compounds of formula XVaa, B-16.001 to B-16.004, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0253] Table B-17 provides four compounds of formula XVaa, B-17.001 to B-17.004, where R 1 is cyclopropylmethyl, R 2 is [3-chloro-5-(trifluoromethoxy)phenyl], and Z 1 is as defined in Table W.

[0254] Table B-18 provides four compounds of formula XVaa, B-18.001 to B-18.004, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0255] Table B-19 provides four compounds of formula XVaa, B-19.001 to B-19.004, where R 1 is cyclopropylmethyl, R 2 is [3-bromo-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0256] Table B-20 provides four compounds of formula XVaa, B-20.001 to B-20.004, where R 1 is cyclopropylmethyl, R 2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], and Z 1 is as defined in Table W.

[0257] Table B-21 provides four compounds of formula XVaa, B-21.001 to B-21.004, where R 1 is cyclopropylmethyl, R 2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], and Z 1 is as defined in Table W.

[0258] The compounds of formula I according to the invention are preventively and / or therapeutically useful active ingredients in the field of pest control, even at low application rates, which have a very favorable biocidal spectrum and are well tolerated by warm-blooded animal species, fish and plants.The active ingredients according to the invention act not only against normally susceptible animal pests, such as insects or representatives of the order Acarina, but also against all or individual developmental stages of resistant animal pests.The insecticidal or acaricidal activity of the active ingredients according to the invention can be manifested directly, i.e. immediately or only after some time, as destruction of the pest, which occurs, for example, during molting, or indirectly, for example, as reduced egg-laying and / or hatching rate.

[0259] Examples of the above animal pests are: From the order Acarina, for example, Acalitus spp., Aculus spp., Acaricalus spp., Aceria spp., Acarus siro, Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia spp., Calipitrimerus spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides spp., Eotetranychus spp. spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Olygonychus spp., Ornithodoros spp., Polyphagotarsone latus, Panonychus spp., Phyllocoptruta oleivora, Phytonemus spp., Polyphagotarsonemus spp., Psoroptes spp., Rhipicephalus spp. spp.), Rhizoglyphus spp., Sarcoptes spp., Steneotarsonemus spp., Tarsonemus spp. and Tetranychus spp.; From the order of the Anoplura, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.; 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. 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., Melighetes aeneus, Melolontha spp., Myochrous armatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp., Phlyctinus spp.), Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabaeidae, Sitophilus spp., Sitotroga spp., Somaticus spp., Sphenophorus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp. and Trogoderma spp.;. From the order Diptera, for example, Aedes spp., Anopheles spp., Antherigona soccata, Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp. 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. spp.), Rhagoletis spp., Rivelia quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.; From the order Hemiptera, for example, Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Amblypelta nitida, Bathycoelia thalassina, Blissus spp., Cimex spp., Clavigrella tomentosicollis, Creontiades spp., Distantiella theobroma, Dichelops furcatus, Dysdercus spp. spp.), Edessa spp., Euchistus spp., Eurydema pulchrum, Eurygaster spp., Halyomorpha halys, Horcias nobilellus, Leptocorisa spp., Lygus spp., Margarodes spp., Murgantia histrionic, Neomegalotomus spp., Nesidiocoris tenuis, Nezara spp., Nysius simulans simulans, Oebalus insularis, Piesma spp., Piezodorus spp., Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophara spp.), Thyanta spp., Triatoma spp., Vatiga illudens;. Acyrthosium pisum, Adalges spp, Agalliana ensigera, Agonoscena targionii, Aleurodicus spp, Aleurocanthus spp, Aleurolobus barodensis, Aleurothrixus floccosus, Aleyrodes brassicae, Amarasca biguttula, Amritodus atkinsoni, Aonidiella spp. spp.), Aphididae, Aphis spp., Aspidiotus spp., Aulacorthum solani, Bactericera cockerelli, Bemisia spp., Brachycaudus spp., Brevicoryne brassicae, Cacopsylla spp., Cavariella aegopodii Scop., Ceroplaster spp.), Chrysomphalus aonidium, Chrysomphalus dictyospermi, Cicadella spp., Cofana spectra, Cryptomyzus spp., Cicadulina spp., Coccus hesperidum, Dalbulus maidis, Dialeurodes spp., Diaphorina citri, Diuraphis noxia, Dysaphis spp., Empoasca spp., Eriosoma larigerum, Erythroneura spp., Gascardia spp., Glycaspis brimblecombei, Hyadaphis pseudobrassicae, Hyalopterus spp., Hyperomyzus pallidus, Idioscopus clypealis, Jacobiasca lybica, Laodelphax spp., Corn scale (Lecanium corni), Lepidosaphes spp., False radish aphid (Lopaphis erysimi, Lyogenys maidis, Macrosiphum spp., Mahanarva spp., Metcalfa pruinosa, Metopolophium dirhodum, Myndus crudus, Myzus spp.), Neotoxoptera sp., Nephotettix spp., Nilaparvata spp., Nippolachnus piri Mats, Odonaspis ruthae, Oregma lanigera Zehnter, Bayberry whitefly, Parabemisia myricae, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., Corn planthopper, Peregrinus maidis, Perkinsiella spp., Hop wart aphid, Phorodon humuli, Phylloxera spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Pseudatomoscelis seriatus, Psylla spp., Pulvinaria aethiopica, Quadraspidiotus spp., Quesada gigas, Recilia dorsalis, Rhopalosiphum spp., Saissetia spp., Scaphoideus spp. spp.), Schizaphis spp., Sitobion spp.), Sogatella furcifera, Spisstilus festinus, Tarophagus Proserpina, Toxoptera spp, Trialeurodes spp, Tridiscus sporoboli, Trionymus spp, Trioza erytreae, Unaspis citri, Zygina flammigera, Zyginidia scutellaris;. From the order of 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.; From the order Isoptera, for example, Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Solenopsis geminate. From the order Lepidoptera, for example, the genera Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyresthia spp., Argyrotaenia spp., Autographa spp., Bucculatrix thurberiella, Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Chrysoteuchia topiaria, Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp., Colias lesbia, Cosmophila flava, Crambus spp., Crocidolomia binotalis, Cryptophlebia leucotoleta leucotreta, Cydalima perspectalis, Cydia spp., Diaphania perspectalis, Diatraea spp., Diparopsis castanea, Earias spp.), Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., Epinotia spp., Estigmene acrea, Etiella zinckinella, Eucosma spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia jaculiferia, Grapholita spp., Hedya nubiferana, Heliothis spp. spp.), Hellula undalis, Herpetogramma spp., Hyphantria cunea, Keiferia lycopersicella, Lasmopalpus lignosellus, Leucoptera scitella, Lithocollethis spp., Lobesia botrana, Loxostege bifidalis, Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta, Mythimna spp., Noctua spp., Operophtera spp., Orniodes indica, Ostrinia nubilalis, Pammene spp., Pandemis spp.), pine sawfly moth (Panolis flammea), Papaipema nebris, red cotton bug (Pectinophora gossypiela), coffee leafminer (Perileucoptera coffeella), Pseudaletia unipuncta, potato tuber moth (Phthorimaea operculella), cabbage white butterfly (Pieris rapae), Pieris spp., diamondback moth (Plutella xylostella), Prays spp., Pseudoplusia spp., Rachiplusia nu, Richia albicosta, Scirpophaga spp., Sesamia spp.), Sparaganothis spp., Spodoptera spp., Sylepta derogate, Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni, Tuta absoluta and Yponomeuta spp.;. From the order Mallophaga, for example, Damalinea spp. and Trichodectes spp.; From the order of Orthoptera, for example, the genera Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp. and Schistocerca spp.; From the order Psocoptera, for example Liposcelis spp.; From the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp. and Xenopsylla cheopis; From the order Thysanoptera, for example, Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.; From the order Thysanura, for example, the silverfish (Lepisma saccharina).

[0260] In a further aspect, the present invention also relates to plant parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the root-knot nematode, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other Meloidogyne species; cyst forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera clover cyst nematode, Heterodera trifolii, and other cyst nematodes (Heterodera species); seed gall nematodes, Anguina species; stem and peel nematodes, Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; pinewood nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus spp.; ring nematodes, Criconema spp., Criconemella spp., Criconemoides spp., Mesocriconema spp.; stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus spp.; fire nematodes, Dolichodorus spp.;Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species;Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species;Hirshmanniella species;Spiny nematodes, Hoploaimus species;False root-knot nematodes, Nacobbus species;Tyrannomatodes, Longidorus elongatus elongatus and other Longidorus species; pin nematodes, Pratylenchus species; root-lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; root-lesion nematodes, Radopholus similis and other Radopholus species; false leaf nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Trichodorus primitivus and other Trichodorus species, Paratrichodorus species;plant parasitic nematodes such as Claytonia spp., Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus spp.; Claytonia spp., Tylenchulus spp.; Xiphinema spp., Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp. and Quinisulcius spp. spp.;

[0261] The compounds of the invention may also have activity against mollusks, examples of which include, for example, the family Ampullariidae; the genus Arion (A. ater, A. circumscriptus, A. hortensis, A. rufus); the family Bradybaenidae (Bradybaena fruticum); the genus Cepaea (C. hortensis, C. rufus ... nemoralis);ochlodina;Deroceras (D.agrestis, D.empiricorum, D.laeve, D.reticulatum);Discus (D.rotundatus);Euomphalia;Galba (G.trunculata);Helicelia (H.itala, H.obvia);Helicidae (Helicigona albustrum) arbustorum); Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Monoa These include the genera Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0262] The active ingredients according to the invention can be used to control, i.e. suppress or destroy, pests of the above-mentioned types which occur in particular on plants, in particular on useful plants and ornamental plants in agriculture, horticulture and forestry, or on organs such as the fruits, flowers, leaves, stems, tubers or roots of such plants, in some cases even plant organs which are formed at a later time remain protected from these pests.

[0263] Suitable target crops are in particular cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beets such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, for example apple, pear, plum, peach, almond, cherry or berries, for example strawberry, raspberry or blackberry; legumes, such as beans, lentils, peas or soybeans; rapeseed, mustard, poppy, olive, sunflower, palm, castor, cocoa or ground yam. nut; cucurbits, such as pumpkin, cucumber or melon; fibre plants, such as cotton, flax, hemp or jute; citrus fruits, such as orange, lemon, grapefruit or tangerine; vegetables, such as spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato or pepper; plants of the Lauraceae family, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugar cane, tea, pepper, grapes, hops, plantain and latex plants.

[0264] The compositions and / or methods of the present invention may be used with any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees and evergreens.

[0265] For example, the present invention relates to the use of the following ornamental species: Ageratum spp., Alonsoa spp., Anemone spp., Anisodontea capsenisis, Anthemis spp., Antirrhinum spp., Aster spp., Begonia spp. (e.g. B. elatior, B. semperflorens, B. tubereux), Bougainvillea spp., Brachycome spp., and the like. spp.), Brassica spp. (ornamental), Calceolaria spp., Capsicum annuum, Catharanthus roseus, Canna spp., Centaurea spp., Chrysanthemum spp., Cineraria spp. (C. maritime), Coreopsis spp., Crassula coccinea, Cuphea ignea, Dahlia spp., Delphinium spp., Bleeding hearts, Dicentra spectabilis, Dorotheantus spp., Eustoma grandiflorum, Forsythia spp., Fuchsia spp., Geranium gnaphalium, Gerbera spp., Gomphrena globosa, Heliotropium spp., Helianthus spp., Hibiscus spp.), Hortensia spp., Hydrangea spp., Hypoestes phyllostachya, Impatiens spp. (I. Walleriana), Iresines spp., Kalanchoe spp., Lantana camara, Lavatera trimestris, Leonotis leonurus, Lilium spp., Mesembryanthemum spp., Mimulus spp., Monarda spp. spp.), Nemesia spp., Tagetes spp., Dianthus spp. (Carnations), Canna spp., Oxalis spp., Bellis spp., Pelargonium spp. (Ivy Geranium (P. peltatum), P. Zonale), Viola spp. (Pansies), Petunia spp., Phlox spp., Plecthranthus spp., Poinsettia spp. spp.), Parthenocissus spp. (P. quinquefolia, P. tricuspidata), Primula spp., Ranunculus spp., Rhododendron spp., Rosa spp. (roses), Rudbeckia spp., Saintpaulia spp., Salvia spp.), Scaevola aemola, Schizanthus wisetonensis, Sedum spp., Solanum spp., Surfinia spp., Tagetes spp., Nicotinia spp., Verbena spp., Zinnia spp. and other bedding plants.

[0266] For example, the present invention relates to the use of the following vegetable species: Allium spp. (garlic (A. sativum), onion (A. cepa), shallot (A. oschaninii), leek (A. Porrum), scallion (A. ascalonicum), green onion (A. fistulosum)), chervil (Anthriscus cerefolium), celery (Apium graveolus), asparagus (Asparagus officinalis), beet (Beta vulgarus), Brassica spp. (B. Oleracea, B. Pekinensis, B. rapa), Capsicum annuum, chickpea (Cicer arietinum), endive (Cichorium endivia), Cichorum spp. spp.) (chicory (C. intybus), endive (C. endivia)), watermelon (Citrillus lanatus), Cucumis spp. (saffron (C. sativus), melon (C. melo)), Cucurbita spp. (Cucurbita pepo, C. maxima), Cyanara spp. (artichoke (C. scolymus), cardoon (C. cardunculus)), carrot (Daucus carota), fennel (Foeniculum vulgare), Hypericum spp., lettuce (Lactuca sativa), tomato spp. spp.) (tomato (L. esculentum), tomato (L. lycopersicum)), mint species (Mentha spp.), basil (Ocimum basilicum), parsley (Petroselinum crispum), Phaseolus spp. (P. vulgaris, runner bean (P.coccineus), pea (Pisum sativum), radish (Raphanus sativus), rheum rhaponticum, Rosemarinus spp., Salvia spp., Scorzonera hispanica, eggplant (Solanum melongena), spinach (Spinacea oleracea), Valerianella spp. (V. locusta, V. eriocarpa) and broad bean (Vicia faba).

[0267] Preferred ornamental species include Saintpaulia, Begonia, Dahlia, Gerbera, Hydrangea, Vervain, Rosa, Kalanchoe, Poinsettia, Aster, Centaurea, Coreopsis, Delphinium, Monarda, Phlox, Rudbeckia, Sedum, Petunia, Viola, Impatiens, Geranium, Chrysanthemum, Ranunculus, Fuchsia, Salvia, Hydrangea, Rosemary, Sage, Hypericum perforatum, Mint, Bell pepper, Tomato and Cucumber.

[0268] The active ingredients according to the invention are particularly suitable for controlling Aphis craccivora, Diabrotica balteata, Heliothis virescens, Myzus persicae, Plutella xylostella and Spodoptera littoralis in cotton, vegetable, corn, rice and soybean crops. The active ingredients according to the invention are particularly suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potato) and Chilo supressalis (preferably in rice).

[0269] The compounds of formula I are particularly suitable for controlling: Hemiptera pests, such as one or more of Bemisia tabaci, Aphis craccivora, Myzus persicae, Rhopalosiphum padi, Nilaparvata lugens and Euschistus heros (preferably on vegetables, soybeans and sugarcane) Lepidoptera pests, for example one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Cydia pomonella, Chrysodeixis includes, Chilo suppressalis, Elasmopalpus lignosellus, Pseudoplusia includesns and Tuta absoluta (preferably in vegetables and corn). Thysanoptera pests such as Thripidae, for example Thrips tabaci and Frankliniella occidentalis (preferably on vegetables), and Soil pests (such as those of the Coleoptera order), for example the species Diabrotica balteata, Agriotes spp. and Leptinotarsa ​​decemLineata (preferably in vegetables and corn)

[0270] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be capable of synthesizing one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria, particularly bacteria of the genus Bacillus.

[0271] Toxins which may be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or δ-endotoxins, such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, insecticidal proteins from Bacillus thuringiensis or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A; or bacterial-colonizing nematodes, such as Photorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus or Xenorhabdus spp. spp.); toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and neurotoxins specific to other insects; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinins; trypsin inhibitors, serine protease inhibitors, proteinase inhibitors, such as patatin, cystatin, papain inhibitors; ricin, maize-RIP, abrin, rufin, saporin, ribosome-inactivating proteins (RIPs) such as bryodin or bryodin; steroid metabolic enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0272] In the context of the present invention, delta-endotoxins are understood to be, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C or plant insecticidal proteins (Vip), such as Vip1, Vip2, Vip3 or Vip3A, and also, explicitly, hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinantly by a new combination of different domains of these proteins (see, for example, WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of the natural toxin are replaced. In such amino acid substitutions, preferably a non-naturally occurring protease recognition sequence is inserted into the toxin, for example in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0273] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP 0 374 753, WO 93 / 07278, WO 95 / 34656, EP 0 427 529, EP 451 878 and WO 03 / 052073.

[0274] Methods for the preparation of such transgenic plants are generally known to those skilled in the art and are described, for example, in the above-mentioned publications. Deoxyribonucleic acids of the CryI type and their preparation are known, for example, from WO 95 / 34656, EP 0 367 474, EP 0 401 979 and WO 90 / 13651.

[0275] The toxins contained in the transgenic plants confer resistance to the plants against pests found in a range of insect taxa, but are most commonly found in beetles (Coleoptera), two-winged insects (Diptera) and moths (Lepidoptera).

