Pesticidally active azole-amide compounds

Abstract

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

Description

[0001] This application is a divisional application of the parent case, Chinese invention patent application No. 201980070157.2.

[0002] The present invention relates to pesticidally active, in particular insecticidal, azole-amide compounds, to a process for their preparation, to compositions comprising those compounds, and to their use for controlling animal pests, including arthropods and in particular insects or representatives of the order Acarina.

[0003] WO 2017192385 describes certain heteroaryl-1,2,4-triazole and heteroaryl-tetrazolyl compounds for controlling ectoparasites in animals (such as mammals and non-mammals).

[0004] New pesticidally active oxazolidinone compounds have now been discovered.

[0005] Therefore, the present invention relates in a first aspect to compounds having formula I

[0006]

[0007] in:

[0008] R1 is hydrogen, C1-C6 alkyl, C1-C6 cyanoalkyl, aminocarbonyl C1-C6 alkyl, hydroxycarbonyl C1-C6 alkyl, C1-C6 nitroalkyl, trimethylsilyl C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C4 cycloalkyl C1-C2 alkyl wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms, oxetan-3-yl-CH2-, or benzyl optionally substituted with halogen or C1-C6 haloalkyl;

[0009] R2 is phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which C=O is attached, and each substituent is independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 thiohaloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen, NO2, SF5, CN, CONH2, COOH and C(S)NH2;

[0010] R3 is C1-C3 alkyl or C1-C3 haloalkyl;

[0011] R4 is pyridine, pyrimidine, pyrazine or pyridazine, wherein the pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with a substituent selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen or hydroxy;

[0012] Z1 is halogen, CN, NH2C(O), amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NH C(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, (C1-C3 alkyl)C(O), HC(O), diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy; or stereoisomers, enantiomers, tautomers and N-oxides of the compound of formula I, or an agrochemically acceptable salt thereof.

[0013] Compounds of formula I with at least one basic center can form acid addition salts, for example, with strong inorganic acids (e.g. mineral acids, such as perchloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid or hydrohalic acids), strong organic carboxylic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanecarboxylic 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 for example benzoic acid), or organic sulfonic acids (e.g. unsubstituted or, for example, halogen-substituted C1-C4-alkanesulfonic acids or arylsulfonic acids, such as methanesulfonic acid or p-toluenesulfonic acid). Compounds of formula I having at least one acidic group can, for example, form salts with bases, such as mineral salts, for example alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts; or with ammonia or organic amines (for example morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamines, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or mono-, di- or trihydroxy-lower alkylamines, for example monoethanolamine, diethanolamine or triethanolamine).

[0014] In each case, the compounds of formula I according to the invention are in free form, in oxidized form, such as N-oxides, or in salt form (eg in the form of agronomically usable salts).

[0015] N-oxides are oxidized forms of tertiary amines or oxidized forms of nitrogen-containing heteroaromatic compounds. They are described, for example, by A. Albini and S. Pietra in 1991 in the book "Heterocyclic N-oxides", published by CRC Press, Boca Raton.

[0016] The compounds of formula I according to the invention also include hydrates which may be formed during salt formation.

[0017] As used herein, the term "C1-C n The term “alkyl” refers to a saturated straight or branched hydrocarbon group having 1 to n carbon atoms, attached through any carbon atom, such as any one of 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, and 1-ethyl-2-methylpropyl.

[0018] As used herein, the term "C1-C n “Haloalkyl” refers to a straight-chain or branched saturated alkyl group (as defined above) having 1 to n carbon atoms, attached via any of these carbon atoms, wherein some or all of the hydrogen atoms in these groups may be replaced by fluorine, chlorine, bromine and / or iodine, i.e., for example, any of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trichloroethyl, 2-fluoro-2-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoropropyl, 2,3-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-fluoro-2-ethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, 2-fluoro-2-ethyl, 2-fluoro-2 fluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl. Accordingly, the term "Ci-C2 fluoroalkyl" shall mean a Ci-C2 alkyl group having 1, 2, 3, 4 or 5 fluorine atoms, such as any of the following: difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl or pentafluoroethyl.

[0019] As used herein, the term "C1-C n "Alkoxy" refers to a straight or branched saturated alkyl group having 1 to n carbon atoms (as described above) attached via an oxygen atom, i.e., any of methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy. As used herein, the term "halogenated C1-C n "Alkoxy" refers to C1-C n Alkoxy groups wherein one or more hydrogen atoms on the alkyl group are replaced by the same or different halogen atoms - examples include trifluoromethoxy, 2-fluoroethoxy, 3-fluoropropoxy, 3,3,3-trifluoropropoxy, 4-chlorobutoxy.

[0020] As used herein, the term "C1-C n "Cyanoalkyl" refers to a straight or branched chain saturated C1-C nAlkyl groups (as defined above) wherein one of the hydrogen atoms in these groups is replaced by a cyano group: for example, cyanomethyl, 2-cyanoethyl, 2-cyanopropyl, 3-cyanopropyl, 1-(cyanomethyl)-2-ethyl, 1-(methyl)-2-cyanoethyl, 4-cyanobutyl, and the like.

[0021] As used herein, the term "C3-C n "Cycloalkyl" refers to a 3-n-membered cycloalkyl group such as cyclopropane, cyclobutane, cyclopropane, cyclopentane and cyclohexane.

[0022] As used herein, the term "C3-C4 cycloalkyl-C1-C2 alkyl-" refers to a 3- or 4-membered cycloalkyl group having a methylene or ethylene group attached to the rest of the molecule. In this case, the C3-C4 cycloalkyl-C1-C2 alkyl- group is substituted, with the substituent(s) being on the cycloalkyl group.

[0023] As used herein, the term "aminocarbonyl C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a CONH2 group.

[0024] As used herein, the term "hydroxycarbonyl C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a COOH group.

[0025] As used herein, the term "C1-C n "Nitroalkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a NO2 group.

[0026] As used herein, the term "C1-C n "Haloalkylthio" refers to a C1-C3 haloalkyl moiety attached through a sulfur atom.

[0027] As used herein, the term "trimethylsilane C1-C n "Alkyl" refers to an alkyl group in which one of the hydrogen atoms in the group is replaced by a -Si(CH3)3 group.

[0028] As used herein, the term "C2-C n "Alkenyl" refers to a straight or branched alkenyl chain having two to n carbon atoms and one or two double bonds, for example vinyl, prop-1-enyl, but-2-enyl.

[0029] As used herein, the term "C2-C n "Haloalkenyl" refers to a C2-C4 group substituted by one or more halogen atoms which may be the same or different. n Alkenyl moiety.

[0030] As used herein, the term "C2-C n"Alkynyl" refers to a straight or branched alkynyl chain having from two to n carbon atoms and one triple bond, for example ethynyl, prop-2-ynyl, but-3-ynyl,

[0031] As used herein, the term "C2-C n "Haloalkynyl" refers to a C2-C4 substituted by one or more halogen atoms which may be the same or different. n Alkynyl moiety.