[0276] Transgenic plants containing one or more genes encoding insecticidal resistance and expressing one or more toxins are known, and some of them are commercially available. Examples of such plants are YieldGard® (a corn variety expressing the Cry1Ab toxin); YieldGard Rootworm® (a corn variety expressing the Cry3Bb1 toxin); YieldGard Plus® (a corn variety expressing the Cry1Ab and Cry3Bb1 toxins); Starlink® (a corn variety expressing the Cry9C toxin); Herculex I® (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) for resistance to the herbicide glufosinate ammonium); NuCOTN 33B® (a cotton variety expressing the Cry1Ac toxin); Bollgard I® (a cotton variety expressing the Cry1Ac toxin); Bollgard II® (a cotton variety expressing Cry1Ac and Cry2Ab toxins); VipCot® (a cotton variety expressing Vip3A and Cry1Ab toxins); NewLeaf® (a potato variety expressing Cry3A toxin); NatureGard®, Agrisure® GT Advantage (GA21 glyphosate tolerance trait), Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

[0277] Further examples of such transgenic crop plants are: 1. Bt11 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St.Sauveur, France). Transgenic maize conferred resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0278] 2. Bt176 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St.Sauveur, France). Transgenic maize conferred resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia nonagrioides) by transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenicly expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0279] 3. MIR604 maize, registration number C / FR / 96 / 05 / 10, from Syngenta Seeds SAS (Chemin de l'Hobit 27, F-31 790 St. Sauveur, France). Maize made insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by the insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0280] 4. MON 863 maize, registration number C / DE / 02 / 9, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain Coleoptera insects.

[0281] 5. IPC 531 cotton, registration number C / ES / 96 / 02, manufactured by Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium.

[0282] 6. 1507 maize, registration number C / NL / 00 / 10, from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium. Genetically modified maize for expression of the protein Cry1F for resistance to certain Lepidoptera insects and the PAT protein for resistance to the herbicide glufosinate ammonium.

[0283] 7. NK603 x MON 810 maize, registration number C / GB / 02 / M3 / 03, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium. It consists of a conventionally bred hybrid maize variety by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 maize also genetically expresses the protein CP4 EPSPS from Agrobacterium sp. strain CP4, which confers resistance to the herbicide Roundup® (containing glyphosate), and the Cry1Ab toxin from Bacillus thuringiensis subsp. kurstaki, which confers resistance to certain Lepidoptera, including the European Corn Borer.

[0284] 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).

[0285] The term "crop plant" should also be understood to include crop plants that have been transformed by the use of recombinant DNA techniques so as to be able to synthesize antipathogenic substances with selective action, such as, for example, so-called "pathogenicity-related proteins" (PRPs, see, for example, EP-A-0392225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0392225, WO-A-95 / 33818 and EP-A-0353191. Methods for producing such transgenic plants are generally known to the skilled person and are described, for example, in the above-mentioned publications.

[0286] Crops can also be improved to increase resistance to fungal (e.g., Fusarium, anthracnose or Phytophthora), bacterial (e.g., Pseudomonas) or viral (e.g., Potato Leaf Curl Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0287] Crops also include those that have high resistance to nematodes, such as the soybean cyst nematode.

[0288] Crops that are tolerant to abiotic stress include those that have increased tolerance to drought, high salt, heat, cold, frost or light due to, for example, expression of NF-YB or other proteins known in the art.

[0289] Anti-pathogenic substances which may be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium or calcium channels, e.g. viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis related proteins" (PRPs; see, for example, EP 0 392 225); anti-pathogenic substances produced by microorganisms, such as peptide or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors involved in plant pathogen defense (so-called "plant disease resistance genes" as described in WO 03 / 000906).

[0290] Further fields of use of the compositions according to the invention are the protection of storehouses and storage rooms and the protection of raw materials (such as wood and textiles), floor coverings and buildings and in the hygiene sector, in particular the protection of humans, livestock and productive livestock from pests of the abovementioned types.

[0291] 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 ectoparasites on an animal. The present invention further provides a compound of the first aspect for use in the prevention and / or treatment of diseases transmitted by ectoparasites.

[0292] The invention provides the use of a compound of the first aspect for the manufacture of a medicament for controlling parasites in or on an animal.The invention further provides the use of a compound of the first aspect for the manufacture of a medicament for controlling ectoparasites on an animal.The invention further provides the use of a compound of the first aspect for the manufacture of a medicament for preventing and / or treating a disease transmitted by an ectoparasite.

[0293] The invention provides for the use of a compound of the first aspect in the control of parasites in or on an animal.The invention further provides for the use of a compound of the first aspect in the control of ectoparasites on an animal.

[0294] When used in relation to parasites in or on animals, the term "control" refers to the reduction in the number of pests or parasites, the eradication of pests or parasites, and / or the prevention of further pest or parasite infestation.

[0295] When used in reference to parasites in or on an animal, the term "treating" refers to inhibiting, slowing, halting or reversing the progression or severity of an existing condition or disease.

[0296] When used in reference to parasites in or on an animal, the term "prevent" refers to the avoidance of symptoms or disease developing in the animal.

[0297] When used in reference to parasites in or on animals, the term "animal" can refer to mammals and non-mammals such as birds or fish. In the case of mammals, this can be a human or non-human mammal. Non-human mammals include, but are not limited to, livestock animals and companion animals. Livestock animals include, but are not limited to, cows, camelids, pigs, sheep, goats, and horses. Companion animals include, but are not limited to, dogs, cats, and rabbits.

[0298] A "parasite" is a pest that lives in or on a host animal and benefits from nutrients provided at the expense of the host animal. An "endoparasite" is a parasite that lives inside the body of a host animal. An "ectoparasite" is a parasite that lives on a host animal. Ectoparasites include, but are not limited to, mites, insects, and crustaceans (e.g., sea lice). The subclass Acari (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the following genera: Rhipicaphalus, such as Rhipicaphalus (Boophilus) microplus and Rhipicephalus sanguineus; Amblyomma; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the following genera: Chorioptes, such as Chorioptes bovis; Psoroptes, such as Psoroptes ovis; Cheyletiella; Dermanyssus, such as Dermanyssus gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcoptes, such as Sarcoptes scabiei; and Psorergates.Insects include, but are not limited to, members of the following orders: Siphonaptera, Diptera, Chelonaptera, Lepidoptera, Coleoptera, and Homoptera. Members of the Siphonaptera order include, but are not limited to, Ctenocephalides felis and Ctenocephatides canis. Members of the order Diptera include, but are not limited to, Musca spp.; bot flies, such as Gasterophilus intestinalis and Oestrus ovis; stable flies; horseflies, such as Haematopota spp. and Tabunus spp.; haematobia, such as Haematobia irritans; Stomoxys; Lucilia; midges; and mosquitoes. Members of the order Gnathognatha include, but are not limited to, sucking and biting lice, such as Bovicola Ovis and Bovicola Bovis.

[0299] When used in relation to parasites in or on animals, the term "effective amount" refers to an amount or dosage of a compound of the present invention or its salt that, in one or more doses administered to an animal, produces the desired effect in or on the animal. An effective amount can be easily determined by the attending diagnostician, as one skilled in the art, by using known techniques and observing results obtained under analogous circumstances. In determining an effective amount, the attending diagnostician will take into account a number of factors, including, but not limited to, the mammalian species; its size, age and general health; the parasite and level of infestation to be controlled; the specific disease or disorder involved; the extent or complications or severity of the disease or disorder; the individual's response; the specific compound administered; the mode of administration; the bioavailability characteristics of the preparation administered; the selected dosage regimen; the use of concomitant drugs; and other relevant circumstances.

[0300] The compounds of the present invention can be administered to animals by any route that has the desired effect, including, but not limited to, topical, oral, parenteral and subcutaneous. Topical administration is preferred. Formulations suitable for topical administration include, for example, solutions, emulsions and suspensions, and can be in the form of pour-ons, spots, spray-ons, spray laces or dips. Alternatively, the compounds of the present invention can be administered by ear tag or collar.

[0301] The salt forms of the compounds of the present invention include both pharma- ceutically and veterinarily acceptable salts, which may differ from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and the general methodology for preparing them are well known in the art. For example, see 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). Those skilled in the art of synthesis will understand that the compounds of the present invention can be easily converted to salts such as hydrochloride salts and isolated as such salts using techniques and conditions well known to those skilled in the art. In addition, one skilled in the art of synthesis will recognize that compounds of the invention can be readily converted from a corresponding salt to the corresponding free base, and isolated as such a salt.

[0302] The present invention also provides a method 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 pest, its habitat, or a surface or substrate by brushing, rolling, spraying, painting, or immersion. By way of example, IRS (indoor residual spray) application of surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention. In another embodiment, it is contemplated to apply such compositions to substrates such as nonwoven or woven materials in the form of (or that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0303] In one embodiment, the method of controlling such pests comprises applying a pesticidally effective amount of the composition of the present invention to a target pest, its habitat, or a surface or substrate, so as to provide effective residual pest control activity to the surface or substrate. Such application can be performed by brushing, rolling, spraying, painting, or immersing the pesticidal composition of the present invention. By way of example, IRS application on surfaces such as walls, ceilings, or floors is contemplated by the method of the present invention, so as to provide effective residual pest control activity to the surface. In another embodiment, it is contemplated to apply such compositions for residual control of pests on substrates such as fabric materials in the form of (or that can be used to manufacture) netting, clothing, bedding, curtains, and tents.

[0304] The substrates, including nonwovens, fabrics or nets to be treated, can be made of natural fibers such as cotton, raffia, jute, flax, sisal, hemp or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile. Polyesters are particularly suitable. Methods of textile treatment are known, for example, from WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0305] A further field of use for the compositions according to the invention is that of trunk injection / trunk treatment of all ornamental trees and of all kinds of fruit and nut-bearing trees.

[0306] In the field of trunk injection / trunk treatment, the compounds according to the invention are particularly suitable against wood-boring insects of the abovementioned orders Lepidoptera and Coleoptera, in particular the woodborers listed in Tables A and B below.

[0307] [Table 3]

[0308] [Table 4-1] [Table 4-2]

[0309] The present invention may be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, pillbugs, mites, mole crickets, scale insects, mealybugs, mites, foxtails, southern chinch bugs, and grubs. The present invention may also be used to control insect pests in various stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0310] In particular, the present invention relates to the prevention and treatment of earthworms (Cyclocephala spp. (e.g. masked chafer, C. lurida), Rhizotrogus spp. (e.g. European chafer, R. majalis), Cotinus spp. (e.g. blue swallowtail beetle, C. nitida), Popillia spp. (e.g. Japanese beetle, P. japonica), Phyllophaga spp. (e.g. May / June beetle), Ataenius spp. (e.g. cephalosporinus, C. spp.), and the like). spp. (e.g. Black turfgrass ataenius, A. spretulus), Maladera spp. (e.g. red-veined beetle, M. castanea) and Tomarus spp.), cotton scales (Margarodes spp.), mole crickets (tawny, southern and brachypterous; Scapteriscus spp., Gryllotalpa africana) and leatherjackets (European crane fly, Tipula The present invention may be used to control insect pests that feed on the roots of turfgrass, including Pseudomonas spp.

[0311] The present invention may also be used to control straw-dwelling insect pests of turfgrass, including cutworms (such as Spodoptera frugiperda and the common armyworm (such as Pseudaletia unipuncta), cutworms, weevils (such as Sphenophorus spp., S. venatus verstitus and S. parvulus) and sod webworms (such as Crambus spp. and the tropical sod webworm, Herpetogramma phaeopteralis).

[0312] The present invention may also be used to control insect pests that live above ground and feed on turfgrass leaves, including the lesser stink bug (such as the southern kinkbug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), rhodesgrass mealybug (Antonina graminis), two-lined spittlebug (Propsapia bicincta), leafhoppers, cutworms (Noctuidae), and greenbugs.

[0313] The present invention may also be used to control other pests of turfgrass, such as the red fire ant (Solenopsis invicta), which creates ant mounds in turfgrass.

[0314] In the hygiene field, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies mites, chiggers, flies (stable flies and licking flies), parasitic fly larvae, lice, pubic lice, bite lice and fleas.

[0315] Examples of such parasites are: From the order Anoplurida, the genera Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.

[0316] From the order Mallophagida, the genera Trimenopon, Menopon, Trinoton, Bovicola, Werneckiella, Lepikentron, Damalina, Trichodectes and Felicola.

[0317] Among the order Diptera and its suborders Nematocerina and Brachycerina, for example, the genera 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., spp.), Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp. spp.), Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipotena spp. and Melophagus spp.

[0318] Among the order Siphonapterida, for example, the genera Pulex spp., Ctenocephalides spp., Xenopsylla spp., and Ceratophyllus spp.

[0319] From the order Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.

[0320] From the order Blattaridae, for example, Blatta orientalis, Periplaneta americana, Blattela germanica and Supella spp.

[0321] Among the subclass Acaria (Acarida) and the suborders Metastigmata and Mesostigmata, for example, the genera Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., spp.), Pneumonyssus spp., Sternostoma spp. and Varroa spp.

[0322] Among the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, the genera Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., spp.), Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

[0323] The compositions according to the invention are also suitable for protecting against insect infestation in materials such as wood, textiles, plastics, adhesives, glues, paints, paper and cardboard, leather, floor coverings and building materials.

[0324] The compositions according to the invention can be used, for example, against the following pests: 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, Minthesrugicollis, Xyleborus spec., Tryptodendron spec., Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. and Dinoderus minutus as well as beetles such as Sirex juvencus, Urocerus gigas, Urocerus gigas Hymenopteran insects such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, and Urocerus augur, as well as hymenopteran insects such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, andindicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, and Coptotermes formosanus, as well as silverfish such as Lepisma saccharina. The compounds of formula I and I'a or salts thereof are particularly suitable for controlling one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae and Heteroderidae. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-92 and Table P") controls one or more pests selected from the families: Noctuidae, Plutellidae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Crambidae, Meloidogynidae, and Heteroderidae.

[0325] The compounds of formula I and I'a or salts thereof are effective against thrips of the genera Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp. and Chilo spp. spp. In a preferred embodiment of each aspect, the compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-92 and Table P") is selected from the group consisting of Spodoptera spp., Plutella spp., Frankliniella spp., Thrips spp., Euschistus spp., Cydia spp., Nilaparvata spp., Myzus spp., Aphis spp., Diabrotica spp., Rhopalosiphum spp., Pseudoplusia spp., and / or other genus. The present invention relates to a method for controlling one or more pests selected from the group consisting of Chilo spp. and Chilo spp.

[0326] The compounds of formula I and I'a or salts thereof are particularly suitable for controlling one or more of Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padi and Chilo suppressalis.

[0327] In a preferred embodiment of each aspect, the compound TX (wherein the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-92 and Table P") is effective against Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padiata, and / or other insecticides. Padia, Egyptian armyworm (Spodoptera littoralis) + TX, diamondback moth (Plutella xylostella) + TX, and other rice stem borers (Chilo Suppressalis); Frankliniella occidentalis + TX, onion thrips (Thrips tabaci) + TX, Euschistus heros + TX, codling moth (Cydia pomonella) + TX, brown planthopper (Nilaparvata lugens) + TX, green peach aphid (Myzus persicae) + TX, Chrysodeixis includens + TX, bean aphid (Aphis craccivora) + TX, Diabrotica balteata + TX, Rhopalosiphum Padi)+TX and Chilo suppressalis+TX.

[0328] In one embodiment of each aspect, one compound selected from the compounds defined in Tables A-1 to A-92 and Table P is used to inhibit or inhibit Spodoptera littoralis, Plutella xylostella, Frankliniella occidentalis, Thrips tabaci, Euschistus heros, Cydia pomonella, Nilaparvata lugens, Myzus persicae, Chrysodeixis includens, Aphis craccivora, Diabrotica balteata, Rhopalosiphum padiata, ... Thrips tabaci, Thrips tabaci, Thrip Padia and Chilo Suppressalis.

[0329] In one embodiment, one compound selected from the compounds defined in Tables A-1 to A-92 and Table P is suitable for controlling Mamestra (preferably in vegetables), Cydia pomonella (preferably in apple), Empoasca (preferably in vegetables, vineyards), Leptinotarsa ​​(preferably in potato) and Chilo supressalis (preferably in rice).

[0330] The compounds of the present invention may have any number of benefits including, inter alia, advantageous levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., high biological activity, advantageous spectrum of activity, high safety profile (improved physicochemical properties or high biodegradability against above and below ground non-target organisms such as fish, birds and bees). In particular, it has been surprisingly found that certain compounds of formula (I) may exhibit advantageous safety profiles against non-target arthropods, particularly pollinators such as honeybees, solitary bees and bumblebees, most particularly the western honeybee (Apis mellifera).

[0331] The compounds according to the invention can be used as pesticides in their unmodified form, but they are generally formulated into compositions using formulation aids such as carriers, solvents and surface-active substances in various ways. The formulations can be in various physical forms, such as dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent pellets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, oil-based flowables, aqueous dispersions, oil-based dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (containing water or water-miscible organic solvents as carriers), impregnated polymer films or other forms known, 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 diluted before use. Dilution can be carried out, for example, with water, liquid fertilizers, trace elements, biological organisms, oils or solvents.

[0332] The formulations can be prepared, for example, by mixing the active ingredient with compounding auxiliaries to obtain a composition in the form of finely divided solids, granules, solutions, dispersions or emulsions. The active ingredient can also be compounded with other auxiliaries, such as finely divided solids, mineral oils, vegetable or animal oils, vegetable or animal modified oils, organic solvents, water, surface-active substances or combinations thereof.

[0333] The active ingredient may also be contained in very fine microcapsules. Microcapsules contain the active ingredient in a porous carrier. This allows the active ingredient to be released in a controlled amount (e.g., slow release) into the environment. Microcapsules usually have a diameter of 0.1 to 500 microns. They contain the active ingredient in an amount of about 25 to 95% by weight based on the capsule weight. The active ingredient may be in the form of a bulk solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulating membrane may, for example, comprise 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 may be formed containing the active ingredient in the form of fine particles in a solid matrix of the base, but the microcapsules themselves are not encapsulated.

[0334] The formulation auxiliaries suitable for the preparation of the compositions according to the invention are known per se. Liquid carriers include 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 esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietic acid, 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, diproxitol, alkylpyrrolidone, 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, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, octadecanoic acid, octylamine acetate Examples of the solvent that can be used include 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, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, and N-methyl-2-pyrrolidone.

[0335] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, limestone, calcium carbonate, bentonite, calcium montmorillonite, cotton husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar materials.

[0336] A large number of surface-active substances may be advantageously used in both solid and liquid formulations, especially in formulations which may be diluted with a carrier before use. Surface-active substances may be anionic, cationic, nonionic or polymeric and may be used as emulsifying agents, wetting agents or suspending agents or for other purposes. Typical surface-active materials include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide adducts, such as nonylphenol ethoxylate; alcohol / alkylene oxide adducts, such as tridecyl alcohol ethoxylate; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary amines, such as lauryltrimethylammonium 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 di-alkyl phosphate esters; and further materials, such as those described in, for example, McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Corp., Ridgewood New Jersey (1981).

[0337] Further adjuvants that may be used in the pest control formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbing agents, mixing aids, defoamers, complexing agents, neutralizing or pH adjusting and buffering agents, corrosion inhibitors, fragrances, wetting agents, uptake enhancers, trace elements, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, fungicides and liquid and solid fertilizers.

[0338] The composition according to the invention may contain additives including vegetable or animal oils, mineral oils, alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in the composition according to the invention is generally 0.01-10% based on the mixture to be applied. For example, the oil additive can be added in the desired concentration in the spray tank after the spray mixture is prepared. Preferred oil additives include mineral oils or vegetable oils, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable oils, such as methyl derivatives, or animal oils, such as fish oil or beef tallow. Preferred oil additives are C 8 ~C 22 Alkyl esters of fatty acids, especially C 12 ~C 18 Methyl derivatives of fatty acids, such as the methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are described in the Compendium of Herbicide Adjuvants, 10 th Edition, Southern Illinois University, 2010.

[0339] The compositions of the invention generally comprise 0.1-99% by weight, especially 0.1-95% by weight, of the compounds of the invention and 1-99.9% by weight of formulation aids, which preferably include 0-25% by weight of surface active materials. Although commercial products may preferably be formulated as concentrates, end users will usually utilise dilute formulations.

[0340] The application rates vary within wide limits and depend on the nature of the soil, the method of application, the crop plant, the pests to be controlled, the prevailing weather conditions and other factors governed by the method of application, the time of application and the target crop. As a general guideline, the compounds may be applied in amounts of 1 to 2000 l / ha, in particular 10 to 1000 l / ha.

[0341] A preferred formulation may have the following composition (by weight): Emulsifiable concentrate: Active ingredient: 1-95%, preferably 60-90% Surface active agent: 1-30%, preferably 5-20% Liquid carrier: 1-80%, preferably 1-35%

[0342] Powder: Active ingredient: 0.1-10%, preferably 0.1-5% Solid carrier: 99.9-90%, preferably 99.9-99%

[0343] Suspension concentrates: Active ingredient: 5-75%, preferably 10-50% Water: 94-24%, preferably 88-30% Surfactant: 1-40%, preferably 2-30%

[0344] Wettable powder: Active ingredient: 0.5-90%, preferably 1-80% Surface active agent: 0.5-20%, preferably 1-15% Solid carrier: 5-95%, preferably 15-90%

[0345] Granules: Active ingredient: 0.1-30%, preferably 0.1-15% Solid carrier: 99.5-70%, preferably 97-85%

[0346] The following examples further illustrate, but do not limit, the present invention.

[0347] [Table 5]

[0348] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a wettable powder which can be diluted with water to obtain a suspension of the desired concentration.

[0349] [Table 6]

[0350] The complex is thoroughly mixed with the adjuvant and the mixture is thoroughly ground in a suitable mill to obtain a powder which can be directly used as a seed treatment.

[0351] [Table 7]

[0352] Emulsions of any required dilution which can be used for plant protection are available from this concentrate by dilution with water.

[0353] [Table 8]

[0354] Ready-to-use dusts can be obtained by mixing the complex with a carrier and grinding the mixture in a suitable mill. Such dusts can also be used for dry dressing of seeds.

[0355] [Table 9]

[0356] The composite is mixed with the auxiliary and ground, the mixture is moistened with water, the mixture is extruded and then dried in a stream of air.

[0357] [Table 10]

[0358] In a mixer, the finely ground composite is applied uniformly to the kaolin moistened with polyethylene glycol, thus obtaining non-dusty coated granules.

[0359] [Table 11]

[0360] The finely ground composite is thoroughly mixed with adjuvants to give a suspension concentrate which can be diluted with water to give a suspension of any desired dilution, which can be used to treat and protect living plants and plant propagation material against microbial infestation by spraying, pouring or immersion.

[0361] [Table 12]

[0362] This micronized combination is intimately mixed with an adjuvant to obtain a suspension concentrate from which suspensions of any desired dilution rate can be obtained by dilution with water, with which living plants as well as plant propagation material can be treated and protected from microbial infestation by spraying, pouring or immersion.

[0363] Slow-release capsule suspension 28 parts of the complex are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate / polymethylene-polyphenylisocyanate mixture (8:1). The mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size is achieved. A mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water is added to the emulsion. The mixture is stirred until the polymerization reaction is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium-sized capsules is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0364] 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 (EO), emulsions, oil in water (EW), microemulsions (ME), oil dispersions (OD), oil miscible flowables (OF), oil miscible liquids (OL), soluble concentrates (SL), ultra low volume suspensions (SU), ultra low volume liquids (UL), technical concentrates (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG) or any technically preferred formulation in combination with agriculturally acceptable adjuvants. EXAMPLES

[0365] Preparation example: "Mp" means melting point (° C.). The free radical represents a methyl group. 1 H NMR measurements were recorded on a Brucker 400 MHz spectrometer and chemical shifts are given in ppm relative to TMS standard. Spectra were run in deuterated solvents as specified. The following methods were used to characterize the compounds. Characteristic LCMS values ​​obtained for each compound are the retention time ("Rt" recorded in minutes) and the measured molecular ion (M+H). + It was.

[0366] LCMS method: Spectra were recorded on a Waters mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) equipped with an electrospray source (polarity: positive and negative, capillary: 3.00 kV, cone range: 30 V, extractor: 2.00 V, source temperature: 150° C., desolvation temperature: 350° C., cone gas flow: 50 l / h, desolvation gas flow: 650 l / h, mass range: 100-900 Da) and a Waters Acquity UPLC: binary pump, heated column compartment, diode-array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 × 2.1 mm; Temperature: 60 °C; DAD wavelength range (nm): 210–500; Solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; Gradient: 10–100% B in 1.2 min; Flow (ml / min) 0.85.

[0367] Example 1: Preparation of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P3) [ka] Step A: Preparation of 2-(methylamino)propanamide [ka] To a solution of 2-bromopropanamide (10 g, 65.8 mmol) in acetonitrile was added potassium carbonate (27.5 g, 197.4 mmol) and a 2 M solution of methylamine in THF (66 mL, 131.6 mmol). The resulting suspension was stirred at 80° C. for 16 h, filtered, and concentrated in vacuo. The residue was dissolved in ethyl acetate (100 mL), washed successively with water and brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give 2-(methylamino)propanamide as white crystals. 1 H-NMR (400MHz, CDCl 3):δ=3.06(q,J=7.0Hz,1H),2.42(s,3H),1.32(d,J=7.0Hz,3H)ppm.

[0368] Step B: Preparation of N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide [ka] A solution of 2-(methylamino)propanamide (6.7 g, 65.8 mmol), N,N-diisopropylethylamine (34.5 mL, 197 mmol), 3,5-bis(trifluoromethyl)benzoic acid (17 g, 65.8 mmol) in ethyl acetate (230 mL) and N,N-dimethylformamide (164 mL) was cooled to 0° C. and treated dropwise with a 50% solution of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphorinane-2,4,6-trioxide (T3P) in ethyl acetate (47 mL, 79 mmol). The resulting orange solution was stirred at room temperature for 45 min and then concentrated in vacuo. The residue was dissolved in methyl t-butyl ether (200 mL), washed with water (2×30 mL), 2M NaOH (2×30 mL), brine (30 mL) and the organic phase was dried over sodium sulfate, filtered and concentrated in vacuo to give N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide as a crude orange gum which was used in the next step without any further purification. 1 H-NMR (400MHz, CDCl 3 ):δ=7.98(s,1H),7.92(s,2H),5.25-5.15(m,1H),2.95(bs,3H),1.50(d,J=7.0Hz,3H)ppm;LCMS:R t 0.85, m / z=341(MH + , negative mode).

[0369] Step C: Preparation of N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide [ka] To a solution of N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide (19 g, 55.52 mmol) in dichloromethane (285 mL) was added N,N-dimethylformamide dimethyl acetal (11 mL, 83 mmol). The resulting mixture was stirred at 40° C. for 4 h and then concentrated in vacuo to give N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide as a crude orange gum. LCMS:R t 0.89, m / z=398 (M+H + ).

[0370] Step D: Preparation of N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide [ka] To a solution of N-[2-[dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (2 g, 4.78 mmol) in a mixture of 1,4-dioxane (20 mL) and acetic acid (20 mL) was added hydrazine monohydrate (0.465 mL, 9.56 mmol). The reaction mixture was stirred at 65° C. for 2 h and then concentrated in vacuo. Purification by chromatography on silica gel (eluted with ethyl acetate in cyclohexane) gave N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide. LCMS:R t 0.86, m / z=367 (M+H + ).

[0371] Step E: Preparation of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (I6) [ka] To a solution of N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.95 g, 2.6 mmol) in dichloromethane (30 mL) was added a solution of 2 M aqueous NaOH (3.9 mL, 7.8 mmol) and benzyltrimethylammonium tribromide (1.1 g, 2.9 mmol) in dichloromethane (10 mL). The reaction mixture was stirred for 45 min and then carefully quenched with a 2 M aqueous solution of HCl. The organic phase was separated, dried over sodium sulfate, filtered and concentrated in vacuo to give N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide as a yellow solid. LCMS:R t 0.98, m / z=445, 447 (M+H + ).

[0372] Step F: Preparation of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P3) [ka] To a solution of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (0.84 g, 1.9 mmol) in dry DMF (9.4 mL) was added NaH (0.11 g, 2.8 mmol) under argon atmosphere, followed by stirring at room temperature for 30 min. A solution of 2-bromopyrimidine (0.60 g, 3.8 mmol) in dry DMF (2.0 mL) was added to this mixture, and the reaction was stirred at room temperature for 1 h, followed by heating to 120° C. for 15 h. The reaction mixture was taken up in ethyl acetate, washed with water (5×5 mL), once with brine, dried over anhydrous MgSO4, filtered, and concentrated in vacuo. Purification by reverse phase chromatography (eluting with acetonitrile / water) gave N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide. LCMS:R t 1.05, m / z=525 (M+H + ).

[0373] Example 2: Preparation of N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P2) [ka] Step A: Preparation of ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate [ka] To a stirred solution of 3,5-bis(trifluoromethyl)benzoic acid (10.0 g, 38.7 mmol) in dichloromethane (10.0 mL) was added SOCl 2(9.21 g, 77.5 mmol) was added at 0° C. and the resulting mixture was stirred at room temperature for 2 h. Then the mixture was concentrated in vacuum and the resulting residue was added to a stirred solution of ethyl alaninato (5.44 g, 46.5 mmol) in pyridine (100 mL) at 0° C. The reaction mixture was stirred for 2 h at room temperature. After the reaction was complete, the mixture was diluted with water and extracted with ethyl acetate (10 ml×2). The combined organic phase was washed successively with 2N HCl and brine, and then extracted with Na 2 SO 4 After drying at 40° C. and concentrating in vacuo, the crude product was purified by chromatography on silica gel (eluting with ethyl acetate in cyclohexane) to give ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate. LCMS:R t 1.06, m / z=358 ​​(M+H + ).

[0374] Step B: Preparation of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid [ka] Ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate (5.00 g, 14.0 mmol) in THF:H 2 To a stirred solution of LiOH.H2O (1:1, 50 mL) 2 O (1.76 g, 42.0 mmol) was added at 0° C. and the resulting mixture was stirred at room temperature for 2 h. The mixture was concentrated in vacuo and the resulting residue was acidified to pH 1 with 1N HCl. The solid formed was collected by filtration and dried under reduced pressure to give 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid. LCMS:R t 0.91, m / z=330 (M+H + ).

[0375] Step C: Preparation of N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P2) [ka] To a stirred solution of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoic acid (90.0%, 200 mg, 0.547 mmol) in DMF (4.0 mL) was added 2-methoxyacetamidine (48.2 mg, 0.547 mmol), HATU (312 mg, 0.820 mmol) and DIPEA (176 mg, 1.37 mmol) at room temperature. The resulting mixture was stirred at room temperature for 3 hours, then pyrimidin-2-ylhydrazine (72.3 mg, 0.656 mmol) and AcOH (249 mg, 4.16 mmol) were added at room temperature. The reaction mixture was stirred at 80° C. for 1 hour, then cooled at room temperature. Ethyl acetate (25 mL) was added and the organic layer was washed with saturated bicarbonate solution and then with water. Na 2 SO 4 Drying at 40° C. and concentration in vacuo gave the crude product, which was purified by chromatography on silica gel (eluted with ethyl acetate in cyclohexane) to give N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P2). LCMS:R t 0.92, m / z=475 (M+H + );Mp:155-160℃; 1 H NMR (400 MHz, CDCl 3 ):δ 8.92(d,J=4.0Hz 2H),8.29(s,2H),8.01(s,1H),7.67(d,J=8.0Hz,1H),7.41(t,J=4.0Hz,1H) ,6.52(t,J=7.4Hz,1H),4.64(s,2H),3.49(s,3H),1.74(d,J=8.0Hz,3H)ppm.

[0376] Example 3: Preparation of N-methyl-N-[1-(5-phenyl-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P6) [ka] To a stirred solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (60 mg, 0.11 mmol) in dioxane (1.1 mL) was added phenylboronic acid (29 mg, 0.23 mmol), Pd(PPh 3 ) 4 (13 mg, 0.011 mmol) and aqueous potassium carbonate (2 M, 0.17 mmol) were added. The resulting mixture was stirred at reflux for 1 h. After that, LCMS showed complete conversion, isolute® was added to the reaction mixture, and the solvent was removed by concentration in vacuum. The crude product was purified by chromatography on silica gel (eluted with ethyl acetate in cyclohexane) to give N-methyl-N-[1-(5-phenyl-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P6). LCMS:R t 1.15, m / z=521 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.9(d,J=4.77Hz,2H)8.3(dd,J=7.52,2.02Hz,2H)7.9(s,1H)7.7(s,2H)7.4-7.5(m,3H)7.4(br t,J=4.58Hz,1H)6.8(q,J=6.72Hz,1H)2.9(s,3H)1.9(br d,J=6.97Hz,3H)ppm.

[0377] Example 4: Preparation of N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P15). [ka] Step A: Preparation of N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P22). [ka] A stirred solution of N-[1-(3-bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (P1) (100 mg, 0.19 mmol) in toluene (1.9 mL) was added with benzophenone imine (71 mg, 0.38 mmol), Xantphos (23 mg, 0.038 mmol), Pd 2 (dba) 3 (PPh 3 ) 4 (18 mg, 0.019 mmol) and cesium carbonate (19 mg, 0.57 mmol) were added. The resulting mixture was stirred at reflux for 18 h. After which LCMS showed complete conversion, isolute® was added to the reaction mixture and the solvent was removed in vacuo. The crude product was purified by chromatography on silica gel (eluting with ethyl acetate in cyclohexane) to give N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P22) as a gum. LCMS:R t 1.19, m / z=624 (M+H + ).

[0378] Step B: Preparation of N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P7). [ka] To a stirred solution of N-[1-[5-(benzhydrylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide in THF (1.4 mL) was added an aqueous solution of HCl (2N, 0.20 mL, 0.41 mmol) and the resulting mixture was stirred at room temperature for 1 h. Ethyl acetate (20 mL) was added and the organic layer was washed with saturated bicarbonate solution followed by water. Na 2 SO 4 Drying by filtration and concentration in vacuo gave the crude product, which was purified by chromatography on silica gel (eluted with ethyl acetate / hexanes) to give N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P7) as a brownish solid. LCMS:R t 0.88, m / z=460 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.76(br d,J=4.8Hz,2H),7.91(br s,1H),7.69(s,2H),7.2-7.3(m,1H),6.7-6.8(m,1H),4.38(s,2H)2.87(s,3H),1.73(br d,J=7.0Hz,3H)ppm

[0379] Step C: Preparation of N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (P15) [ka] N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (100 mg, 0.22 mmol) and CuCl 2 2H 2To a cooled suspension of O (45 mg, 0.26 mmol) in concentrated HCl (1.0 mL) was added dropwise a solution of sodium nitrite (23 mg, 0.33 mmol) in 0.5 mL of water. The reaction was stirred at room temperature for 12 h. Water was added and the precipitate formed was filtered off. This was purified by chromatography on silica gel (eluted with ethyl acetate / hexanes) to give N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (compound P15). LCMS:R t 1.05, m / z=479 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.86(br d,J=4.4Hz,2H),7.92(br s,1H),7.69(s,2H),7.40(t,J=4.8Hz,1H),6.72(q,J=6.6Hz,1H),2.93(s,3H),1.79(br d,J=7.0Hz,3H)ppm

[0380] Example 5: Preparation of N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P1) [ka] Step A: Preparation of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate [ka] In a metal high pressure reactor, triethylamine (35.6 μL, 255 μmol) and [1,3-bis(diphenylphosphino)propane]palladium(ii) dichloride (8.11 mg, 13.7 μmol) were added to a solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (100 mg, 196 μmol) in methanol (2 mL) at room temperature. The reaction mixture was heated to 100° C. and stirred overnight under a carbon monoxide atmosphere at 10 bar. After cooling at room temperature, the reaction mixture was filtered through Celite and concentrated under reduced pressure. The resulting residue was diluted with ethyl acetate, washed with water and brine, dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography on silica gel (eluted with methanol in dichloromethane) gave the desired product. LCMS:R t 0.99, m / z=489 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.98(d,J=4.77Hz,2H),8.26(s,2H),7.98(s,1H),7.76(br d,J=7.34Hz,1H),7.50(t,J=4.77Hz,1H),6.54(quin,J=7.06Hz,1H),4.02(s,3H),1.82-1.75(m,3H)ppm.