[0032] Halogen is typically fluorine, chlorine, bromine or iodine. This also applies correspondingly to halogen in combination with other meanings, such as haloalkyl.

[0033] As used herein, the term "(C1-C n "C1-C2-alkyl)sulfonylamino" refers to a C1-C2-alkyl group attached to the sulfur atom of the S(O)2 moiety. n Alkyl groups, the sulfur is also attached to the nitrogen atom of an amino (ie, NH) moiety, wherein the nitrogen atom of the amino moiety is bonded to the rest of the molecule, for example, CH3S(O)2NH-.

[0034] As used herein, the term "(C1-C n alkyl)sulfonyl (C1-C n "alkyl)amino" refers to (C1-C n Alkyl)sulfonylamino, wherein the hydrogen atom of the amino group is C1-C n Alkyl substitution, for example CH3S(O)2N(CH3)-.

[0035] As used herein, the term "(C1-C3 alkyl)C(O)(C1-C3 alkyl)N" refers to a C1-C3 alkyl group attached to a carbon atom of a C(=O) moiety. n Alkyl, the carbon is also attached to a nitrogen atom, the nitrogen atom is also attached to a C1-C3 alkyl, and the nitrogen atom is bonded to the rest of the molecule, for example CH3C(O)N(CH3)-.

[0036] Examples of 5-membered heteroaromatic rings include pyrazolyl, furyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, tetrazolyl; preferably pyrazolyl.

[0037] The pyridine, pyrimidine, pyrazine and pyridazine groups (unsubstituted or substituted) of R2 and R4 are each attached to the remainder of the compound through a carbon atom in each ring.

[0038] As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and / or preventing further pest damage, such that damage to plants or to plant-derived products is reduced.

[0039] As used herein, a staggered line, for example in Y1; and R4-1, represents the point of connection / attachment to the rest of the compound.

[0040] As used herein, the term "pest" refers to insects and molluscs found in agriculture, horticulture, forestry, storage of products of plant origin (such as fruit, grain and wood); and those pests associated with damage to man-made structures. The term pest covers all stages of the pest's life cycle.

[0041] As used herein, the term "effective amount" refers to an amount of a compound or a salt thereof that provides the desired effect upon single or multiple administrations.

[0042] An effective amount is readily determined by one skilled in the art by using known techniques and by observing results obtained under similar circumstances. In determining an effective amount, many factors are considered, including, but not limited to: the type of plant or derived product to be applied; the pest to be controlled and its life cycle; the specific compound being applied; the type of application; and other relevant circumstances.

[0043] As will be understood by one of ordinary skill in the art, compounds having Formula I contain stereocenters, which are indicated by asterisks in the following structures:

[0044]

[0045] wherein R1, R2, R3, R4 and Z1 are as defined in the first aspect.

[0046] The present invention contemplates both racemates and individual enantiomers.Compounds with preferred stereochemistry are listed below.

[0047] Particularly preferred compounds of the present invention are compounds having formula I'a:

[0048]

[0049] wherein R1, R2, R3, R4 and Z1 are as defined in the first aspect, and stereoisomers, enantiomers, tautomers and N-oxides of compounds of formula (I'a), and agrochemically acceptable salts thereof.

[0050] As used herein, the term "optionally substituted" means that the referenced group is unsubstituted or substituted with the specified substituent, for example, "C3-C4 cycloalkyl optionally substituted with 1 or 2 halogen atoms" means C3-C4 cycloalkyl, C3-C4 cycloalkyl substituted with 1 halogen atom, and C3-C4 cycloalkyl substituted with 2 halogen atoms.

[0051] Examples according to the present invention are provided as listed below.

[0052] In an embodiment of each aspect of the invention, R1 is

[0053] A. hydrogen; C1-C6 alkyl optionally substituted by a substituent selected from the group consisting of: CN, CONH2, COOH, NO2 and -Si(CH3)3; C1-C6 haloalkyl; C2-C6 alkenyl; C2-C6 alkynyl; C2-C6 haloalkynyl; C3-C4 cycloalkyl-C1-C2 alkyl-, wherein the C3-C4 cycloalkyl- is optionally substituted by 1 or 2 halogen atoms; oxetan-3-yl-CH2-; or benzyl optionally substituted by halogen or C1-C3 haloalkyl; or

[0054] B. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl optionally substituted by CN or Si(CH3)3; C3-C6 alkynyl; C3-C4 cycloalkyl-C1-C2 alkyl, wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms; oxetane-3-yl-CH2-; or benzyl optionally substituted by halogen; or

[0055] C. hydrogen, C1-C6 alkyl, C3-C4 cycloalkyl, C1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; or

[0056] D. hydrogen, C1-C6 alkyl, or C3-C4 cycloalkyl C1-C2 alkyl-; or

[0057] E. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl optionally substituted by CN or Si(CH3)3; C3-C6 alkynyl; or C3-C4 cycloalkyl-C1-C2 alkyl, wherein the C3-C4 cycloalkyl is optionally substituted by 1 or 2 halogen atoms; or

[0058] F. hydrogen; C1-C6 haloalkyl; C1-C6 alkyl; C3-C6 alkynyl; or C3-C4 cycloalkyl-C1-C2 alkyl, wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms; or

[0059] G. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2-, 2,2-dichlorocyclopropyl-CH2-, hydrogen, CH3, (CH3)3SiCH2-, CH3CH2-, or CNCH2-; or

[0060] H. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2- or 2,2-dichlorocyclopropyl-CH2-; or

[0061] I. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, 2,2-difluorocyclopropyl-CH2-, hydrogen, CH3, (CH3)3SiCH2-, or CH3CH2-; or

[0062] J. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, FCH2CH2CH2-, or 2,2-difluorocyclopropyl-CH2-; or

[0063] K. cyclopropyl-CH2-, n-propyl, CH≡CCH2-, CF3CH2CH2-, FCH2CH2-, or FCH2CH2CH2-; or

[0064] L. cyclopropyl -CH2-, CH≡CCH2-, hydrogen or CH3; or

[0065] M.CH≡CCH2- or cyclopropyl-CH2-; or

[0066] N. cyclopropyl-CH2-; or

[0067] O. cyclopropyl-CH2-, hydrogen or CH3; or

[0068] P. Hydrogen.