[0381] Step B: Preparation of 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (compound P37) [ka] To a solution of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate (35 mg, 72 μmol) in aqueous ammonia (0.350 mL) at room temperature was added lanthanum(III) trifluoromethanesulfonate (4.2 mg, 7.2 μmol). The reaction mixture was heated to 70° C. and stirred for 2 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. Precipitation in diethyl ether afforded 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (compound P37) as a white solid. LCMS:R t 0.88, m / z=474 (M+H + ); 1 H NMR (400MHz, methanol-d4) δ=8.99(d,J=5.14Hz,2H),8.42(s,2H),8.15(s,1H),7.62(t,J=4.77Hz,1H),6.31(s,1H),1.79(d,J=6.97Hz,3H)ppm.

[0382] Step C: Preparation of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide [ka] To a solution of 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (110 mg, 0.232 mmol) in toluene (0.93 mL) was added 1,1-dimethoxy-N,N-dimethyl-methanamine (0.062 mL, 0.465 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirred for 2 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure to give (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide as a white solid, which was used without further purification. 1 H NMR(400MHz,DMSO-d6)δ=9.70-9.61(m,1H),9.01(d,J=4.77Hz,2H),8.64(s,1H),8.42(s,2H) ,8.31(s,1H),7.66(s,1H),6.09-5.96(m,1H),3.23-3.09(m,6H),1.69(d,J=6.97Hz,3H)ppm.

[0383] Step D: Preparation of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide [ka] To a solution of hydroxylamine hydrochloride (24.6 mg, 0.355 mmol) in acetic acid (1.25 mL) was added sodium hydroxide (1N in water, 0.355 mL, 0.355 mmol) dropwise. The reaction was slightly exothermic so the reaction mixture was cooled to room temperature and stirred for 15 minutes. A solution of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylaminomethylene)-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (125 mg, 0.237 mmol) in acetic acid (1 mL) was then added and the reaction mixture was stirred at room temperature for 1 h and then concentrated under reduced pressure to provide (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide, which was used without further purification. LCMS:R t 0.93, m / z=517 (M+H + ).

[0384] Step E: Preparation of N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P1) [ka] To a solution of (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino)methylene]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (164 mg, 0.318 mmol) in dioxane (0.79 mL) was added dropwise at room temperature with acetic acid (0.79 mL). The reaction mixture was heated to 90° C. and stirred for 2 h. After cooling to room temperature, the reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were washed with water, dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification of the crude material by reverse phase chromatography (eluting with acetonitrile in water) afforded N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P1) as a beige solid. LCMS:R t 1.01, m / z=499 (M+H + ). 1 H-NMR (400MHz, CDCl 3 ):δ=9.02(d,J=4.77Hz,2H),8.64(s,1H),8.27(s,2H),8.02(s,1H),7.59-7.50(m,2H),6.64-6.57(m,1H),1.84(d,J=6.97Hz,3H)ppm

[0385] Example 6: Preparation of N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30) [ka] Step A: Preparation of N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide [ka] To a solution of methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxylate (119 mg, 0.244 mmol) in methanol (1 mL) at room temperature was added hydrazine hydrate (35%, 52 μL, 0.37 mmol). The reaction mixture was heated to 60° C. and stirred for 1 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure to give N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide as a beige solid, which was used without further purification. LCMS:R t 0.87, m / z=489 (M+H + ).

[0386] Step B: Preparation of N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30) [ka] To a mixture of N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (120 mg, 0.246 mmol) and trimethyl orthoformate (1.38 mL) was added p-toluenesulfonic acid (17 mg, 0.098 mmol) at room temperature. The reaction mixture was heated to 140° C. and stirred for 5 h. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) afforded N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30) as a white solid. LCMS:R t 0.95, m / z=499 (M+H+ ). 1 H-NMR(400MHz,DMSO-d6):δ=9.72(br ppm.

[0387] Example 7: Preparation of N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P28) [ka] Step A: Preparation of 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine [ka] To a suspension of potassium thiocyanate (7.8 g, 79 mmol) in dry acetone (56 mL) at room temperature was added propionyl chloride (7.5 g, 79 mmol). The reaction was heated to 60° C. and stirred for 1 h. After cooling to room temperature, methanol (8.1 mL) was added and the reaction was heated to 60° C. and stirred for 14 h. After cooling to room temperature, the suspension was filtered through Celite and the filtrate was concentrated to give O-methyl N-propanoyl carbamothioate.

[0388] A mixture of O-methyl N-propanoyl carbamothioate (7.0 g, 48 mmol) and 2-hydrazinopyrimidine (CAS7504-94-1, 8.1 g, 71 mmol) in dry ethanol (95 mL) was heated to 90° C. and stirred for 4 h. After cooling to room temperature, the reaction mixture was filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography on silica gel (isopropanol in chloroform) gave 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine. LCMS:Rt 0.62, m / z=206 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.84-8.80(m,2H),7.27-7.24(m,1H),4.11(s,3H),3.28(q,J=7.58Hz,2H),1.38(t,J=7.52Hz,3H)ppm.

[0389] Step B: Preparation of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine [ka] A mixture of 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine (1.50 g, 7.30 mmol), N-bromosuccinimide (2.1 g, 12 mmol) and benzoyl peroxide (0.18 g, 0.73 mmol) in acetonitrile (8.5 mL) was irradiated under a 230 Watt white lamp for 30 min. The reaction mixture was concentrated under reduced pressure. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) gave 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine as a yellow solid. LCMS:R t 0.75, m / z=284, 286 (M+H + ); 1 H-NMR (400MHz, DMSO-d6): δ=8.98(d,J=4.77Hz,2H),7.61(s,1H),6.30(q,J=6.97Hz,1H),3.97(s,3H),2.05(d,J=6.60Hz,3H)ppm.

[0390] Step C: Preparation of 1-(5-Methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine; hydrobromide salt [ka] A solution of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine (2.1 g, 7.4 mmol) in ammonia (7 M in methanol, 110 mL) was stirred at room temperature for 40 h. The reaction mixture was concentrated under reduced pressure. Trituration in diethyl ether gave 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine; hydrobromide, which was used without further purification. LCMS:R t 0.18, m / z=221 (M+H + ).

[0391] Step D: Preparation of N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide [ka] To a solution of 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine; hydrobromide (2.20 g, 6.56 mmol) and triethylamine (2.51 mL, 17.9 mmol) in dry dichloromethane (60 mL) was added 3-5-bis(trifluoromethyl)benzoyl chloride (CAS 785-56-8, 1.08 mL, 5.97 mmol) dropwise at 0-5° C. The reaction mixture was stirred at room temperature for 1 h. After concentration under reduced pressure, the crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide as a yellow solid. LCMS:R t 0.99, m / z=461 (M+H + ); 1 H-NMR (400MHz, CDCl 3):δ=8.97-8.81(m,2H),8.33-8.19(m,2H),8.08-7.97(m,1H),7.60-7.46(m,1H) ,7.44-7.31(m,1H),6.58-6.33(m,1H),4.26-4.08(m,3H),1.80-1.68(m,3H)ppm; 19 F NMR (377MHz, CDCl 3 ) δ = -62.86(s,6 F) ppm.

[0392] Step E: Preparation of N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P26) [ka] To a solution of N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.43 mmol) in acetic acid (2.2 mL) was added hydrobromic acid (33% in acetic acid, 0.76 mL, 4.3 mmol) at room temperature. The reaction mixture was first stirred at room temperature for 18 hours and then at 40° C. for 5 hours. After concentration under reduced pressure, the crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P26) as a yellow solid. LCMS:R t 0.92, m / z=447 (M+H + ); 1 H-NMR(400MHz,DMSO-d6):δ=11.6(s,1H),9.51(d,J=6.97Hz,1H),8.90(d,J=4.77Hz,2H),8.46( s,2H),8.31(s,1H),7.50(t,J=4.77Hz,1H),6.03(t,J=6.97Hz,1H),1.63(d,J=6.97Hz,3H)ppm; 19F NMR (377MHz, DMSO-d6): δ=-61.30(s,6F)ppm.

[0393] Step F: Preparation of N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide [ka] A solution of N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.45 mmol), chlorodifluoroacetic acid (0.30 g, 2.2 mmol) and potassium carbonate (0.63 g, 4.5 mmol) in N,N-dimethylformamide (5 mL) was heated to 80° C. and stirred for 16 h. After cooling to room temperature, the reaction mixture was diluted in ethyl acetate and washed with water and brine. The combined organic layers were dried over sodium sulfate, filtered and concentrated under reduced pressure. Purification of the crude material by flash chromatography on silica gel (ethyl acetate in cyclohexane) gave N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide. LCMS:R t 1.07, m / z=497 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.94(d,J=5.14Hz,2H),8.25(s,2H),8.05(s,1H),7.43(d,J=4.77Hz,1H),7.07-7.25-7.45(br t,1H,CHF 2 ),6.47(dd,J=8.25,6.79Hz,1H),1.76(d,J=6.60Hz,3H)ppm; 19 F-NMR (377MHz, CDCl 3 ):δ=-61.30(s,6 F),-86.16(d,2 F)ppm.

[0394] Example 8: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19) [ka] Step A: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (P20) [ka] To a solution of N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (0.20 g, 0.38 mmol) in dry 1,4-dioxane (11 mL) was added trifluoromethylthiolate(2,2-bipyridine)copper(I) (CAS 1413732-47-4, 0.18 g, 0.57 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirred for 20 hours. After cooling to room temperature, the reaction mixture was filtered through Celite and concentrated under reduced pressure. Purification of the crude material first by flash chromatography on silica gel (ethyl acetate in cyclohexane) and then by reverse phase chromatography (acetonitrile in water) afforded N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (P20) as a gum. LCMS:R t 1.15, m / z=545 (M+H + ); 1 H-NMR (400MHz, CDCl 3):δ=8.90(br d,J=4.40Hz,2H),7.97-7.85(m,1H),7.70(s,2H),7.44(br t,J=4.58Hz,1H),6.75(br d,J=6.97Hz,1H),2.95(s,3H),1.82(d,J=7.34Hz,3H)ppm; 19 F-NMR (377MHz, CDCl 3 ):δ=-39.77(s,3 F),-63.02(s,6 F).

[0395] Step B: Preparation of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19) [ka] To a solution of N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (55 mg, 0.10 mmol) in dichloromethane (3 mL) was added 3-chloroperbenzoic acid (29 mg, 0.12 mmol) in three portions at 0° C. The reaction mixture was allowed to reach room temperature and stirred for 6 days. The reaction mixture was quenched with saturated sodium bicarbonate solution. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure. The crude material was purified by reverse phase chromatography (acetonitrile in water) to give N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P19) as an oil. LCMS:R t 1.17, m / z=577 (M+H + ).

[0396] Example 9: Preparation of N-[(1S)-1-[2-pyrimidin-2-yl-5-(trifluoromethoxy)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P23) [ka] To a solution of N-[(1S)-1-(2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (0.547 g, 1.27 mmol) in acetonitrile (13 mL) at room temperature, 1-(trifluoromethoxy)pyridine-4-carbonitrile; 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.200 g, 0.424 mmol) and tris(2,2'-bipyridine)ruthenium(II) hexafluorophosphate (0.018 g, 0.021 mmol) were added. The reaction mixture was stirred at room temperature for 2 hours under irradiation of blue LED light. After concentration under reduced pressure, the crude material was purified by flash chromatography on silica gel (methanol in dichloromethane) to give N-[(1S)-1-[2-pyrimidin-2-yl-5-(trifluoromethoxy)-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide as a yellow solid. LCMS:R t 1.10, m / z=515 (M+H + ); 1 H-NMR (400MHz, CDCl 3 ):δ=8.96(d,J=4.8Hz,2H),8.27(s,2H),8.05(s,1H),7.50-7.44(m,1H),7.41-7.34(m,1H),6.56-6.43(m,1H),1.77(d,J=7.0Hz,3H)ppm.

[0397] [Table 13-1] [Table 13-2] [Table 13-3] [Table 13-4] [Table 13-5] [Table 13-6] [Table 13-7] [Table 13-8]

[0398] [Table 14-1] [Table 14-2]

[0399] The activity of the composition according to the invention can be considerably broadened and adapted to the general situation by adding other insecticidal, acaricidal and / or fungicidal active ingredients.The mixture of the compound of formula I with other insecticidal, acaricidal and / or fungicidal active ingredients can also have further unexpected advantages, which may be described as synergistic activity in a broader sense.For example, it is better tolerated by plants, reduces phytotoxicity, insects can be controlled at different developmental stages, or it behaves better during their preparation, for example during grinding or mixing, during their storage or during their use.

[0400] Suitable additives to the active ingredients herein are, for example, exemplified by the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, urea, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylurea, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0401] The following mixtures of compounds of formula I with active ingredients are preferred (the abbreviation "TX" means "one compound selected from the compounds defined in Tables A-1 to A-92 and Table P"): an adjuvant selected from the group of substances consisting of petroleum (alternative name) (628) + TX, Abamectin+TX, Acequinocyl+TX, Acetamiprid+TX, Acetoprole+TX, Acrinathrin+TX, Acinonapyr+TX, Afidopiropen+TX, Afoxalanal+TX, Alanycarb+TX, Allethrin+TX, α-Cypermethrin+TX, α-Methrin+TX, Amidoflumet+TX, Aminocarb+TX, Azocyclotine+TX, Bensultap+TX, Benzochimate+TX, Benzpyrimoxane+TX, β-Cyfluthrin+TX, β-Cypermethrin+TX, Bifenazate+TX, Bifenthrin+TX, Binapacryl+ TX, Bioallethrin + TX, Bioallethrin S)-Cyclopentyl Isomer + TX, Bioresmethrin + TX, Bistrifluron + TX, Brofuranilide + TX, Broflutrinate + TX, Bromophos-ethyl + TX, Buprofezin + TX, Butocarboxim + TX, Cadusafos + TX, Carbaryl + TX, Carbosulfan + TX, Cartap + TX, CAS Number: 1472050-04-6 + TX, CAS Number: 1632218-00-8 + TX, CAS Number: 1808115-49-2 + TX, CAS Number: 2032403-97-5 + TX, CAS Number: 2044701-44-0+TX, CAS Number: 2128706-05-6+TX, CAS Number: 2249718-27-0+TX, Chlorantraniliprole+TX, Chlordane+TX, Chlorfenapyr+TX, Chlorprallethrin+TX, Chromafenozide+TX, Clempirin+TX, Cloetocarb+TX, Clothianidin+TX, 2-Chlorophenyl N-methylcarbamate (CPMC)+TX, Cyanofenphos+TX, Cyantraniliprole+TX, Cyclaniliprole+TX, Cycloprothrin+TX, Cyclo Xapride + TX, Cycloxapride + TX, Cyenopyrafen + TX, Cyetoprafen (or Etopirafen) + TX, Cyflumetofen + TX, Cyfluthrin + TX, Cyhalodiamide + TX, Cyhalothrin + TX, Cypermethrin + TX, Cyphenothrin + TX, Cyromazine + TX, Deltamethrin + TX, Diafenthiuron + TX, Dialifos + TX, Dibrom + TX, Dichloromezothiaz + TX, Diflovidazin + TX, Diflubenzuron + TX, Dimepropyridaz + TX, Dinactin + TX, Dinocap + TX, Dinotefuran + TX,Dioxabenzophos+TX, Emamectin+TX, Empentrin+TX, ε-Monfluorotrin+TX, ε-Metofluthrin+TX, Esfenvalerate+TX, Ethion+TX, Ethiprole+TX, Etofenprox+TX, Etoxazole+TX, Fanfur+TX, Fenazaquin+TX, Fenfluthrin+TX, Fenitrothion+TX, Fenobucarb+TX, Fenothiocarb+TX, Fenoxycarb+TX, Fenpropathrin+TX, Fenproximate+TX, Fensulfothion+TX, Fenthion+TX, Fentin acetate +TX, Fenvalerate +TX, Fipronil +TX, Flomethoquin +TX, Flonicamid +TX, Fluacrypyrim +TX, Fluazaindolizine +TX, Fluazuron +TX, Flubendiamide +TX, Flubenzimine +TX, Flucythrinate +TX, Flucycloxuron +TX, Flucythrinate +TX, Fluensulfone +TX, Flufenerim +TX, Flufenprox +TX, Flufiprole +TX, Fluhexafon +TX, Flumethrin +TX, Fluopyram +TX, Flupyradifurone +TX, Flupiry amine+TX, fluralaner+TX, fluvalinate+TX, fluxamethamide+TX, fosthiazate+TX, gamma-cyhalothrin+TX, gossiplur(trademark)+TX, guadipyr+TX, halofenozide+TX, halofenprox+TX, heptafluthrin+TX, hexythiazox+TX, hydramethylnon+TX, imicyafos+TX, imidacloprid+TX, imiprothrin+TX, indoxacarb+TX, iodomethane+TX, iprodione+TX, isocycloceram+TX, isothioate+TX, ibel Mectin + TX, κ-bifenthrin + TX, κ-tefluthrin + TX, lambda-cyhalothrin + TX, lepimectin + TX, lufenuron + TX, metaflumizone + TX, metaldehyde + TX, metam + TX, methomyl + TX, methoxyfenozide + TX, metofluthrin + TX, metolcarb + TX, mexacarbate + TX, milbemectin + TX, momfluorotrin + TX, niclosamide + TX, nitenpyram + TX, nithiazine + TX, omethoate + TX, oxamyl + TX, oxazosphyl + TX, parathion-ethyl + TX,Permethrin+TX, Fenothrin+TX, Phosphocarb+TX, Piperonylbutoxide+TX, Pirimicarb+TX, Pirimiphos-ethyl+TX, Polyhedrovirus+TX, Prallethrin+TX, Profenofos+TX, Profenofos+TX, Profluthrin+TX, Propargite+TX, Propetamphos+TX, Propoxur+TX, Prothiofos+TX, Protrifenbut+TX, Piflubumid+TX, Pymetrozine+TX, Pyraclofos+TX, Pyrafluprole+TX, Pyridaben+TX, Pyridalyl+TX, Pyrifluquinazon+TX TX, pyrimidifen+TX, pirimostrobin+TX, pyriprole+TX, pyriproxyfen+TX, resmethrin+TX, sarolaner+TX, selamectin+TX, silafluofen+TX, spinetoram+TX, spinosad+TX, spirodiclofen+TX, spiromesifen+TX, spiropydione+TX, spirotetramat+TX, sulfoxaflor+TX, tebufenozide+TX, tebufenpyrad+TX, tebupirimiphos+TX, tefluthrin+TX, temephos+TX, tetrachloraniliprole+TX, tetradifon+TX , tetramethrin+TX, tetramethylfluthrin+TX, tetranactin+TX, tetraniliprole+TX, θ-cypermethrin+TX, thiacloprid+TX, thiamethoxam+TX, thiocyclam+TX, thiodicarb+TX, thiofanox+TX, thiometon+TX, thiosultap+TX, thioxazaphen+TX, tolfenpyrad+TX, toxaphene+TX, tralomethrin+TX, transfluthrin+TX, triazamate+TX, triazophos+TX, trichlorfon+TX, trichloronate+TX, trichloro phosphatidylcholine+TX, triflumezopyrin+TX, cyclopyrazoflor+TX, zeta-cypermethrin+TX, seaweed extract and fermentation product from melasse+TX, seaweed extract and fermentation product from melasse containing urea+TX, amino acids+TX, potassium and molybdenum and EDTA-chelated manganese+TX, seaweed extract and fermented plant product+TX, seaweed extract and fermented plant product containing plant hormones+TX, vitamins+TX, EDTA-chelated copper+TX, zinc+TX, and iron+TX, azadirachtin+TX, Bacillus aizawai+TX,Bacillus chitinosporus AQ746 (NRRL accession number B-21618) + TX, Bacillus firmus + TX, Bacillus kurstaki + TX, Bacillus mycoides AQ726 (NRRL accession number B-21664) + TX, Bacillus pumilus (NRRL accession number B-30087) + TX, Bacillus pumilus AQ717 (NRRL accession number B-21662) + TX, Bacillus sp. AQ178 (ATCC accession number 53522) + TX, Bacillus sp. AQ175 (ATCC accession number 55608) + TX, Bacillus sp. AQ177 (ATCC accession number 55609) + TX, Bacillus subtilis unspecified + TX, Bacillus subtilis AQ153 (ATCC accession number 55614) + TX, Bacillus subtilis AQ30002 (NRRL accession number B-50421) + TX, Bacillus subtilis AQ30004 (NRRL accession number B-50455) + TX, Bacillus subtilis AQ713 (NRRL accession number B-21661) + TX, Bacillus subtilis AQ743 (NRRL accession number B-21665) + TX, Bacillus thuringiensis AQ52 (NRRL accession number B-21619) + TX, Bacillus thuringiensis BD#32 (NRRL accession number B-21530) + TX, Bacillus thuringiensis subspec. kurstaki BMP 123 + TX, Beauveria bassiana + TX, D-limonene + TX, granulovirus + TX, harpin + TX,Helicoverpa armigera nucleopolyhedron virus +TX, Helicoverpa zea nucleopolyhedron virus +TX, Heliothis virescens nucleopolyhedron virus +TX, Heliothis punctigera nucleopolyhedron virus +TX, Metarhizium spp. +TX, Muscodor albus 620 (NRRL Accession No. 30547) +TX, Muscodor roseus A3-5 (NRRL Accession No. 30548) +TX, Neem tree products +TX, Paecilomyces fumosoroseus +TX, Paecilomyces lilacinus +TX, lilacinus+TX, Pasteuria nishizawae+TX, Pasteuria penetrans+TX, Pasteuria ramosa+TX, Pasteuria thornei+TX, Pasteuria usgae+TX, P-cymene+TX, Plutella xylostella granulosis virus+TX, Plutella xylostella nuclear polyhedrosis virus+TX, Polyhedrovirus+TX, Jochuan daisy+TX, QRD 420 (Terpenoid Blend)+TX, QRD 452 (Terpenoid Blend)+TX, QRD 460 (Terpenoid Blend)+TX, Quillaja saponaria+TX, Rhodococcus globerus globerulus AQ719 (NRRL accession number B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces galbus (NRRL accession number 30232) + TX, Streptomyces sp. (NRRL accession number B-30145) + TX,Terpenoid blend + TX, and an insect control active agent selected from Verticillium spp.; an algicide selected from the group of substances consisting of bethoxadin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, sibutrin [CCN] + TX, dichloron (1052) + TX, dichlorophen (232) + TX, endothal (295) + TX, fentin (347) + TX, hydrated lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamide (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, an anthelmintic selected from the group of substances consisting of abamectin (1) + TX, crufomate (1011) + TX, doramectin (alternative name) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alternative name) [CCN] + TX, ivermectin (alternative name) [CCN] + TX, milbemycin oxime (alternative name) [CCN] + TX, moxidectin (alternative name) [CCN] + TX, piperazine [CCN] + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX, an avian repellent selected from the group of substances consisting of chloralose (127)+TX, endrin (1122)+TX, fenthion (346)+TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745)+TX, 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, dichlorophene (232) + TX, dipyrithione (1105) + TX, dodysine (1112) + TX, phenaminosulf (1144) + TX, formaldehyde (404) + TX, hydrargafen (alternative name) [CCN] + a fungicide selected from the group of substances consisting of 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, tecloftalam (766) + TX and thiomersal (alternative name) [CCN] + TX; Adoxophyes orana GV (alternative name) (12) + TX, Agrobacterium radiobacter (alternative name) (13) + TX, Amblyseius spp. (alternative name) (19) + TX, Anagrapha falcifera NPV (alternative name) (28) + TX, Anagrus atomus (alternative name) (29) + TX, Aphelinus abdominalis (alternative name) (33) + TX, Aphidius colemani (alternative name) (34) + TX, Aphidoletes aphidimisa aphidimyza (alternative name) (35) + TX, Autographa californica NPV (alternative name) (38) + TX, Bacillus firmus (alternative name) (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 (51)+TX, Bacillus thuringiensis subsp. japonensis (51)+TX, Bacillus thuringiensis subsp. kurstaki (51)+TX, Bacillus thuringiensis subsp. tenebrionis (51)+TXtenebrionis (scientific name) (51) + TX, Beauveria bassiana (alternative name) (53) + TX, Beauveria brongniartii (alternative name) (54) + TX, Chrysoperla carnea (alternative name) (151) + TX, Cryptolaemus montrouzieri (alternative name) (178) + TX, Cydia pomonella GV (alternative name) (191) + TX, Dacnusa sibirica (alternative name) (212) + TX, Diglyphus isaea (alternative name) (254) + TX, Encarsia formosa (scientific name) (293)+TX, Eretmocerus eremicus (alternative name) (300)+TX, Helicoverpa zea NPV (alternative name) (431)+TX, Heterorhabditis bacteriophora and H. megidis (alternative name) (433)+TX, Hippodamia convergens (alternative name) (442)+TX, Leptomastix dactylopii (alternative name) (488)+TX, Macrolophus caliginosus (alternative name) (491)+TX, Mamestra brassicae NPV (alternative name) (494) + TX, Metaphycus helvolus (alternative name) (522) + TX, Metarhizium anisopliae var. acridum (scientific name) (523) + TX, Metarhizium anisopliae var. anisopliae (scientific name) (523) + TX, Neodiprion sertifer NPV and N. lecontilecontei NPV (alternative name) (575)+TX, Orius spp. (alternative name) (596)+TX, Paecilomyces fumosoroseus (alternative name) (613)+TX, Phytoseiulus persimilis (alternative name) (644)+TX, Spodoptera exigua multicapsid nuclear polyhedrosis virus (scientific name) (741)+TX, Steinernema bibionis (alternative name) (742)+TX, Steinernema carpocapsae (alternative name) (742)+TX, Steinernema felchiae (alternative name) (742)+TX, feltiae (alternate name) (742)+TX, Steinernema glaseri (alternate name) (742)+TX, Steinernema riobrave (alternate name) (742)+TX, Steinernema riobravis (alternate name) (742)+TX, Steinernema scapterisci (alternate name) (742)+TX, Steinernema spp. (alternate name) (742)+TX, Trichogramma spp. (alternate name) (826)+TX, Typhlodromus a biological agent selected from the group of substances consisting of Verticillium lecanii (alternative name) (848) + TX, a soil sterilant selected from the group of substances consisting of iodomethane (IUPAC name) (542) and methyl bromide (537) + TX; sterilizing agents selected from the group of substances consisting of Afolate [CCN] + TX, Visadyl (alternative name) [CCN] + TX, Busulfan (alternative name) [CCN] + TX, Diflubenzuron (250) + TX, Dimatif (alternative name) [CCN] + TX, Hemel [CCN] + TX, Hempa [CCN] + TX, Metepa [CCN] + TX, Methiotepa [CCN] + TX, Methyl Afolate [CCN] + TX, Morzide [CCN] + TX, Penfluron (alternative name) [CCN] + TX, Tepa [CCN] + TX, Thiohempa (alternative name) [CCN] + TX, Thiotepa (alternative name) [CCN] + TX, Tretamine (alternative name) [CCN] and Uredepa (alternative name) [CCN] + TX, (E)-Deca-5-en-1-yl acetate and (E)-deca-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-4,1 0-Dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-Dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-Hexadec-11-enal (IUPAC name) (436) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (437) + TX, (Z)-Hexadec-11-en-1-yl acetate (IUPAC name) (438) + TX Sadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) + TX, (Z)-Icos-13-en-10-one (IUPAC name) (448) + TX, (Z)-Tetradeca-7-en-1-al (IUPAC name) (782) + TX, (Z)-Tetradeca-9-en-1-ol (IUPAC name) (783) + TX, ( Z)-Tetradeca-9-en-1-yl acetate (IUPAC name) (784) + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate (IUPAC name) (283) + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate (IUPAC name) (780) + TX, (9Z,12E)-tetradeca-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, α-multistriatin (alternative name) [CCN] + TX, Brevicomin (alternative name) [CCN] + TX, Codrelure (alternative name) [CCN] + TX, Codlemone (alternative name) (167) + TX, Curua ( Alternative name) (179) + TX, Disparlure (277) + TX, Dodec-8-en-1-yl acetate (IUPAC name) (286) + TX, Dodec-9-en-1-yl acetate (IUPAC name) (287) + TX, Dodec-8 + TX, 10-dien-1-yl acetate (IUPAC name) (284) + TX, Dominicalure (alternative name) [CCN] + TX, Ethyl 4-methyloctanoate (IUPAC name) (317) + TX, Eugenol (alternative name) )[CCN]+TX, Frontalin (alternative name)[CCN]+TX, Gossip Lua (alternative name)(420)+TX, Grand Lua (421)+TX, Grand Lua I (alternative name)(421)+TX, Grand Lua II (alternative name)(421)+TX, Grand Lua III (alternative name)(421)+TX, Grand Lua IV (alternative name)(421)+TX, Hexalua[CCN]+TX, Ipsdienol (alternative name)[CCN]+TX, Ipsenol (alternative name[ CCN] + TX, Japonirua (alternative name) (481) + TX, Lineatin (alternative name) [CCN] + TX, Litrur (alternative name) [CCN] + TX, Lupulur (alternative name) [CCN] + TX, Medulur [CCN] + TX, Megatomoic acid (alternative name) [CCN] + TX, Methyleugenol (alternative name) (540) + TX, Muscarua (563) + TX, Octadeca-2,13-dien-1-yl acetate (IUPAC name) (588) + TX, Octadeca-3,13-dien-1-yl acetate (IUPAC name) (589) + TX, Olfrular (alternative name) [CCN] + TX, Orictalure (alternative name) (317) + TX, Ostramon (alternative name) [CCN] + TX, Siglua [CCN] + TX, Soldigin (alternative name) (736) + TX, Sulcatol (alternative name) [CCN] + TX, Tetradec-11-en-1-yl acetate (IUPAC name) (785) + TX, Trimedulure (839) + TX, Trimedulure A (alternative name) (839) + TX, Trimedulure B, 1 (Alternative name)(839)+TX, Trimedrua B 2 an insect pheromone selected from the group of substances consisting of (alternative name) (839) + TX, trimedlure C (alternative name) (839) and trunc-call (alternative name) [CCN] + TX; Bis(tributyltin)oxide (IUPAC name) (913) + TX, Bromoacetamide [CCN] + TX, Calcium arsenate [CCN] + TX, Cloethocarb (999) + TX, Copper acetarsenite [CCN] + TX, Copper sulfate (172) + TX, Fentin (347) + TX, Ferric phosphate (IUPAC name) (352) + TX, Metaldehyde (518) + TX, Methiocarb (530) + TX, Niclosamide (576) + TX, Niclosamide-olamine (576) + TX, Pentachloroethane (518) + TX, a molluscicide selected from the group of substances consisting of: thazimcarb (623) + TX, sodium pentachlorophenoxide (623) + TX, thazimcarb (1412) + TX, thiodicarb (799) + TX, tributyltin oxide (913) + TX, triphenmorph (1454) + TX, trimethacarb (840) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX, pyriprole [394730-71-3] + TX, 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) (1062) + TX, (substruct name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alternative name) (210) + TX, abamectin (1) + TX, acetoprole [CCN] + TX, alanycarb (15) + TX, aldicarb (16) + TX, aldoxicarb (863) + TX, AZ60541 (compound code) + TX, benclothiaz [CCN] + TX, benomyl (62) + TX, butylpyridaben (alternative name) + TX, cadusafos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, cloethocarb (999) + TX, cytokinin (alternative name) (210) + TX, dazomet (216 )+TX, DBCP(1045)+TX, DCIP(218)+TX, Diamidaphos(1044)+TX, Diclofenthion(1051)+TX, Dicrifos(alternative name)+TX, Dimethoate(262)+TX, Doramectin(alternative name)[CCN]+TX, Emamectin(291)+TX, Emamectin benzoate(291)+TX, Eprinomectin(alternative name)[CCN]+TX, Ethoprophos(312)+TX, Ethylene dibromide(316) +TX, Fenamiphos (326) +TX, Fenpyrad (alternative name) +TX, Fensulfothion (1158) +TX, Hostiazate (408) +TX, Hostiethane (1196) +TX, Furfural (alternative name) [CCN] +TX, GY-81 (development code) (423) +TX, Heterofos [CCN] +TX, Iodomethane (IUPAC name) (542) +TX, Isamidophos (1230) +TX, Isazophos (1231) +TX, Ivermectin CCN+TX, Kinetin(alternative name)(210)+TX, Mecarfone(1258)+TX, Metam(519)+TX, Metam-potassium(alternative name)(519)+TX, Metam-sodium(519)+TX, Methyl bromide(537)+TX, Methyl isothiocyanate(543)+TX, Milbemycin oxime(alternative name)(CCN)+TX, Moxidectin(alternative name)(CCN)+TX, Myrotheciumverrucaria composition (alternative name) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphocarb [CCN] + TX, cebufos (alternative name) + TX, selamectin (alternative name) [CCN] + TX, spinosad (737) + TX, terbam (alternative name) + TX, terbufos (773) + TX, tetrachlorothiophene (IU a nematicide selected from the group of substances consisting of PAC / Chemical Abstracts Name (1422) + TX, Thiafenox (alternative name) + TX, Thionazine (1434) + TX, Triazophos (820) + TX, Triazuron (alternative name) + TX, Xylenol [CCN] + TX, YI-5302 (compound code) and Zeatin (alternative name) (210) + TX, Fluensulfone [318290-98-1] + TX, Fluopyram + TX, a nitrification inhibitor selected from the group of substances consisting of potassium ethylxanthate [CCN] and nitrapyrin (580)+TX; a plant activator selected from the group of substances consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alternative name) (720) + TX, 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, antu (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, bisthiosemi (912) + TX, brodifacoium (89) + TX, bromadiolone (91) + TX, brome Talin (92) + TX, Calcium cyanide (444) + TX, Chloralose (127) + TX, Chlorophacinone (140) + TX, Cholecalciferol (alternative name) (850) + TX, Coumachlor (1004) + TX, Coumafuryl (1005) + TX, Coumatetralyl (175) + TX, Crimidine (1009) + TX, Difenacoum (246) + TX, Difethialone (249) + TX, Diphacinone (273) + TX, Ergocalciferol (301) + TX, Flocoumafe Fluoroacetamide (379) + TX, flupropidine (1183) + TX, flupropidine 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, norboramide (1318) + TX, fosacetim (1336) + TX, phosphinium rodenticides selected from the group of substances consisting of arsenic (IUPAC name) (640) + TX, phosphorus [CCN] + TX, pindone (1341) + TX, potassium arsenite [CCN] + TX, pyrinuron (1371) + TX, sciliroside (1390) + TX, sodium arsenite [CCN] + TX, sodium cyanide (444) + TX, sodium fluoroacetate (735) + TX, strychnine (745) + TX, thallium sulfate [CCN] + TX, warfarin (851) and zinc phosphide (640) + TX; a synergist selected from the group of substances consisting of 2-(2-butoxyethoxy)ethyl piperonylate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol and nerolidol (alternative names) (324) + TX, MB-599 (development code) (498) + TX, MGK 264 (development code) (296) + TX, piperonyl butoxide (649) + TX, piperotal (1343) + TX, propyl isomer (1358) + TX, S421 (development code) (724) + TX, sesamex (1393) + TX, sesamolin (1394) and sulfoxide (1406) + TX, an animal repellent selected from the group of substances consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper naphthenate [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, thiram (804) + TX, trimethacarb (840) + TX, zinc naphthenate [CCN] and ziram (856) + TX; A virucidal agent selected from the group of substances consisting of Imanin (alternative name) [CCN] and Ribavirin (alternative name) [CCN] + TX; a wound protectant selected from the group of substances consisting of mercuric oxide (512)+TX, octhilinone (590) and thiophanate-methyl (802)+TX, and 1,1-Bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-Dichlorophenylbenzenesulfonate+TX, 2-Fluoro-N-methyl-N-1-cinnamaldehyde+TX, 4-Chlorophenylphenylsulfone+TX, Acetoprole+TX, Aldoxicarb+TX, Amidithione+TX, Amidothioate+TX, Amiton+TX, Amiton hydrogen oxalate+TX, Amitraz+TX, Aramite+TX, Arsenic trioxide+TX, Azobenzene+TX, Azotoate+TX, Benomyl+TX, Benoxafos+TX, Benzylbenzoate Oxalate +TX, Bixafen +TX, Brofenvalerate +TX, Bromocyclen +TX, Bromophos +TX, Bromopropylate +TX, Buprofezin +TX, Butocarboxim +TX, Butoxycarboxim +TX, Butylpyridaben +TX, Calcium polysulfate +TX, Camphechlor +TX, Carbanolate +TX, Carbophenothione +TX, Cymiazole +TX, Thiomethionate +TX, Chlorbeside +TX, Chlordimeform +TX, Chlordimeform hydrochloride +TX, Chlorphenetole +TX, Chlorphenson +TX , Chlorphenesulfide+TX, Chlorobenzilate+TX, Chlormebuform+TX, Chlormethiuron+TX, Chloropropylate+TX, Chlorthiophos+TX, Cinerin I+TX, Cinerin II+TX, Cinerins+TX, Closantel+TX, Coumaphos+TX, Crotamiton+TX, Crotoxyphos+TX, Kufraeb+TX, Cyanthoate+TX, DCPM+TX, DDT+TX, Demefion+TX, Demefion-O+TX, Demefion-S+TX, Demeton-methyl+TX, Demeton-O+TX, Demeton-O-methyl+TX , Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methylsulfone+TX, Dichlofluanid+TX, Dichlorvos+TX, Dicrifos+TX, Dienochlor+TX, Dimefox+TX, Zinex+TX, Zinex-diclexin+TX, Dinocap-4+TX, Dinocap-6+TX, Dinocton+TX, Dinopenton+TX, Dinosulfone+TX, Dinotervone+TX, Dioxathion+TX, Diphenylsulfone+TX, Disulfiram+TX, DNOC+TX, Dofenapine+TX, Doramectin+TX, Endothion+TX,Epirinomectin + TX, Ethoate-methyl + TX, Etrimphos + TX, Fenazaflor + TX, Fenbutatin oxide + TX, Fenothiocarb + TX, Fenpyrad + TX, Fenpyroximate + TX, Fenpyrazamine + TX, Fenson + TX, Fentrifanil + TX, Flubenzimine + TX, Flucycloxuron + TX, Fluenethyl + TX, Fluorobenside + TX, FMC 1137+TX, formetanate+TX, formetanate hydrochloride+TX, formoparanate+TX, gamma-HCH+TX, gliodin+TX, halfenprox+TX, hexadecylcyclopropanecarboxylate+TX, isocarbophos+TX, jasmolin I+TX, jasmolin II+TX, jodofenphos+TX, lindane+TX, malonoven+TX, mecarbam+TX, mefosfolan+TX, mesulfen+TX, methacrifos+TX, methyl bromide+TX, metolcarb+TX, mexacarbate+TX, milbemycin oxime+TX, Mipafox + TX, Monocrotophos + TX, Morphothion + TX, Moxidectin + TX, Naled + TX, 4-Chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, Nifluridide + TX, Nikkomycin + TX, Nitrilacarb + TX, Nitrilacarb 1:1 zinc chloride complex + TX, Omethoate + TX, Oxydeprophos + TX, Oxydisulfoton + TX, pp'-DDT + TX, Parathion + TX, Permethrin + TX, Fencaptone + TX, Phosalone + TX, Phosphorane + TX, Phosphamidon + TX, Polychloroterpenes + TX, Poly Linactin+TX, Proclonol+TX, Promacyl+TX, Propoxur+TX, Protidathion+TX, Protoate+TX, Pyrethrin I+TX, Pyrethrin II+TX, Pyrethrin+TX, Pyridafenthion+TX, Pirimitate+TX, Quinalphos+TX, Quinthiophos+TX, R-1492+TX, Phosglycine+TX, Rotenone+TX, Shladan+TX, Cebufos+TX, Selamectin+TX, Sofamido+TX, SSI-121+TX, Sulfiram+TX, Sulfuramide+TX, Sulfotep+TX, Sulfur+TX, Diflobidazin+TX, τ-Fulvalinate+TX, TEPP+TX, Therbam+TX,Tetradifon+TX, Tetrasul+TX, Thiafenox+TX, Thiocarboxim+TX, Thiofanox+TX, Thiometon+TX, Thioquinox+TX, Thuringiensin+TX, Triamiphos+TX, Triaratene+TX, Triazophos+TX, Triazuron+TX, Trifenophos+TX, Trinactin+TX, Vamidothion+TX, Vaniliprole+TX, Bethoxazin+TX, Copper dioctanoate+TX , Copper sulfate + TX, Sibutrin + TX, Dichlorne + TX, Dichlorophen + TX, Endothal + TX, Fentin + TX, Hydrated lime + TX, Nabam + TX, Quinoclamine + TX, Quinoneamide + TX, Simazine + TX, Triphenyltin acetate + TX, Triphenyltin hydroxide + TX, Crufomate + TX, Piperazine + TX, Thiophanate + TX, Chloralose + TX, Fenthion + TX, Pyridin-4-amine + T X, 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, doditin + TX, phenaminosulf + TX, formaldehyde + TX, hydralgafen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, nitrapyrin + TX, octhilinone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, probenazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, tecloftalam + TX, thiomersal + TX, Adoxophyes orana GV+TX, Agrobacterium radiobacter+TX, Amblyseius spp.