[0069] In an embodiment of each aspect of the invention, R2 is

[0070] A. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to three substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded, and the one to three substituents are each independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 thiohaloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halo, NO2, SF5, CN, CONH2, COOH and C(S)NH2; or

[0071] B. phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to two substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which C═O is attached, and each substituent is independently selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen or CN; or

[0072] C. phenyl, 3-pyridine or 4-pyridine substituted with one or two substituents independently selected from the group consisting of C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen, CN or C(S)NH2, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0073] D. phenyl, 3-pyridine or 4-pyridine substituted with one or two substituents independently selected from the group consisting of C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen or CN, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0074] E. phenyl or 3-pyridine substituted with one or two substituents independently selected from the group consisting of: C1-C3 haloalkyl, C1-C3 haloalkoxy, halogen, or CN, provided that the one or more substituents are not on any carbon adjacent to the carbon to which the -C(O)- group is bonded; or

[0075] 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

[0076] G. 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 or 3-cyano-5-trifluoromethyl-phenyl; or

[0077] 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

[0078] I. is 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

[0079] J. 3,5-bis(trifluoromethyl)phenyl, 3-chloro-5-trifluoromethylphenyl, 3-chloro-5-trifluoromethoxyphenyl or 5-trifluoromethylpyridin-3-yl; or

[0080] K. 3,5-bis(trifluoromethyl)phenyl; or

[0081] L.Y1 to Y 21 one of; or

[0082]

[0083] M.Y1, Y2, Y3, Y5, Y6, Y7, Y 11 、Y 13 or Y 15 one of; or

[0084] N.Y1、Y3、Y5、Y6、Y 11 、Y 13 or Y 15 one of; or

[0085] O.Y1, Y3, or Y 11 one of; or

[0086] P.Y1, Y5, Y6, Y 11 、Y 13 、Y 15 、Y 19 , or Y 20 one of;

[0087] Q.Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 one of;

[0088] R.Y1,Y 15 , or Y 20 one of

[0089] S.Y1.

[0090] In an embodiment of each aspect of the invention, R3 is

[0091] A. C1-C3 alkyl or C1-C3 haloalkyl; or

[0092] B. C1-C3 alkyl; or

[0093] C. Methyl.

[0094] In an embodiment of each aspect of the invention, R4 is

[0095] A. pyridine or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; or

[0096] B. 2-pyridine, 2-pyrimidine, 2-pyrazine or 2-pyridazine, each optionally substituted by C1-C3 alkoxy or halo; or

[0097] C. pyridine or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted with a halogen;

[0098] D. 2-pyridine or 2-pyrimidine, each optionally substituted by C1-C3 alkoxy or halo; or

[0099] E. Selected from J1 to J8; or

[0100]

[0101] F. Selected from J1, J2, J3, J4, J6, J7 and J8 or

[0102] G. Selected from J2, J3, J4 and J7; or

[0103] H.J3 or J7; or

[0104] I. J2 or J4; or

[0105] J. 2-pyridine (ie, J1) or 2-pyrimidine (ie, J3); or

[0106] K. 2-Pyrimidine.

[0107] In an embodiment of each aspect of the invention, Z1 is

[0108] A. Halogen, CN, NH2 C(O), amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl) 2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, (C1-C3 alkyl)C(O), HC(O), diphenylcarbamate, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring selected from the group consisting of pyrazolyl, furanyl, thienyl, imidazolyl, isoxazolyl, oxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl and tetrazolyl, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy

[0109] B. Halogen, CN, NH2C(O), amino, (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy -C1-C3 alkoxy, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, (C1-C3 alkyl)C(O), HC(O), or diphenylmethanamine; or

[0110] C. Halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, (C1-C3 alkyl) (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylmethanimine; or

[0111] D. Halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl) Sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylamine; or

[0112] E. halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylmethanamine; or

[0113] F. halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylmethanamine; or

[0114] G. halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylmethanamine; or

[0115] H. halogen, CN, amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C1-C3 haloalkoxy, or C3-C4 cyanocycloalkyl; or

[0116] I. halogen, CN, amino, C3-C4 halocycloalkyl, C1-C3 haloalkoxy, or C3-C4 cyanocycloalkyl; or

[0117] J. halogen, amino, C3-C4 halocycloalkyl, C1-C3 haloalkoxy, or C3-C4 cyanocycloalkyl; or

[0118] K. halogen, amino or C1-C3 haloalkoxy; or

[0119] L. trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, fluoro, amino, 2,2,2-trifluoroethoxy, bromo, or iodo; or

[0120] M. trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, 2,2,2-trifluoroethoxy, bromo, iodo or amino; or

[0121] N. bromine, chlorine, iodine, difluoromethoxy, trifluoromethoxy, or amino; or

[0122] O. bromine, chlorine, iodine, difluoromethoxy, or trifluoromethoxy; or

[0123] P. Bromine, chlorine, or iodine.

[0124] Thus, the present invention provides compounds of formula I having substituents R1, R2, R3, R4 and Z1 as defined above (in all combinations / permutations). Thus, for example, compounds of formula I are available wherein R1 is embodiment D (i.e., hydrogen, C1-C6 alkyl or C3-C4 cycloalkylC1-C2 alkyl-); R2 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); R3 is embodiment C (i.e., methyl); R4 is embodiment C (i.e., pyridine or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted with one C1-C3 alkoxy or halogen); and Z1 is embodiment E (i.e., halogen, CN, amino, di(C1-C3 alkyl) (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, C1-C3 haloalkoxy, or diphenylamine).

[0125] In embodiments of each aspect of the invention, the compound of formula I has as R1 hydrogen, C1-C6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C4 cycloalkylC1-C2 alkyl- (wherein the C3-C4 cycloalkyl is optionally substituted with 1 or 2 halogen atoms), or oxetan-3-yl-CH2-; as R2 phenyl, pyridine, pyrimidine, pyrazine or pyridazine, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to two substituents, provided that the one or more substituents are not adjacent to the carbon to which C=O is attached. On any carbon, and the substituents are each independently selected from: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, halogen or CN; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted with a C1-C3 alkoxy or halogen; and halogen, CN, amino (i.e. NH2), (C1-C3 alkyl) amino, di (C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkene C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O) , (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylmethane, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0126] In an embodiment of each aspect of the invention, the compound of formula I has hydrogen, methyl, allyl, proparyl or cyclopropylmethyl- as R1; phenyl, pyridine, pyrimidine, pyrazine or pyridazine as R2, wherein the phenyl, pyridine, pyrimidine, pyrazine or pyridazine is optionally substituted with one to two substituents, provided that the one or more substituents are not on any carbon adjacent to the carbon to which C=O is attached, and each substituent is independently selected from the group consisting of: C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 as Z1, halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1- C4-haloalkylsulfanyl, C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfanyl, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C3-alkoxy-C1-C3-alkyl, (C1-C3-alkyl)sulfonylamino, (C1-C3-alkyl)sulfonyl(C1-C3-alkyl)amino, (C1-C3-alkyl)NHC(O), (C1-C3-alkyl)2NC(O), (C1-C3-cycloalkyl)NHC(O) , (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylmethane, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0127] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21as one of; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; and as Z1 halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1 -C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0128] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; and Y1, Y5, Y6, Y7, Y8, Y9, Y10, Y11, Y12, Y13, Y14, Y15, Y16, Y17, Y18, Y19, Y20, Y21, Y22, Y23, Y24, Y25, Y26, Y27, Y28, 11 、Y 13 、Y 15 、Y 19 and Y 20as one of; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; and as Z1 halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1 -C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0129] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y5, Y6, Y7, Y8, Y9, Y10, Y11, Y12, Y13, Y14, Y15, Y16, Y17, Y18, Y19, Y20, Y21, Y22, Y23, Y24, Y25, Y26, Y27, Y28, Y2 11 、Y 13 、Y 15 、Y 19 , or Y 20as one of; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; and as Z1 halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1 -C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0130] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; and as Z1 halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1 -C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0131] In embodiments of each aspect of the invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 as R2; C1-C3 alkyl as R3; pyridine or pyrimidine as R4, wherein the pyridine or pyrimidine is optionally substituted with one C1-C3 alkoxy or halogen; and halogen, CN, amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl C1-C3 alkyl)C(O)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0132] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; methyl as R3; pyridine or pyrimidine as R4, wherein the pyridine, pyrimidine is optionally substituted by a C1-C3 alkoxy group or halogen; and halogen, CN, amino (i.e., NH2), (C1-C3 alkyl) amino, di(C1-C3 alkyl) amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0133] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; methyl as R3; 2-pyridine or 2-pyrimidine as R4, each optionally substituted by C1-C3 alkoxy or halo; and halogen, CN, amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl) )sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0134] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; methyl as R3; as R4, selected from J1 to J8; and as Z1, halogen, CN, amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C4 C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0135] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; methyl as R3; as R4, selected from J1 to J8; and as Z1, halogen, CN, amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0136] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as one of; methyl as R3; as R4, selected from J1 or J3; and as Z1, halogen, CN, amino (i.e., NH2), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxyl, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylsulfanyl, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, (C1-C3 alkyl)sulfonylamino, (C1-C4 C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 cycloalkyl)NHC(O), (C1-C3 cycloalkyl)(C1-C3 alkyl)NC(O), (C1-C3 alkyl)C(O)(C1-C3 alkyl)N, (C1-C3 alkyl)C(O)NH, diphenylformimine, C1-C3 haloalkoxy, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy.