+TX, Anagrapha falcifera NPV+TX, Anagrus atomus+TX, Aphelinus abdominalis+TX, Aphidius colemani+TX,Aphidoletes aphidimyza + TX, Autographa californica NPV + TX, Bacillus sphaericus Neide + TX, Beauveria brongniartii + TX, Chrysoperla carnea + TX, Cryptolaemus montrouzieri + TX, Cydia pomonella GV + TX, Dacnusa sibirica + TX, Diglyphus isaea + TX, Encarsia formosa + TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H. megidis+TX, Hippodamia convergens+TX, Leptomastix dactylopii+TX, Macrolophus caliginosus+TX, Mamestra brassicae NPV+TX, Metaphycus helvolus+TX, Metarhizium anisopliae var. acridum+TX, Metarhizium anisopliae var. anisopliae+TX, Neodiprion sertifer NPV and N. lecontei NPV + TX, Orius spp. + TX, Paecilomyces fumosoroseus + TX, Phytoseiulus persimilis + TX, Steinernema bibionis + TX,Steinernema carpocapsae + TX, Steinernema feltiae + TX, Steinernema glaseri + TX, Steinernema riobrave + TX, Steinernema riobravis + TX, Steinernema scapterisci + TX, Steinernema spp. + TX, Trichogramma spp. + TX, Typhlodromus occidentalis + TX, Verticillium lecanii)+TX, apholate+TX, visadil+TX, busulfan+TX, dimatif+TX, hemel+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholate+TX, molzide+TX, penfluron+TX, tepa+TX, thiohempa+TX, thiotepa+TX, tretamine+TX, uredepa+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)-Icos-13-en-10-one + TX, (Z)-Tetradeca-7-en-1-al + TX, (Z)-Tetradeca-9-en-1-ol + TX, ( Z)-Tetradeca-9-en-1-yl acetate + TX, (7E,9Z)-dodeca-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradeca-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradeca-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX,4-Methylnonan-5-ol and 4-methylnonan-5-one + TX, α-multistriatin + TX, Brevicomin + TX, Codrelure+TX, Codremon+TX, Querle+TX, Disparlure+TX, Dodec-8-en-1-yl acetate+TX, Dodec-9-en-1-yl acetate+TX, Dodec-8+TX, 10-dien-1-yl acetate+TX, Dominicalure+TX, Ethyl 4-methyloctanoate+TX, Eugenol+TX, Frontalin+TX, Grandrua+TX, Grandrua I+TX, Grandrua II+TX, Grandrua III+TX, Grandrua IV+TX, Hexalure+TX, Ipsdienol+TX, Ipsenol+ TX, Japonirua+TX, Lineatin+TX, Litirua+TX, Loupurua+TX, Medurua+TX, Megatomoic acid+TX, Methyleugenol+TX, Muscarua+TX, Octadeca-2,13-dien-1-yl acetate+TX, Octadeca-3,13-dien-1-yl acetate+TX, Olphularua+TX, Orictalua+TX, Ostramon+TX, Siglua+TX, Soldidin+TX, Sulcatol+TX, Tetradec-11-en-1-yl acetate+TX, Trimedurua+TX, Trimedurua A+TX, Trimedurua B 1 +TX, Trimedrua B 2+TX, trimedlure C +TX, trunc-call +TX, 2-(octylthio)ethanol +TX, butapyronoxyl +TX, butoxy(polypropylene glycol) +TX, dibutyl adipate +TX, dibutyl phthalate +TX, dibutyl succinate +TX, diethyl toluamide +TX, dimethylcarbate +TX, dimethyl phthalate +TX, ethyl hexanediol +TX, hexamide +TX, methoquin-butyl +TX, methyl neodecane amide +TX, oxamate +TX, picaridi 1-Dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-bis(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethylthiocyanate + TX, ate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3,5-xylyloxy)ethanol + TX, 2-chlorovinyldiethylphosphate + TX, 2-imidazolidone + TX, 2-isovalerylindan-1,3-dione + TX, 2-methyl(prop-2-ynyl)aminophenylmethylcarbamate + TX, 2-thiocyanatoethyl laurate + TX, 3-bromo-1-chloroprop-1-ene + TX, 3-methyl-1-phenylpyrazole- 5-yldimethylcarbamate + TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate + TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate + TX, acetione + TX, acrylonitrile + TX, aldrin + TX, allosamidin + TX, alixycarb + TX, α-ecdysone + TX, aluminum phosphide + TX, aminocarb + TX, anabasine + TX, atidathion + TX, azamethiphos + TX, Bacillus thuringiensis δ endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX,Bartholin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, sodium borate + TX, bromfenvinphos + TX, bromo-DDT + TX, bufencarb + TX, butacarb + TX, butathiophos + TX, butonate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, cartap hydrochloride + TX, sebazine + TX, chlorbicyclen + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chlorphoxim + TX, chlorprazophos + TX, cis-resmethrin + TX, cismethrin + TX, clocitrin + TX, acetonitrile + TX, Copper arsenite + TX, copper arsenate + TX, copper oleate + TX, chumithoate + TX, cryolite + TX, CS708 + TX, cyanofenphos + TX, cyanophos + TX, ciclethrin + TX, cithioate + TX, d-tetramethrin + TX, DAEP + TX, dazomet + TX, decarbofuran + TX, diamidaphos + TX, dikapton + TX, dichlorophenthion + TX, dicresyl + TX, dicyc Ranil+TX, Dieldrin+TX, Diethyl 5-methylpyrazol-3-yl phosphate+TX, Dirol+TX, Dimefluthrin+TX, Dimethane+TX, Dimethryn+TX, Dimethylvinphos+TX, Dimethyllan+TX, Dinoprop+TX, Dinosam+TX, Dinoseb+TX, Diofenolan+TX, Dioxabenzophos+TX, Dicyclophos+TX, DSP+TX, Ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, Ethaphos+TX, Ethiofencarb+TX, Ethyl Formate+TX, Ethylene Dibromide+TX, Dichloroethane+TX, Ethylene Oxide+TX, EXD+TX, Fenchlorphos+TX, Fenetacarb+TX, Fenitrothion+TX, Fenoxacrim+TX, Fenpyritrin+TX, Fensulfothion+TX, Fenthion-Ethyl+TX, Flucofuron+TX, Fosmetilan+TX, Fospirate+TX, Fostietan+TX, Furathiocarb+TX, Frethrin+TX, Guazatine+TX, Guazatine Acetate+TX,Sodium tetrathiocarbonate+TX, Halfenprox+TX, HCH+TX, HEOD+TX, Heptachlor+TX, Heterofos+TX, HHDN+TX, Hydrogen cyanide+TX, Hikincarb+TX, IPSP+TX, Isazophos+TX, Isobenzane+TX, Isodrin+TX, Isofenphos+TX, Isorane+TX, Isoprothiolane+TX, Isoxathion+TX, Juvenile hormone I+TX, Juvenile hormone II+TX, Juvenile Insect hormone III + TX, Kereban + TX, Kinoprene + TX, Lead arsenate + TX, Leptophos + TX, Lilimphos + TX, Ritidathion + TX, m-Cumenyl methylcarbamate + TX, Magnesium phosphide + TX, Magidox + TX, Mecarfone + TX, Menazone + TX, Mercurous chloride + TX, Mesulfenphos + TX, Metam + TX, Metam-potassium + TX, Metam-sodium + TX, Methanesulfonyl fluoride + TX, Metoclotophos + TX, Methoprene + TX, Methotrin + TX, Methoxychlor + TX, Methyl isothiocyanate + TX, Methyl chloroform + TX, Methylene chloride + TX, Methoxadiazone + TX, Mirex + TX, Naphthalophos + TX, Naphthalene + TX, NC-170 + TX, Nicotine + TX, Nicotine sulfate + TX, Nithiazine + TX, Nornicotine + TX, O-5-Dichloro-4-iodophenyl O-Ethyl Ethyl Phosphonothioate + T X, O,O-Diethyl O-4-methyl-2-oxo-2H-chromen-7-yl phosphorothioate + TX, O,O-Diethyl O-6-methyl-2-propylpyrimidin-4-yl phosphorothioate + TX, O,O,O',O'-Tetrapropyldithiopyrophosphate + TX, Oleic acid + TX, para-dichlorobenzene + TX, parathion-methyl + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, Fenkapton+TX, Phosnichlor+TX, Phosphine+TX, Phoxim-methyl+TX, Pyrimetaphos+TX, Polychlorodicyclopentadiene isomers+TX, Potassium arsenite+TX, Potassium thiocyanate+TX, Precocene I+TX, Precocene II+TX, Precocene III+TX, Pyrimidophos+TX, Profluthrin+TX, Promecarb+TX, Prothiophos+TX, Pyrazophos+TX, Pyresmethrin+TX,Cassia + TX, Quinalphos-methyl + TX, Quinothione + TX, Rafoxanide + TX, Resmethrin + TX, Rotenone + TX, Cadetrin + TX, Riania + TX, Ryanodine + TX, Sabadira + TX, Shradan + TX, Cebufos + TX, SI-0009 + TX, Tiapronil + TX, Sodium arsenite + TX, Sodium cyanide + TX, Sodium fluoride + TX, Sodium hexafluorosilicate + TX, Sodium pentachlorophenoxide salt + TX, Sodium selenate + TX, Sodium thiocyanate + T X, Sulcofuron+TX, Sulcofuron-sodium+TX, Sulfuryl fluoride+TX, Sulprofos+TX, Tar oil+TX, Thionazine+TX, TDE+TX, Tebupirimfos+TX, Temephos+TX, Telarethrin+TX, Tetrachloroethane+TX, Cyclofos+TX, Thiocyclam+TX, Thiocyclam hydrogen oxalate+TX, Thionazine+TX, Thiosultap+TX, Thiosultap-sodium+TX, Tralomethrin+TX, Transpermethrin+TX, Triazamate+TX, Trichlormethaphos -3+TX, trichloronathate+TX, trimethacarb+TX, tolprocarb+TX, triclopyricarb+TX, triplen+TX, veratridine+TX, veratrine+TX, XMC+TX, zetamethrin+TX, zinc phosphide+TX, zolaprophos+TX, and meperfluthrin+TX, tetramethylfluthrin+TX, bis(tributyltin)oxide+TX, bromoacetamide+TX, ferric phosphate+TX, niclosamide-olamine+TX, tributyltin oxide+TX, pyrimorph+TX, triphenmorph+T X, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazinan-3-ylacetic acid + TX, 6-isopentenylaminopurine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, rufural + TX, isamidophos + TX, kinetin + TX, Myrothecium verrucaria composition + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX,Potassium ethylxanthate + TX, Acibenzolar + TX, Acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, α-chlorohydrin + TX, Anth + TX, Barium carbonate + TX, Bisthiosemi + TX, Brodifacoum + TX, Bromadiolone + TX, Bromethalin + TX, Chlorophacinone + TX, Cholecalciferol + TX, Coumachlor + TX, Coumafuryl + TX, Coumatetralyl + TX, Crimidine + TX, Difenacoum + TX, Difethialone + TX, Diphacinone + TX, Ergocalciferol + TX, Flocoumafen + TX, Fluoroacetamide + TX, Flupropazine + TX, Flupropazine hydrochloride + TX, Norbormide + TX, Fosacetim + TX, Phosphate + TX, Pindone + TX, Pyrinuron + TX, Scililoside + TX, Sodium Fluoroacetate + TX, Thallium Sulfate + TX, Warfarin + TX, 2-(2-Butoxyethoxy)ethyl Piperonylate + TX, 5-(1,3-Benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, Farnesol and Nerolidol + TX, Verbutin + TX, MGK 264+TX, piperonyl butoxide+TX, piprotal+TX, propyl isomer+TX, S421+TX, sesamex+TX, sesamolin+TX, sulfoxide+TX, anthraquinone+TX, copper naphthenate+TX, copper oxychloride+TX, dicyclopentadiene+TX, thiram+TX, zinc naphthenate+TX, ziram+TX, imanin+TX, ribavirin+TX, mercury(II) oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bitertanol+TX, bromuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furametpyr+TX, hexaconazo ol+TX, imazalil+TX, imibenconazole+TX, ipconazole+TX, metconazole+TX, myclobutanil+TX, paclobutrazol+TX, pefurazoate+TX, penconazole+TX, prothioconazole+TX, pyrifenox+TX, prochloraz+TX, propiconazole+TX, pyrisoxazole+TX, simeconazole+TX, tebuconazole+TX, tetraconazole+TX, triadimefon+TX, triadimenol+TX, triflumizole+TX, triticonazole+TX, ancymidol+TX, fenarimol+TX, nuarimol+TX, bupirimate+TX, dimethirimol+TX, ethirimol+TX, dodemorph+TX, fenpropidin+TX, fenpropimorph+TX, spiroxamine+TX,Tridemorph+TX, Cyprodinil+TX, Mepanipyrim+TX, Pyrimethanil+TX, Fenpiclonil+TX, Fludioxonil+TX, Benalaxyl+TX, Furalaxyl+TX, Metalaxyl+TX, R-Metalaxyl+TX, Ofrace+TX, Oxadixyl+TX, Carbendazim+TX, Debacarb+TX, Fuberidazole+TX, Thiabendazole+TX, Chlozolinate+TX, Diclozolin+TX, Mycrozolin+TX, Procymidone+TX, Vinclozolin+TX, Boscalid+TX, Carboxin+TX, Fenfuram+T X, Flutolanil + TX, Mepronil + TX, Oxycarboxin + TX, Penthiopyrad + TX, Thifluzamide + TX, Dodine + TX, Iminoctadine + TX, Azoxystrobin + TX, Dimoxystrobin + TX, Enestrobulin + TX, Phenaminestrobin + TX, Flufenoxystrobin + TX, Fluoxastrobin + TX, Kresoxim-methyl + TX, Metominostrobin + TX, Trifloxystrobin + TX, Oryzastrobin + TX, Picoxystrobin + TX, Pyraclostrobin + TX, Pyrametstrobin + TX, Pi Laxystrobin+TX, Ferbam+TX, Mancozeb+TX, Maneb+TX, Metiram+TX, Propineb+TX, Zineb+TX, Captafol+TX, Captan+TX, Fluorimide+TX, Folpet+TX, Tolylfluanid+TX, Bordeaux mixture+TX, Copper oxide+TX, Mancopper+TX, Oxine copper+TX, Nitrothal-isopropyl+TX, Edifenphos+TX, Iprobenfos+TX, Phosdifen+TX, Turcophos-methyl+TX, Anilazine+TX, Benthiavalicarb+TX, Blasticidin-S+TX, Chloroform+TX, Loneb+TX, Chlorothalonil+TX, Cyflufenamid+TX, Cymoxanil+TX, Diclocymet+TX, Diclomedine+TX, Dicloran+TX, Diethofencarb+TX, Dimethomorph+TX, Flumorph+TX, Dithianon+TX, Ethaboxam+TX, Etridiazole+TX, Famoxadone+TX, Fenamidon+TX, Fenoxanil+TX, Ferimzone+TX, Fluazinam+TX, Fluopicolide+TX, Flusulfamide+TX, Fluxapyroxad+TX, Fenhexamid+TX, Fosetyl-aluminum+TX,Hymexazol + TX, Iprovalicarb+TX, Cyazofamid+TX, Methasulfocarb+TX, Metrafenone+TX, Pencycuron+TX, Phthalide+TX, Polyoxin+TX, Propamocarb+TX, Pyribencarb+TX, Proquinazid+TX, Pyroquilon+TX, Pyriophenone+TX, Quinoxyfen+TX, Quintozene+TX, Tiadinil+TX, Triazoxide+TX, Tricyclazole+TX, Triforine+TX, Validamycin+TX, Valifenalate+TX, Zoxamide+TX, Benzylpropamide + TX, Isopyrazam + TX, Sedaxane + TX, Benzovindiflupyr + TX, Pydiflumetofen + TX, 3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide + TX, Isoflucipram + TX, Isotianil + TX, Dipimethitrone + 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, methoxystrobin (jiaxiangjunzhi) + TX, lvbenmixianan + TX, diclobenziazox + TX, mandestrobin + TX, 3-(4,4-difluoro-3,4-dihydro-3,3-Dimethylisoquinolin-1-yl)quinolone + TX, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol + TX, oxathiapiproline + TX, t-butyl N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, pyraziflumide + TX, impirfluxam + TX, tulorprocarb + TX, mefentrifluconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl 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-piperidyl]thiazol-4-yl]-4,5-dihydro- Soxazol-5-yl]-3-chloro-phenyl]methanesulfonic acid + TX, but-3-ynyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate + TX, methyl N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamate + TX, 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine + TX, pyridaclomethyl + 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, amethoctrazine + TX, amisulbrom + TX, penflufen + TX, (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide + TX, florylpicoxamide + TX, fenpicoxamide + TX, tebufloquine + TX, ipurfenoquine + TX, quinofumelin + TX, isofetamide + TX, 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) 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethyl ... Pyridine-3-carboxamide + 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, Methyltetraprole + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-biphenyl]-4-yl]-5-pyrimidinemethanol + TX, fluoxapiproline + TX, enoxastrobin + 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, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-sulfanyl-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-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX,1-Difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac + TX, cumoxystrobin + TX, zhongshengmycin + TX, copper thiodiazole + TX, zinc thiazole + TX, amethotractin + TX, iprodione + TX, (N-methoxy-N-[[4-[5-(trifluoro N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide + TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide + 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]propanamide + 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, ethyl 1-[[4 N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine + TX) (wherein the compounds in the mixture other than TX are not shown in WO 2017 / 055473, WO 2017 / 055469, WO 2017 / 055472, WO 2017 / 055473, WO 2017 / 055474, WO 2017 / 055475, WO 2017 / 055476, WO 2017 / 055477, WO 2017 / 055478, WO 2017 / 055479 ... and 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 methods described in WO 2016 / 156290), (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3-carboxylate +TX (this compound can be prepared by the methods described in WO 2014 / 006945), 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetrone +TX (this compound can be prepared by the methods described in WO 2011 / 138281), N-methyl-4-[ 5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzenecarbothioamide + 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)- a biologically active substance selected from N-ethyl-N-methyl-formamidine + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (which compound may be prepared by the method described in WO 2016 / 202742), and 2-(difluoromethyl)-N-[(3S)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX (which compound may be prepared by the method described in WO 2014 / 095675),Macrobials including: Aphelinus abdominalis + TX, Aphidius ervi (Aphelinus-System®) + TX, Acerophagus papaya + TX, Adalia bipunctata (Adalia-System®) + TX, Adalia bipunctata (Adaline®) + TX, Adalia bipunctata (Aphidalia®) + TX, Ageniaspis citricola + TX, Ageniaspis fuscicollis + TX, Amblyseius andersonii andersoni (Anderline®+TX, Andersoni-System®)+TX, Amblyseius californicus (Amblyline®+TX, Spical®)+TX, Amblyseius cucumeris (Thripex®+TX, Bugline cucumeris®)+TX, Amblyseius fallacis (Fallacis®)+TX, Amblyseius swirskii (Bugline swirskii®+TX, Swirskii-Mite®)+TX, Amblyseius womersleyi (WomerMite®)+TX, Amitus hesperidum hesperidum+TX, Anagyrus atomus+TX, Anagyrus fusciventris+TX, Anagyrus kamali+TX, Anagyrus loecki+TX, Anagyrus pseudococcuspseudococci (Citripar®) + TX, Anicetus benefices + TX, Anisopteromalus calandrae + TX, Anthocoris nemoralis (Anthocoris-System®) + TX, Aphelinus abdominalis (Apheline® + TX, Aphiline®) + TX, Aphelinus asychis + TX, Aphidius colemani (Aphipar®) + TX, Aphidius ervi (Ervipar®) + TX, Aphidius gifuensis + TX, Aphidius matricariae matricariae (Aphipar-M®) + TX, Aphidoletes aphidimyza (Aphidend®) + TX, Aphidoletes aphidimyza (Aphidoline®) + TX, Aphytis lingnanensis + TX, Aphytis melinus + TX, Aprostocetus hagenowii + TX, Atheta coriaria (Staphyline®) + TX, Bombus spp. + TX, Bombus terrestris (Natupol Beehive®) + TX, Bombus terrestris (Beeline® + TX, Tripol®) + TX, Cephalonomia stephanoderis + TX, Chilocorus nigritus + TX, Chrysoperlacarnea (Chrysoline®) + TX, Chrysoperla carnea (Chrysopa®) + TX, Chrysoperla rufilabris + TX, Cirrospilus ingenuus + TX, Cirrospilus quadristriatus + TX, Citrostichus phyllocnistoides + TX, Closterocerus chamaeleon + TX, Closterocerus spp. + TX, Coccidoxenoides perminutus (Planopar®) + TX, Coccophagus cowperi + TX, Coccophagus lycimnia + TX, Cotesia flavipes + TX, Cotesia plutellae + TX, Cryptolaemus montrouzieri (Cryptobug (registered trademark) + TX, Cryptoline (registered trademark)) + TX, Cybocephalus nipponicus + TX, Dacnusa sibirica + TX, Dacnusa sibirica (Minusa (registered trademark)) + TX, Diglyphus isaea (Diminex (registered trademark)) + TX, Delphastus catalinae catalinae (Delphastus®) + TX, Delphastus pusillus + TX, Diachasmimorpha krausii + TX, Diachasmimorpha longicaudata + TX, Diaparsisjucunda + TX, Diaphorencyrtus aligarhensis + TX, Diglyphus isaea + TX, Diglyphus isaea (Miglyphus® + TX, Digline®) + TX, Dacnusa sibirica (DacDigline® + TX, Minex®) + TX, Diversinervus spp. + TX, Encarsia citrina + TX, Encarsia formosa (Encarsia max® + TX, Encarline® + TX, En-Strip®) + TX, Eretmocerus eremicus (Enermix®) + TX, Encarsia guadeloupae + TX, Encarsia haitiensis + TX, Episyrphus balteatus (Syrphidend®) + TX, Eretmoceris siphonini + TX, Eretmocerus californicus + TX, Eretmocerus eremicus (Ercal® + TX, Eretline e®) + TX, Eretmocerus eremicus (Bemimix®) + TX, Eretmocerus hayati + TX, Eretmocerus mundus mundus (Bemipar®+TX, Eretline m®)+TX, Eretmocerus siphonini+TX, Exochomus quadripustulatus+TX, Feltiellaacarisuga (Spidend®) + TX, Feltiella acarisuga (Feltiline®) + TX, Fopius arisanus + TX, Fopius ceratitivorus + TX, Formononetin (Wirless Beehome®) + TX, Franklinothrips vespiformis (Vespop®) + TX, Galendromus occidentalis + TX, Goniozus legneri + TX, Habrobracon hebetor + TX, Harmonia axyridis (HarmoBeetle®) + TX, Heterorhabditis spp. (Lawn Patrol®) + TX, Heterorhabditis bacteriophora (NemaShield HB® + TX, Nemaseek® + TX, Terranem-Nam® + TX, Terranem® + TX, Larvanem® + TX, B-Green® + TX, NemAttack® + TX, Nematop®) + TX, Heterorhabditis megidis (Nemasys H® + TX, BioNem H (registered trademark) + TX, Exhibitline hm (registered trademark) + TX, Larvanem-M (registered trademark) + TX, Hippodamia convergens (Hypoaspis aculeifer) (Aculeifer-System (registered trademark) + TX, Entomite-A (registered trademark)) + TX, Hypoaspis miles (Hypoline m (registered trademark) + TX, Entomite-M (registered trademark)) + TX, Lbalia leucospoides (Lebalia leucospoides) + TX, Lecanoideus floccissimus (Lecanoideus floccissimus) + TX, Lemophagus errabundus (Leptomastidea abnormis + TX, Leptomastix dactylopii (Leptopar®) + TX, Leptomastix epona + TX, Lindorus lophantaelophanthae+TX, Lipolexis oregmae+TX, Lucilia caesar (Natufly®)+TX, Lysiphlebus testaceipes+TX, Macrolophus caliginosus (Mirical-N®+TX, Macroline c®+TX, Mirical®)+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, Micromus angulatus (Milacewing®)+TX, Microterys flavus+TX, Muscidifurax raptorellus and Spalangia cameroni (Biopar®)+TX, Neodryinus typhlocybae+TX, Neoseiulus californicus+TX, Neoseiulus cucumeris (THRYPEX®)+TX, Neoseiulus fallacis+TX, Nesideocoris tenuis (NesidioBug®+TX, Nesibug®)+TX, Ophyra aenescens aenescens (Biofly®) + TX, Orius insidiosus (Thripor-I® + TX, Oriline i®) + TX, Orius laevigatus (Thripor-L® + TX, Oriline l®) + TX, Orius majusculus (Orilinem®) + TX, Orius strigicollis (Thripor-S®) + TX, Pauesia juniperorum + TX, Pediobius foveolatus + TX, Phasmarhabditis hermaphrodita (Nemaslug®) + TX, Phymastichus coffea + TX, Phytoseiulus macropilus + TX, Phytoseiulus persimilis (Spidex® + TX, Phytoline p®) + TX, Podisus maculiventris (Podisus®)+TX, Pseudacteon curvatus+TX, Pseudacteon obtusus+TX, Pseudacteon tricuspis+TX, Pseudaphycus maculipennis+TX, Pseudleptomastix mexicana+TX, Psyllaephagus pilosus+TX, Psyttalia concolor (complex)+TX, Quadrastichus spp.+TX, Rhyzobius lophanthae+TX, Rodolia ladybird beetle (Rodolia spp.)+TX, cardinalis+TX, Rumina decollate+TX, Semielacher petiolatus+TX, Sitobion avenae (Ervibank®)+TX, Steinernema carpocapsae (NematacC®+TX, Millenium®+TX, BioNem C®+TX, NemAttack®+TX, Nemastar®+TX, Capsanem®)+TX, Steinernema feltiae (NemaShield®+TX, Nemasys F®+TX, BioNem F®+TX, Steinernema-System®+TX, NemAttack®+TX, Nemaplus®+TX, Exhibitline sf®+TX, Scia-rid®+TX, Entonem®)+TX, Steinernema kraussei (Nemasys L®+TX, BioNem L®+TX, Exhibitline srb®)+TX, Steinernema riobrave (Steinernema riobrave (BioVector®+TX, BioVektor®)+TX, Steinernema scapterisci (Nematac S®)+TX, Steinernema spp.+TX, Steinernema spp. (Guardian Nematodes®)+TX, Stethorus punctillum (Stethorus®)+TX, Tamarixia radiate+TX, Tetrastichus setifer+TX, Thripobius semiluteus+TX, Torymus sinensis+TX, Trichogramma brassicae) (Tricholine b®) + TX, Trichogramma brassicae) (Tricho-Strip®) + TX, Trichogrammaevanescens+TX, Trichogramma minutum+TX, Trichogramma ostriniae+TX, Trichogramma platneri+TX, Trichogramma pretiosum+TX, Xanthopimpla stemmator; and Other biological products include: Abscisic acid +TX, bioSea® +TX, Chondrostereum purpureum (Chontrol Paste®) +TX, Colletotrichum gloeosporioides (Collego®) +TX, Copper octanoate (Cueva®) +TX, Delta Trap (Trapline d®) +TX, Erwinia amylovora (Harpin) (ProAct® +TX, Ni-HIBIT Gold CST®) +TX, Ferri-phosphate (Ferramol®) +TX, Funnel Trap (Trapline y®) +TX, Gallex® +TX, Grower's Secret®+TX, Homo-brassonolide+TX, Iron Phosphate (Lilly Miller Worry Free Ferramol Slug&Snail Bait®)+TX, MCP hail trap (Trapline f®)+TX, Microctonus hyperodae+TX, Mycoleptodiscus terrestris (Des-X®)+TX, BioGain®+TX, Aminomit®+TX, Zenox®+TX, Pheromone trap (Thripline ams®) + TX, potassium bicarbonate (MilStop®) + TX, potassium salts of fatty acids (Sanova®) + TX, potassium silicate solution (Sil-Matrix®) + TX, potassium iodide + potassium thiocyanate (Enzicur®) + TX, SuffOil-X® + TX, spider venom + TX, Nosema locustae (Semaspore Organic Grasshopper Control®) + TX, sticky traps (Trapline YF® + TX, RebellAmarillo(registered trademark))+TX and trap (Takitrapline y+b(registered trademark))+TX.