[0137] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J1 to J8; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0138] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 as R3 methyl; as R4, selected from J1 to J8; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0139] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20as R3 methyl; as R4, selected from J1 to J8; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0140] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J1 to J8; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0141] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J1 to J8; and as Z1 trifluoromethoxy, difluoromethoxy, chlorine, bromine, iodine or amino.

[0142] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J2, J3, J4 and J7; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0143] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 as R3 methyl; as R4, selected from J2, J3, J4 and J7; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0144] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 as R3 methyl; as R4, selected from J2, J3, J4 and J7; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0145] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J2, J3, J4 and J7; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0146] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4, selected from J2, J3, J4 and J7; and as Z1 trifluoromethoxy, difluoromethoxy, chlorine, bromine, iodine or amino.

[0147] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4 J1 or J3; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0148] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 as R3 methyl; as R4 J1 or J3; and as Z1 halogen, amino, or C1-C3 haloalkoxy.

[0149] In an embodiment of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1, Y6, Y 11 、Y 15 、Y 19 , or Y 20 as R3 methyl; as R4 J1 or J3; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0150] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4 J1 or J3; and as Z1 trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chlorine, 2,2,2-trifluoroethoxy, bromine, iodine or amino.

[0151] In embodiments of each aspect of the present invention, the compound of formula I has hydrogen, methyl, or cyclopropylmethyl- as R1; Y1 to Y2 as R2 21 as R3 methyl; as R4 J1 or J3; and as Z1 trifluoromethoxy, difluoromethoxy, chlorine, bromine, iodine or amino.

[0152] In a second aspect, the present invention provides for use 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 further active ingredients.

[0153] In a third aspect, the present invention provides a method for combating and controlling insects, acarines, nematodes or molluscs, which method comprises applying to the pest, the locus of the pest, or a plant susceptible to attack by the pest an insecticidally, acaridically, nematicidally or molluscicidally effective amount of a compound as defined in the first aspect or a composition as defined in the second aspect.

[0154] In a fourth aspect, the present invention provides a method for protecting plant propagation material from attack by insects, mites, nematodes or molluscs, which method comprises treating the propagation material or the site in which the propagation material is planted with an effective amount of a compound of formula I as defined in the first aspect or a composition as defined in the second aspect.

[0155] In a fifth aspect, the present invention provides for the use of plant propagation material (such as seeds) comprising a compound of formula I as defined in the first aspect or a composition as defined in the second aspect, or treated with a compound of formula I as defined in the first aspect or a composition as defined in the second aspect, or having a compound of formula I as defined in the first aspect or a composition as defined in the second aspect attached thereto.

[0156] In another aspect, the present invention provides a method for controlling parasites in or on an animal in need thereof, the method comprising administering an effective amount of a compound of the first aspect. The present invention further provides a method for controlling external parasites in an animal in need thereof, the method comprising administering an effective amount of a compound of formula I as defined in the first aspect. The present invention further provides a method for preventing and / or treating a disease transmitted by external parasites, the method comprising administering an effective amount of a compound of formula I as defined in the first aspect to an animal in need thereof.

[0157] Compounds of Formula I can be prepared by those skilled in the art according to known methods. More specifically, compounds of Formula I and I'a and intermediates thereof can be prepared as described below in the Schemes and Examples. For the sake of clarity, certain stereocenters are not specified and are not intended to limit the teachings of these Schemes in any way.

[0158] The process for preparing the compound of formula I according to the present invention is carried out by methods known to those skilled in the art.

[0159]

[0160] It can be prepared by the reaction of: Amines having formula II

[0161]

[0162] wherein R1, R3, R4, and Z1 are as described in Formula I, and are prepared by reacting with a carboxylic acid derivative having Formula III

[0163]

[0164] wherein R2 is as described above for Formula I. This chemistry is described in more detail in Scheme 1.

[0165] Option 1:

[0166]

[0167] In Scheme 1, a compound of formula III (wherein R2 is as described 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, a compound wherein X0 is a halogen is formed by treating a compound of formula III with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of DMF in an inert solvent such as dichloromethane or THF at a temperature between 20° C. and 100° C. (preferably 25° C.). Treatment of IIIa with a compound of formula II (wherein R1, R3, R4 and Z1 are as defined above) optionally in the presence of a base such as triethylamine or pyridine produces a compound of formula I. Alternatively, compounds of formula III can be prepared by treating them with 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) in an inert solvent such as pyridine, DMF, acetonitrile, CH2Cl2 or THF, optionally in the presence of a base such as triethylamine, at temperatures between 30°C and 180°C to give activated species IIIa (wherein X0 is X 01 、X 02 and X 03 ) to prepare compounds of formula I. Finally, acids of formula III can also be prepared by reacting with coupling agents such as propanephosphonic anhydride ) reaction is activated to provide a compound of formula IIIa, wherein X0 is X 04 , as described, for example, in Synthesis 2013, 45, 1569. Further reaction with amines of formula II provides compounds of formula I.

[0168] Compounds of formula II (wherein R1, R3, R4 and Z1 are 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.

[0169] Option 2.

[0170]

[0171] For example, a compound of formula II can be prepared by reacting a compound of formula VI (wherein R3, R4 and Z1 are as defined in formula I) with a compound of formula VIII (wherein R1 is as defined in formula I) in a suitable solvent (which can include, 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)) 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.