[0402] The reference numbers in square brackets after the active ingredient, e.g. [3878-19-1], refer to Chemical Abstracts Registration Numbers. The above mixture partners are known. When the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual-A World Compendium; Thirteenth Edition; Editor: CDS Tomlin; The British Crop Protection Council], they are listed therein under the section number shown in parentheses above for the specific compound; for example, the compound "Abamectin" is listed under section number (1). When "[CCN]" is added above to a specific compound, the corresponding compound is included in the "Compendium of Pesticide Common Names", which is accessible on the Internet [A. Wood; Compendium of Pesticide Common Names, (Copyright) 1995-2004]; for example, the compound "acetoprole" is listed at the Internet address: http: / / www.alanwood.net / pesticides / acetoprole.html.

[0403] Most of the active ingredients mentioned above are referred to above by so-called "common names", and the relevant "ISO common names" or another "common name" is used in individual cases. If the designation is not a "common name", the nature of the designation used instead is indicated in parentheses for the particular compound; in that case, the IUPAC name, IUPAC / Chemical Abstracts name, "chemical name", "common name", "compound name" or "development code" is used, or if neither one of these designations nor a "common name" is used, an "alternative name" is used. "CAS Registry Number" means Chemical Abstracts Registry Number.

[0404] The active ingredient mixtures of the compounds of formula I selected from the compounds defined in Tables A-1 to A-92 and Table P and the active ingredients as defined above are preferably in a mixing ratio of 100:1 to 1:6000, in particular 50:1 to 1:50, more in particular 20:1 to 1:20, even more in particular 10:1 to 1:10, very in particular 5:1 and 1:5 (a ratio of 2:1 to 1:2 is particularly preferred, a ratio of 4:1 to 2:1 is likewise preferred), in particular 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 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. These mixing ratios are by weight.

[0405] The mixture may be used in a method of controlling pests, the method comprising the step of applying a composition comprising the mixture to the pest or its environment, excluding methods of treatment of the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0406] Mixtures comprising a compound of formula I selected from the compounds defined in Tables A-1 to A-92 and Table P and one or more of the active ingredients described above can be applied, for example, in a single ready-mix form, as a combined spray mixture composed of separate formulations of a single active ingredient, such as a "tank mix", and in combination with a single active ingredient when applied sequentially, i.e., one after the other over a fairly short period of time, such as a few hours or days. The order of application of the compound of formula I and the active ingredients described above is not critical to the practice of the invention.

[0407] The compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized palm oil, rapeseed oil or soybean oil), antifoaming agents, for example silicone oils, preservatives, viscosity regulators, binders and / or tackifiers, fertilizers or other active ingredients for obtaining specific effects, for example bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0408] The compositions according to the invention are prepared in a manner known per se, both in the absence of auxiliaries, for example by grinding, sieving 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 auxiliaries and / or grinding.These methods for the preparation of the compositions and the use of compound I for the preparation of these compositions are also the subject of the present invention.

[0409] The application methods for the compositions, i.e. spraying, misting, dusting, brushing, dusting, spreading or pouring (which should be selected according to the intended purpose in the prevailing situation), are other subjects of the present invention, as well as the use of the compositions for controlling the above-mentioned types of pests. Typical concentration rates are 0.1-1000 ppm, preferably 0.1-500 ppm, of active ingredient. The application rate per hectare is generally 1-2000 g of active ingredient per hectare, in particular 10-1000 g / ha, preferably 10-600 g / ha.

[0410] The preferred method of application in the field of crop protection is application to the foliage of the plant (foliar application), the frequency and rate of application being chosen to suit the risk of infestation by the relevant pest. Alternatively, the active ingredient can reach the plant via the root system (systemic action) by irrigating the plant habitat with a liquid composition or by introducing the active ingredient in solid form into the plant habitat, for example the soil, for example in the form of granules (soil application). In the case of rice plants, such granules can be metered into the paddy field.

[0411] The compounds of formula I of the present invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds or seedlings such as fruits, tubers or grains, from the above-mentioned types of pests. The propagation material can be treated with the compounds before planting, for example seeds can be treated before sowing. Alternatively, the compounds can be applied to the seed kernels by immersing the latter in a liquid composition or by applying a layer of a solid composition (coating). If the propagation material is planted at the site of application, it is also possible to apply the compositions in the furrows, for example during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the present invention. Typical treatment rates depend on the plant and the pests / fungi to be controlled and are generally between 1 and 200 grams per 100 kg of seeds, preferably between 5 and 150 grams per 100 kg of seeds, such as between 10 and 100 grams per 100 kg of seeds.

[0412] The term seed encompasses all types of seeds and plant propagules, including but not limited to true seeds, seed pieces, suckers, corn kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings, and the like, and in a preferred embodiment refers to true seeds.

[0413] The present invention also includes seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and / or containing" generally indicates that the active ingredient is most often on the surface of the seed when applied, but depending on the application method, some of the ingredient may penetrate more or less into the seed material. When the seed product is (re)planted, the active ingredient may be absorbed. In one embodiment, the present invention makes available a plant propagation material to which a compound of formula I is attached. Furthermore, this makes available a composition comprising a plant propagation material treated with a compound of formula I.

[0414] 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 application of the compound of formula I can be carried out by any known method, such as by spraying or dusting the seeds before sowing or at the time of sowing / planting the seeds.

[0415] The compounds of the invention are distinguishable from other similar compounds by their higher efficacy at low application rates and / or by different pest control, which can be achieved, if desired, at lower concentrations, e.g. 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm; or 300, 200 or 100 mg AI / m 2 Higher efficacy can be observed by a person skilled in the art using experimental techniques using lower application rates such as: Higher efficacy can be observed by a higher safety profile (improved physicochemical properties or higher biodegradability for above- and below-ground non-target organisms such as fish, birds and bees).

[0416] Biological Examples: The following examples illustrate the present invention. Certain compounds of the present invention can be distinguished from known compounds by their high efficacy at low application rates, which can be verified by those skilled in the art using the experimental procedures outlined in the examples, and using lower application rates, such as 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm, if necessary.

[0417] Example B1: Diabrotica balteata (corn rootworm) Corn sprouts placed on agar layers in 24-well microtiter plates were treated by spraying with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (6-10 per well). Four days after infestation, samples were assessed for mortality and growth inhibition compared to untreated samples.

[0418] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P2, P3, P4, P5, P6, P7, P8, P14, P15, P16, P17, P18, P19, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35

[0419] Example B2: Euschistus heros (Neotropical Brown Stink Bug) Soybean leaves on agar in 24-well microtiter plates were sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N2 nymphs. Samples were assessed for mortality and growth inhibition compared to untreated samples 5 days after infestation.

[0420] The following compounds provided at least 80% control in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P1, P2, P3, P7, P11, P12, P16, P17, P18, P22, P25, P29, P32, P33, P37, P38

[0421] Example B3: Frankliniella occidentalis (Western flower thrips): Feeding / contact activity Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with test solutions prepared from a 10,000 DMSO stock solution. After drying, the leaf discs were infested with Frankliniella populations of various ages. Samples were assessed for mortality 7 days after infestation.

[0422] The following compounds caused at least 80% mortality at a rate of 200 ppm: P1, P4, P12, P16, P28, P37

[0423] Example B4: Chilo suppressalis (rice stem borer) 24-well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 larvae (6-8 per well). Samples were assessed for mortality, antifeedant effect and growth inhibition 6 days after infestation compared to untreated samples. Control of Chilo suppressalis by the test sample was achieved if at least one of the categories (mortality, antifeedant effect and growth inhibition) was higher than that of untreated samples.

[0424] The following compounds provided at least 80% control in at least one of the categories (mortality, antifeedant effect or growth inhibition) at a rate of 200 ppm: P1, P3, P4, P8, P11, P12, P14, P19, P21, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37

[0425] Example B5: Plutella xylostella (Diamond back moth) 24-well microtiter plates containing artificial diet were treated by pipette with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, diamondback moth eggs were pipette through a plastic stencil onto gel blotter paper and the plate was closed with this. Samples were assessed for mortality and growth inhibition compared to untreated samples 8 days after infestation.

[0426] The following compounds provided at least 80% efficacy in at least one of two categories (mortality or growth inhibition) at a rate of 200 ppm: P1, P2, P3, P4, P5, P7, P8, P9, P14, P15, P16, P17, P18, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36

[0427] Example B6: Myzus persicae (Green peach aphid): Feeding / contact activity Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with aphid populations of various ages. Samples were assessed for mortality 6 days after infestation.

[0428] The following compounds caused at least 80% mortality at a rate of 200 ppm: P3, P4, P7, P11, P12, P16, P17, P18, P21, P22

[0429] Example B7: Myzus persicae (Green peach aphid). Systemic activity Roots of pea seedlings infested with aphid populations of various ages were placed directly into test solutions prepared from DMSO stock solutions at 10,000. Samples were assessed for mortality 6 days after the seedlings were placed in the test solutions.

[0430] The following compounds produced at least 80% mortality at a test rate of 24 ppm: P2, P12, P16, P17, P21

[0431] Example B8: Myzus persicae (Green peach aphid). Intrinsic activity Test compounds prepared from 10,000 ppm DMSO stock solutions were applied by pipette to 24-well microtiter plates and mixed with the sucrose solution. The plates were closed with stretched Parafilm. A plastic stencil with 24 holes was placed on the plate and infested pea seedlings were placed directly on the Parafilm. The infested plates were closed with gel blotter paper and another plastic stencil and then inverted. Samples were assessed for mortality 5 days after infestation.

[0432] The following compounds produced at least 80% mortality at test rates of 12 ppm: P2, P3, P4, P7, P11, P12, P16, P17, P18, P21, P22, P28, P30, P31, P32, P34, P36, P37, P38

[0433] Example B9: Spodoptera littoralis (Egyptian cotton leaf worm) Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with five L1 larvae. Samples were assessed for mortality, antifeedant effect and growth inhibition 3 days after infestation compared to untreated samples. Control of Spodoptera littoralis by the test sample was provided if at least one of the categories (mortality, antifeedant effect and growth inhibition) was higher than the untreated sample.

[0434] The following compounds provided at least 80% control in at least one of the categories (mortality, antifeedant effect or growth inhibition) at a rate of 200 ppm: P2, P3, P4, P5, P7, P15, P16, P17, P18, P20, P21, P22, P23, P24, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36

[0435] Example B10: Spodoptera littoralis (Egyptian cotton leaf worm) Test compounds were applied by pipette from a 10,000 ppm DMSO stock solution to the 24-well plate and mixed with the agar. Lettuce seeds were placed on the agar and the multi-well plate was closed with another plate also containing agar. After 7 days, the compounds were absorbed by the roots and lettuce grew into the lid plate. Lettuce leaves were then cut into the lid plate. Spodoptera eggs were pipette onto moist gel blotter paper through a plastic stencil and the lid plate was closed with this. Samples were evaluated for mortality, antifeedant effects and growth inhibition 6 days after infestation compared to untreated samples.

[0436] The following compounds produced at least an 80% effect in at least one of the three categories (mortality, feeding inhibition or growth inhibition) at the test rate of 12.5 ppm: P3, P15, P32

[0437] Example B11: Tetranychus urticae (two-spotted spider mite): Feeding / contact activity French bean leaf discs on agar in 24-well microtiter plates were sprayed with aqueous test solutions prepared from a 10'000 ppm DMSO stock solution. After drying, the discs were infested with mite populations of various ages. Samples were assessed for mortality in the mixed population (mobile) 8 days after infestation.

[0438] The following compounds caused at least 80% mortality at a rate of 200 ppm: P36

[0439] Example B12: Thrips tabaci (onion thrips) feeding / contact activity Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with thrips populations of various ages. Samples were assessed for mortality 6 days after infestation.

[0440] The following compounds caused at least 80% mortality at a rate of 200 ppm: P5, P7, P17, P18, P22

[0441] Example B13: Myzus persicae (Green Peach Aphid): Test compounds prepared from 10,000 ppm DMSO stock solutions were applied by a liquid handling robot into 96-well microtiter plates and mixed with the sucrose solution. Parafilm was stretched over the 96-well microtiter plates and a plastic stencil with 96 holes was placed over the plate. Aphids were sieved directly onto the Parafilm into the wells. The infested plates were closed with gel blotter cardboard and a second plastic stencil and then inverted. Samples were assessed for mortality 5 days after infestation.

[0442] The following compounds caused at least 80% mortality at an application rate of 50 ppm: P2, P3, P5, P7, P11, P12, P14, P15, P16, P17, P18, P21, P22, P30, P32, P33, P37, P38

[0443] Example B14: Plutella xylostella (Diamondback Moth): 96-well microtiter plates containing artificial diet were treated with aqueous test solutions prepared from a 10,000 ppm DMSO stock solution by a liquid handling robot. After drying, eggs (approximately 30 per well) were infested onto a netted lid, which was suspended above the diet. Upon egg attachment, L1 larvae descended onto the diet. Samples were assessed for mortality 9 days after infestation.

[0444] The following compounds produced an average mortality effect of at least 80% at an application rate of 500 ppm: P2, P3, P5, P6, P7, P9, P15, P16, P17, P18, P20, P22, P24, P25, P30, P31, P32, P33, P38

Claims

1. Compounds of Formula I 【Chemistry 1】 (In the formula: R 1 is hydrogen, C 1 ~C 6 Alkyl, C 1 ~C 6 Cyanoalkyl, aminocarbonyl C 1 ~C 6 Alkyl, Hydroxycarbonyl C 1 ~C 6 Alkyl, C 1 ~C 6 Nitroalkyl, trimethylsilane C 1 ~C 6 Alkyl, C 1 ~C 6 Haloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl; 3 ~C 4 Cycloalkyl C 1 ~C 2 Alkyl- (wherein the C 3 ~C 4 Cycloalkyl is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH 2 -; or halo or C 1 ~C 6 benzyl optionally substituted with haloalkyl; R 2 is phenyl, pyridine, pyrimidine, pyrazine, or pyridazine, wherein said phenyl, pyridine, pyrimidine, pyrazine, or pyridazine is optionally substituted with 1 to 3 substituents, provided that said substituents are not on any carbon adjacent to the carbon to which C=O is attached, and each substituent is selected from the group consisting of C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Thiohaloalkyl, C 1 ~C 3 Alkoxy, C 1 ~C 3 Haloalkoxy, halogen, NO 2 , S.F. 5 , C.N., C.O.N.H. 2 , COOH and C(S)NH 2 are independently selected from; R 3 is C 1 ~C 3 Alkyl or C 1 ~C 3 haloalkyl; R 4 is pyridine, pyrimidine, pyrazine or pyridazine, where pyridine, pyrimidine, pyrazine or pyridazine is C 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 optionally substituted with one substituent selected from cycloalkyl, halogen, or hydroxy; Z 1 is halogen, CN, NH 2 C(O), amino (i.e., NH 2 ), (C 1 ~C 3 Alkyl)amino, diC 1 ~C 3 Alkyl)amino, hydroxy, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkoxy, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 N.C. (O), (C 1 ~C 3 cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl) (C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, (C 1 ~C 3 alkyl)C(O), HC(O), diphenylmethanimine, C 1 ~C 3 haloalkoxy, phenyl or a 5-membered aromatic heterocycle, wherein said phenyl or said 5-membered aromatic heterocycle is 1 ~C 3 Alkyl, C 1 ~C 3 Haloalkyl, C 1 ~C 3 Alkoxy, C 3 ~C 4 or a stereoisomer, enantiomer, tautomer and N-oxide of a compound of formula I, or an agrochemically acceptable salt thereof.

2. R 3 The compound of claim 1 , wherein is methyl.

3. R 1 is hydrogen; CN, CONH 2 , COOH, NO 2 and -Si(CH 3 ) 3 C optionally substituted with one substituent selected from 1 ~C 6 Alkyl; C 1 ~C 6 Haloalkyl; C 2 ~C 6 Alkenyl; C 2 ~C 6 Alkynyl; C 2 ~C 6 Haloalkynyl; 3 ~C 4 Cycloalkyl-C 1 ~C 2 Alkyl- (wherein the C 3 ~C 4 cycloalkyl- is optionally substituted with 1 or 2 halo atoms; oxetan-3-yl-CH 2 -; or halo or C 1 ~C 3 3. The compound of claim 1 or 2 which is benzyl optionally substituted with haloalkyl.

4. R 2 Is Y 1 ~Y 21 【Chemistry 2】 The compound according to any one of claims 1 to 3, which is one of:

5. R 4 J 1 ~J 8 The compound according to any one of claims 1 to 4, selected from: 【Chemistry 3】

6. R 4 J 1 , J 2 , J 3 , J 4 , J 6 , and J 7 and J. 8 The compound according to any one of claims 1 to 5, selected from:

7. R 1 is cyclopropyl-CH 2 -, CH≡CCH 2 -, CH 2 =CHCH 2 7. The compound according to claim 1, wherein R is -, hydrogen or methyl.

8. Z 1 is halogen, CN, amino, (C 1 ~C 3 alkyl)amino, di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, C 2 ~C 6 Alkenyl, C 2 ~C 6 Haloalkenyl, C 2 ~C 6 Alkynyl, C 2 ~C 6 Haloalkynyl, C 1 ~C 4 Haloalkylsulfanyl, C 1 ~C 4 Haloalkylsulfinyl, C 1 ~C 4 Haloalkylsulfonyl, C 1 ~C 4 Alkylsulfanyl, C 1 ~C 4 Alkylsulfinyl, C 1 ~C 4 Alkylsulfonyl, C 1 ~C 3 Alkoxy-C 1 ~C 3 Alkyl, (C 1 ~C 3 alkyl)sulfonylamino, (C 1 ~C 3 Alkyl)sulfonyl(C 1 ~C 3 alkyl)amino, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), NH 2 C(O), (C 1 ~C 3 cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl) (C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 Haloalkoxy, (C 1 ~C 3 alkyl)C(O), C 1 ~C 3 Alkoxy-C 1 ~C 3 The compound according to any one of claims 1 to 7, which is alkoxy, HC(O) or diphenylmethanimine.

9. Z 1 is halogen, CN, amino, di(C 1 ~C 3 Alkyl)amino, hydroxyl, C 3 ~C 4 Halocycloalkyl, C 3 ~C 4 Cyanocycloalkyl, (C 1 ~C 3 alkyl)NHC(O), (C 1 ~C 3 Alkyl) 2 NC(O), NH 2 C(O), (C 1 ~C 3 cycloalkyl)NHC(O), (C 1 ~C 3 Cycloalkyl) (C 1 ~C 3 alkyl)NC(O), (C 1 ~C 3 alkyl)C(O)(C 1 ~C 3 Alkyl)N, (C 1 ~C 3 alkyl)C(O)NH, C 1 ~C 3 Haloalkoxy, (C 1 ~C 3 alkyl)C(O), C 1 ~C 3 Alkoxy-C 1 ~C 3 The compound according to any one of claims 1 to 7, which is alkoxy, HC(O) or diphenylmethanimine.

10. A composition comprising a compound according to any one of claims 1 to 9, one or more auxiliaries and diluents and optionally one or more other active ingredients.

11. 13. A method for combating and controlling insects, acarids, nematodes or molluscs, comprising the step of applying to the pest, the pest's habitat or to plants susceptible to attack by the pest an insecticidally, acaricidally, nematicidally or molluscicidally effective amount of a compound as claimed in any one of claims 1 to 9 or a composition as claimed in claim 10.

12. A method for the protection of plant propagation material from attack by insects, acarids, nematodes or mollusks, comprising the step of treating the propagation material or the locus in which it is planted with an effective amount of a compound according to any one of claims 1 to 9 or a composition according to claim 10.

13. 11. Plant propagation material, such as a seed, comprising, treated with or having attached thereto a compound according to any one of claims 1 to 9 or a composition according to claim 10.

14. A method for controlling parasites in or on an animal in need thereof comprising administering an effective amount of a compound according to any one of claims 1 to 9 or a composition according to claim 10.

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