[0172] Compounds of formula VI (wherein R3, R4 and Z1 are as defined above) can be prepared by reacting a compound of formula IVa (wherein R3 and Z1 are as defined in formula I) with a compound of formula VII (wherein R4 is as defined in formula I) in a suitable solvent (which may include, 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). Such methods have been previously described, for example, in Tetrahedron 2017, 73, 750.

[0173] Compounds of formula IVa (wherein R3 and Z1 are as defined above) can be prepared by reacting a compound of formula IV (wherein R3 is as defined in formula I) with a compound of formula V (wherein Z1 is as defined in formula I) in a suitable solvent (which may include, for example, DMF) in the presence of a suitable base (e.g., DIPEA) at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture. This method has been previously described, for example, in Journal of Organic Chemistry, 2011, 76, 1177.

[0174] Alternatively, compounds of Formula I (wherein R1, R2, R3, R4 and Z1 are as defined above) can also be prepared by the method shown in Scheme 3.

[0175] Option 3.

[0176]

[0177] For example, a compound of formula I (wherein R1, R2, R3, R4 and Z1 are as defined above) can be prepared by reacting a compound of formula XIII (wherein R1, R2, R3 and Z1 are as defined above) with a compound of formula VII (wherein R4 is as defined in formula I) in a suitable solvent (which may include, 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, optionally under microwave heating conditions. Such methods have been previously described, for example, in Tetrahedron 2017, 73, 750.

[0178] Compounds of formula XIII (wherein R1, R2, R3 and Z1 are as defined above) can be prepared by reacting a compound of formula XII (wherein R1, R2 and R3 are as defined above) with a compound of formula V (wherein Z1 is as defined in formula I) in a suitable solvent (which may include, for example, DMF) in the presence of a suitable base (e.g., DIPEA) at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture. Such methods have been previously described, for example, in J. Org. Chem., 2011, 76, 1177.

[0179] Compounds of formula XII (wherein R1, R2 and R3 are as defined above) can be prepared by reaction between a compound of formula XI (wherein R1, R2 and R3 are as defined above) and a base (e.g. lithium hydroxide or sodium hydroxide) in a suitable solvent (which may include a mixture of THF / H2O), typically with heating at a temperature between room temperature and 200°C.

[0180] Compounds of formula XI (wherein R1, R2 and R3 are as defined above) can be prepared by reaction between a compound of formula IIIa (wherein R2 and Xo are as defined above) and a compound of formula X (wherein R1 and R3 are as defined in formula I) in a suitable inert solvent (which may include, for example, pyridine, DMF, acetonitrile, CH2Cl2 or THF), optionally in the presence of a base (such as triethylamine or pyridine), typically with heating at a temperature between room temperature and 200°C. Compounds of formula X (wherein R1 and R3 are as defined above) can be prepared by reaction between a compound of formula IX (wherein R3 is as defined in formula I) and a compound of formula VIII (wherein R1 is as defined in formula I) in a suitable solvent (which may include, for example, acetonitrile or dioxane) in the presence of a suitable base (e.g., sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate)), typically with 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).

[0181] Alternatively, compounds of Formula I (wherein R1, R2, R3, R4 and Z1 are as defined above) can also be prepared by the method shown in Scheme 4.

[0182] Solution 4.

[0183]

[0184] For example, a compound of formula I (wherein R1, R2, R3, R4 and Z1 are as defined above) can be prepared by reacting a compound of formula XV (wherein R1, R2, R3 and Z1 are as defined above) with a compound of formula XVI (wherein R4 is as defined in formula I and wherein Hal is a halogen, such as, for example, chlorine, bromine or iodine), optionally in the presence of a copper catalyst (e.g., CuI), in the presence of a suitable solvent (e.g., DMF or NMP), in the presence of a suitable base (e.g., sodium hydride, potassium carbonate or cesium carbonate), typically at temperatures between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture, optionally under microwave heating conditions. Such methods have been previously described, for example, in Chem. Asian J. 2014, 9, 166 and in WO 2013161904 and WO 2009131173.

[0185] Compounds of formula XV (wherein R1, R2, R3 and Z1 are as defined above) can be prepared by reaction between a compound of formula XIV (wherein R1, R2 and R3 are as defined above) and a compound of formula V (wherein Z1 is as defined above) in the presence of a base (e.g., sodium hydride) in a suitable solvent (e.g., DMF), typically with heating at a temperature between room temperature and 200°C.

[0186] Compounds of formula XIV (wherein R1, R2 and R3 are as defined above) can be prepared by reacting a compound of formula XII (wherein R1, R2 and R3 are as defined above), ethyl chloroformate and hydrazine in the presence of a base (e.g., trimethylamine or DIPEA) in a suitable solvent (e.g., methanol or ethanol), typically with heating at a temperature between room temperature and 200° C. Such methods have been previously described, for example, in WO 2008055013.

[0187] Compounds of formula Ia, wherein R1, R2, R3 and R4 are as defined above and Xa is halogen, such as chlorine, bromine or iodine, can be prepared by the method shown in Scheme 5.

[0188] Option 5.

[0189]

[0190] For example, compounds of formula Ia (wherein R1, R2, R3 and R4 are as defined above and Xa is halogen, such as chlorine, bromine or iodine) can be prepared by reacting a compound of formula XVa (wherein R1, R2 and R3 are as defined above and Xa is halogen, such as chlorine, bromine or iodine) with a compound of formula XVI (wherein R4 is as defined above and wherein Hal is halogen, such as chlorine, bromine or iodine) in the presence of a suitable base (such as sodium hydride, potassium carbonate or cesium carbonate), preferably in the presence of a copper catalyst (such as CuI), in the presence of a suitable solvent (such as DMF or NMP), 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). Such methods have been previously described, for example, in Chem. Asian J. 2014, 9, 166 and WO 2013161904 and WO 2009131173.

[0191] There is a compound of formula XVa (wherein R1, R2, R3 and Xa are as defined above) can be prepared by halogenating a compound of formula XVIII (wherein R1, R2 and R3 are as defined above) with a halogenating agent (such as tribromobenzyltrimethylammonium, N-iodosuccinimide) in a suitable solvent (which may include, for example, CH2Cl2), in 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). Such methods have previously been described in, for example, US2014206700 (see pages 37-38).

[0192] Compounds of formula XVIII (wherein R1, R2 and R3 are as defined above) can be prepared by reacting a compound of formula XVII (wherein R1, R2 and R3 are as defined above) with hydrazine in a suitable solvent (which may include, for example, acetic acid, a mixture of acetic acid and 1,4-dioxane, or a mixture of acetic acid and toluene), typically at temperatures 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). Such methods have been previously described, for example, in J. Heterocyclic Chem. 2008, 45, 887; Bioorg. Med. Chem. Lett. 2015, 25, 5121.

[0193] Intermediates of formula XVII (wherein R1, R2 and R3 are as defined above) can be prepared by the method shown in Scheme 6.

[0194] Option 6.

[0195]

[0196] Compounds of formula XVII (wherein R1, R2 and R3 are as defined above) can be prepared by reacting a compound of formula XXI (wherein R1, R2 and R3 are as defined above) with N,N-dimethylformamide dimethyl acetal (DMF-DMA) in a suitable solvent (which may include, for example, dichloromethane), typically at a temperature between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture. Such methods have been previously described, for example, in Tetrahedron 2017, 73,750 and US2016296501, Preparation 7, page 29.

[0197] Compounds of formula XXI (wherein R1, R2 and R3 are as defined above) can be prepared by reaction between a compound of formula XX (wherein R1 and R3 are as defined above) and a compound of formula IIIa (wherein R2 and Xo are as defined in Scheme 1) in a suitable inert solvent (which may include, for example, pyridine, DMF, acetonitrile, CH2Cl2 or THF), optionally in the presence of a base (such as triethylamine or pyridine), typically with heating at a temperature between room temperature and 200°C.

[0198] Compounds of formula XX (wherein R1 and R3 are as defined above) can be prepared by reaction between a compound of formula XIX (wherein R3 is as defined in formula I) and a compound of formula VIII (wherein R1 is as defined in formula I) in a suitable solvent (which may include, for example, acetonitrile or dioxane) in the presence of a suitable base (e.g., sodium carbonate, potassium carbonate or cesium carbonate (or sodium bicarbonate or potassium bicarbonate)), typically with 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).

[0199] Alternatively, a compound of formula I (wherein R1, R2, R3, R4 are as defined above and Z 1a is diphenylformimine, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 alkoxyalkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy) can be prepared by the method shown in Scheme 7.

[0200] Plan 7.

[0201]

[0202] Compounds of Formula I (wherein R1, R2, R3, R4 are as defined above and Z 1a is diphenylformimine, C3-C4 halocycloalkyl, C3-C4 cyanocycloalkyl, C2-C6 alkenyl, C2-C6 alkoxyalkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, phenyl or a 5-membered heteroaromatic ring, wherein the phenyl or the 5-membered heteroaromatic ring may be optionally substituted with one to three substituents selected from the group consisting of C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C3-C4 cycloalkyl, halogen, CN or hydroxy) can be prepared as depicted in Scheme 7 by a compound having Formula Ia (wherein R1, R2, R3, R4 and X a described above) and a compound of formula XXII (wherein Z 1a is described above and W0 is a boronic acid or borate or tin compound or hydrogen). The reaction is carried out in the presence of a palladium catalyst (e.g., Pd(PPh3)4), in the presence of a suitable solvent (e.g., dioxane or toluene), in the presence of a suitable base (e.g., potassium carbonate or cesium carbonate), 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). Such methods have been previously described, for example, in WO2016006523 or J.Med.Chem., 2014, 57, 3687-3706.

[0203] Compounds of Formula Ic (wherein R1, R2, R3, R4 are as defined above and Z 1b is amino, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)C(O)(C1-C3 alkyl)N or (C1-C3 alkyl)C(O)NH) can be prepared by the method shown in Scheme 8.

[0204] Plan 8.

[0205]

[0206] Compounds of Formula Ic (wherein R1, R2, R3, R4 are as defined above and Z 1b(C1-C3 alkyl)amino, (C1-C3 alkyl)sulfonylamino, (C1-C3 alkyl)sulfonyl(C1-C3 alkyl)amino, (C1-C3 alkyl)C(O)(C1-C3 alkyl)N or (C1-C3 alkyl)C(O)NH) can be reacted with compound Ib" (wherein R1, R2, R3, R4 are as defined above) and compound XXIII (wherein X0 is as described in Scheme 1 and can also be X as described in Scheme 1) 01 、X 02 、X 03 and X 04 and Z2 is (C1-C3 alkyl), (C1-C3 alkyl)sulfonyl or (C1-C3 alkyl)C(O)). The reaction is carried out in a suitable solvent (e.g., dichloromethane or DMF) in the presence of a suitable base (e.g., trimethylamine or pyridine), typically under heating at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture. The resulting compound can be optionally alkylated in a second step by treating the resulting compound with compound XXIV (wherein LG is a leaving group, e.g., chloro, methanesulfonyloxy or toluenesulfonyloxy) in a suitable solvent (e.g., THF or DMF) in the presence of a suitable base (e.g., sodium hydride), typically under heating at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture. Such transformations can be easily performed by those skilled in the art or are described in detail in WO 2010010186 or Eur. J. Med. Chem, 2013, 67, 243-251.

[0207] Compounds of formula Ib" (wherein R1, R2, R3, R4 are as defined above) can be prepared by compound Ib' (wherein R1, R2, R3, R4 are as defined above and Z 1aa The reaction is carried out in a suitable solvent (e.g., THF) in the presence of an acid (e.g., hydrochloric acid or citric acid), typically at a temperature between room temperature and 200° C., preferably between 20° C. and the boiling point of the reaction mixture. Such methods have been previously described, for example, in WO 2018067432 or Eur. J. Med. Chem, 2018, 144, 151-163.

[0208] Compounds of Formula Id (wherein R1, R2, R3, R4 are as defined above and Z 1c is halogen (eg, chlorine, bromine, or iodine), CN, (C1-C3 alkyl)amino, C2-C6 alkenyl, or C1-C4 alkylsulfanyl) can be prepared by the method shown in Scheme 9.

[0209] Plan 9.

[0210]

[0211] Compounds of Formula Id (wherein R1, R2, R3, R4 are as defined above and Z 1c is halogen (e.g., chlorine, bromine, or iodine), CN, (C1-C3 alkyl)amino, C2-C6 alkenyl, or C1-C4 alkylsulfanyl) can be prepared by reacting a compound of formula Ib' wherein R1, R2, R3, and R4 are as previously described with a compound of formula XXV wherein Z 1c is as described above and W1 is hydrogen, an alkali metal or copper). The reaction can be carried out as follows: 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), usually at a temperature between 0° and room temperature, a compound of formula Ib' is treated with a suitable nitrosating agent (such as sodium nitrite, tert-butyl nitrite or isoamyl nitrite). The diazo intermediate is usually heated at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture with a compound of formula XXV (wherein Z 1c and W1 is the above-described) treatment. Such methods have been previously described, for example, in WO 2010141796 or J. Med. Chem. [Journal of Medicinal Chemistry] 1990, 33, 1230-41.

[0212] Compounds of Formula Ie (wherein R1, R2, R3, R4 are as defined above and Z 1d is hydroxy, C1-C3 alkoxy-C1-C3 alkyl or C1-C3 haloalkoxy) can be prepared by the method shown in Scheme 10.

[0213] Plan 10.

[0214]

[0215] Compounds of Formula Ie (wherein R1, R2, R3, R4 are as defined above and Z 1d is hydroxy, C1-C3 alkoxy-C1-C3 alkyl or C1-C3 haloalkoxy) can be obtained by reacting a compound of formula Ic" (wherein R1, R2, R3 and R4 are as previously described) with a compound of formula XXVI (wherein Z 1dis as described above and LG is a leaving group, such as chloro, trifluoromethanesulfonate, methanesulfonyloxy or tosyloxy), or alternatively, by the reaction between the above compound Ic "and 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), typically at a temperature between room temperature and 200 ° C, preferably between 20 ° C and the boiling point of the reaction mixture.

[0216] Compounds of formula Ic" can be prepared by treating a compound of formula Ic' (wherein R1, R2, R3 and R4 are described above) with a suitable acid (e.g., hydrobromic acid or hydrochloric acid) in a suitable solvent (e.g., acetic acid or water), typically at a temperature between room temperature and 200°C, preferably between 20°C and the boiling point of the reaction mixture. This method has been previously described, for example, in US20090291967 or Bioorganic & Medicinal Chemistry 2018, 26, 3321-3344.

[0217] Compounds of formula III1 (wherein R2 is Y1, Y3, Y5 or Y 11 ) is commercially available and was not prepared by us.

[0218] Compounds of formula III2 (wherein R2 is Y6) can be prepared by the method shown in Scheme 11

[0219] Plan 11.

[0220]

[0221] Compounds of formula III2, wherein R2 is Y6, can be prepared by conversion of compound XXVIII by treatment with 1,3-dibromo-5,5-dimethylhydantoin and hydrogen fluoride in a suitable solvent, which may include, for example, dichloromethane, typically at low temperatures between -78° C. and 0° C. The resulting compound is then hydrolyzed to the corresponding carboxylic acid using classical conditions known to those skilled in the art (sodium hydroxide or lithium hydroxide, MeOH / THF / H2O).

[0222] Compounds of formula XXVIII can be prepared by reacting compound XXVII with carbon disulfide in a suitable solvent (which may include, for example, DMF) in the presence of a suitable base (e.g., sodium hydride), typically with heating at a temperature between room temperature and 200° C., followed by a methylation step with methyl iodide as the methylating agent. Such methods have been previously 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.

[0223] A compound of formula III3 (wherein R2 is Y 13 ) can be prepared by the method shown in Scheme 12

[0224] Plan 12.

[0225]

[0226] A compound of formula III3 (wherein R2 is Y 13 ) 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 MeOH, THF, H2O or a mixture of the three), typically with heating at a temperature between room temperature and reflux.

[0227] Compounds of formula XXX can be prepared by reacting compound XXIX with a suitable trifluoromethylthiolate copper reagent (e.g., (bpy)CuSCF 3 ) in a suitable solvent (which may include, for example, acetonitrile), typically at temperatures between room temperature and 200° C., preferably between 40° C. and the boiling point of the reaction mixture. Such methods have been previously described, for example, in Angew. Chem. Int. Ed. [German Applied Chemistry] 2013, 52, 1548-1552.

[0228] A compound of formula III4 (wherein R2 is Y 15 ) can be prepared by the method shown in Scheme 13

[0229] Plan 13.

[0230]

[0231] A compound of formula III4 (wherein R2 is Y 15) can be prepared by reacting compound XXXI with compound XXXII in a suitable solvent (which may include, for example, chloroform) in the presence of a suitable base (e.g., sodium hydroxide), typically under heating at a temperature between room temperature and reflux. Such methods have been previously described, for example, in WO 2002044145.

[0232] Depending on the procedure or reaction conditions, the reactants may be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines. Examples that may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0233] These reactants can react with each other as is, i.e. without adding solvents or diluents. However, in most cases, it is advantageous to add inert solvents or diluents or mixtures of these. If the reaction is carried out in the presence of a base, the base used in excess (e.g., triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline) can also serve as a solvent or diluent.

[0234] These reactions are advantageously carried out in a temperature range of from about -80°C to about +140°C, preferably from about -30°C to about +100°C, in many cases in a range between ambient temperature and about +80°C.

[0235] Depending on the reaction conditions and starting materials chosen as appropriate in the respective case, it is possible, for example, to replace only one substituent with another substituent according to the invention in one reaction step or to replace several substituents with other substituents according to the invention in one and the same reaction step.

[0236] 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 are obtained by treatment with a suitable acid or a suitable ion exchanger reagent, and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.

[0237] Salts of compounds of the formula I can be converted in a customary manner into the free compounds I, acid addition salts (for example by treatment with suitable basic compounds or with suitable ion exchange reagents) and salts with bases (for example by treatment with suitable acids or with suitable ion exchange reagents).

[0238] Salts of compounds of the formula I can be converted in a manner known per se into other salts, acid addition salts of compounds of the formula I, for example into other acid addition salts, for example by treating salts of inorganic acids (such as hydrochlorides) with suitable metal salts of the acid (such as sodium, barium or silver salts, for example with silver acetate) in a suitable solvent in which the inorganic salt formed (such as silver chloride) is insoluble and therefore precipitates from the reaction mixture.

[0239] Depending on the procedure or reaction conditions, those compounds of the formula I which have salt-forming properties can be obtained in free form or in the form of salts.

[0240] Depending on the number of asymmetric carbon atoms present in the molecule, the absolute and relative configuration and / or on the configuration of non-aromatic double bonds present in the molecule, the compounds of the formula I and, where appropriate, their tautomers (in each case in free form or in salt form) may be present in the form of one of the possible isomers or as a mixture of these, for example in the form of pure isomers, such as enantiomers and / or diastereomers, or as isomer mixtures, such as enantiomeric mixtures, for example racemates, diastereomeric mixtures or racemic mixtures; the present invention relates to the pure isomers and also to all possible isomer mixtures, and the above and below are to be understood as such in each case, even if stereochemical details are not explicitly mentioned in each case.

[0241] Diastereomeric mixtures or racemic mixtures of compounds of formula I in free form or in salt form, the acquisition of which may depend on the starting materials and procedures chosen, can be separated in a known manner into the pure diastereomers or racemates on the basis of the physicochemical differences of the components, for example, by fractional crystallization, distillation and / or chromatography.

[0242] Enantiomeric mixtures obtainable in an analogous manner (e.g., racemates) can be resolved into the optical antipodes by known methods, for example, by recrystallization from optically active solvents; by chromatography on chiral adsorbents, for example, high performance liquid chromatography (HPLC) on acetylcellulose; by cleavage with specific immobilized enzymes with the aid of suitable microorganisms; by forming inclusion compounds, for example, using chiral crown ethers, in which only one enantiomer is complexed; or by conversion into diastereomeric salts, for example, by reacting the basic end product racemate with an optically active acid (e.g., a carboxylic acid, for example, camphoric acid, tartaric acid or malic acid, or a sulfonic acid, for example, camphorsulfonic acid) and separating the diastereomeric mixtures obtainable in this way, for example, by fractional crystallization on the basis of their different solubilities, thereby obtaining the diastereomers from which the desired enantiomer can be freed by the action of suitable reagents (e.g., basic reagents).

[0243] Pure diastereomers or enantiomers can be obtained according to the invention not only by separation of the appropriate isomer mixtures, but also by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the method according to the invention with starting materials having the appropriate stereochemistry.

[0244] N-oxides can be prepared by reacting a compound of formula I with a suitable oxidizing agent (e.g. H O / urea adduct) in the presence of an anhydride (e.g. trifluoroacetic anhydride). Such oxidations are known from the literature, for example from J. Med. Chem., 32 (12), 2561-73, 1989 or WO 2000 / 15615.

[0245] If the individual components have different biological activities, it is advantageous to isolate or synthesize the biologically more effective isomers, such as enantiomers or diastereomers or isomer mixtures, such as enantiomeric mixtures or diastereomeric mixtures, in each case.

[0246] If appropriate, the compounds of formula I and, where appropriate, their tautomers (in each case in free form or in salt form) can also be obtained in the form of hydrates and / or include other solvents, such as those which can be used for crystallization of compounds present in solid form.

[0247] In another aspect, the present invention provides a compound having formula XV

[0248]

[0249] wherein R1, R2, R3 and Z1 are as defined for formula (I) in the first aspect; or stereoisomers, enantiomers, tautomers and N-oxides of the compound of formula I, or an agrochemically acceptable salt thereof. The embodiments described for R1, R2, R3 and Z1 with respect to formula (I) also apply to formula (XV).

[0250] In a preferred embodiment, the compound of Formula XV has Embodiment L as R2; Embodiment L as R1, Embodiment C as R3; and one of Embodiments A through M as Z1.

[0251] In another aspect, the present invention provides compounds having formula II

[0252]

[0253] wherein R1, R3, R4 and Z1 are as defined for formula (I) in the first aspect; or stereoisomers, enantiomers, tautomers and N-oxides of the compound of formula I, or agrochemically acceptable salts thereof. The embodiments described for R1, R2, R3 and Z1 with respect to formula (I) also apply to formula (II).

[0254] In a preferred embodiment, the compound of Formula II has Embodiment L as R1, Embodiment C as R3; Embodiment G as R4; and one of Embodiments A through P as Z1.

[0255] The compounds of formula I according to the following tables A-1 to A-92 can be prepared according to the above-described methods. The following examples are intended to illustrate the present invention and show preferred compounds of formula I (in the form of compounds of formula Ia)

[0256]

[0257] Table A-1 45 compounds A-1.001 to A-1.045 of formula Iaa are provided, wherein R1 is H, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z. For example, A-1.009 is

[0258]

[0259] Table Z: Definition of substituents for Z1:

[0260]

[0261]

[0262] Table A-2Provided are 45 compounds A-2.001 to A-2.045 of formula Iaa wherein R1 is H, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl) and Z1 is as defined in Table Z.

[0263] Table A-3 Provided are 45 compounds A-3.001 to A-3.045 of formula Iaa, wherein R1 is H, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0264] Table A-4 Provided are 45 compounds A-4.001 to A-4.045 of formula Iaa, wherein R1 is H, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0265] Table A-5 Provided are 45 compounds A-5.001 to A-5.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0266] Table A-6 Provided are 45 compounds A-6.001 to A-6.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0267] Table A-7 Provided are 45 compounds A-7.001 to A-7.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0268] Table A-8 Provided are 45 compounds A-8.001 to A-8.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0269] Table A-9 Provided are 45 compounds A-9.001 to A-9.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0270] Table A-10Provided are 45 compounds A-10.001 to A-10.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0271] Table A-11 Provided are 45 compounds A-11.001 to A-11.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0272] Table A-12 Provided are 45 compounds A-12.001 to A-12.045 of formula Iaa, wherein R1 is H, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0273] Table A-13 Provided are 45 compounds A-13.001 to A-13.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0274] Table A-14 Provided are 45 compounds A-14.001 to A-14.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0275] Table A-15 Provided are 45 compounds A-15.001 to A-15.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0276] Table A-16 Provided are 45 compounds A-16.001 to A-16.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0277] Table A-17 Provided are 45 compounds A-17.001 to A-17.045 of formula Iaa, wherein R1 is H, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0278] Table A-18 Provided are 45 compounds A-18.001 to A-18.045 of formula Iaa, wherein R1 is H, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0279] Table A-19 Provided are 45 compounds A-19.001 to A-19.045 of formula Iaa, wherein R1 is H, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0280] Table A-20 Provided are 45 compounds A-20.001 to A-20.045 of formula Iaa, wherein R1 is H, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0281] Table A-21 Provided are 45 compounds A-21.001 to A-21.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0282] Table A-22 Provided are 45 compounds A-22.001 to A-22.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0283] Table A-23 Provided are 45 compounds A-23.001 to A-23.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0284] Table A-24 Provided are 45 compounds A-24.001 to A-24.045 of formula Iaa, wherein R1 is H, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0285] Table A-25Provided are 45 compounds A-25.001 to A-25.045 of formula Iaa, wherein R1 is H, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0286] Table A-26 Provided are 45 compounds A-26.001 to A-26.045 of formula Iaa, wherein R1 is H, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0287] Table A-27 Provided are 45 compounds A-27.001 to A-27.045 of formula Iaa, wherein R1 is H, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0288] Table A-28 Provided are 45 compounds A-28.001 to A-28.045 of formula Iaa, wherein R1 is H, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0289] Table A-29 Provided are 45 compounds A-29.001 to A-29.045 of formula Iaa, wherein R1 is CH3, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is 2-pyridyl, and Z1 is as defined in Table Z.

[0290] Table A-30 Provided are 45 compounds A-30.001 to A-30.045 of formula Iaa, wherein R1 is CH3, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl) and Z1 is as defined in Table Z.

[0291] Table A-31 Provided are 45 compounds A-31.001 to A-31.045 of formula Iaa, wherein R1 is CH3, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0292] Table A-32 Provided are 45 compounds A-32.001 to A-32.045 of formula Iaa, wherein R1 is CH3, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0293] Table A-33 Provided are 45 compounds A-33.001 to A-33.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0294] Table A-34 Provided are 45 compounds A-34.001 to A-34.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0295] Table A-35 Provided are 45 compounds A-35.001 to A-35.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0296] Table A-36 Provided are 45 compounds A-36.001 to A-36.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0297] Table A-37 Provided are 45 compounds A-37.001 to A-37.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0298] Table A-38 Provided are 45 compounds A-38.001 to A-38.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0299] Table A-39 Provided are 45 compounds A-39.001 to A-39.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0300] Table A-40 Provided are 45 compounds A-40.001 to A-40.045 of formula Iaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0301] Table A-41 Provided are 45 compounds A-41.001 to A-41.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0302] Table A-42 Provided are 45 compounds A-42.001 to A-42.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0303] Table A-43 Provided are 45 compounds A-43.001 to A-43.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0304] Table A-44 Provided are 45 compounds A-44.001 to A-44.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0305] Table A-45 Provided are 45 compounds A-45.001 to A-45.045 of formula Iaa, wherein R1 is CH3, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0306] Table A-46 Provided are 45 compounds A-46.001 to A-46.045 of formula Iaa, wherein R1 is CH3, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl) and Z1 is as defined in Table Z.

[0307] Table A-47 Provided are 45 compounds A-47.001 to A-47.045 of formula Iaa, wherein R1 is CH3, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0308] Table A-48Provided are 45 compounds A-48.001 to A-48.045 of formula Iaa, wherein R1 is CH3, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0309] Table A-49 Provided are 45 compounds A-49.001 to A-49.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0310] Table A-50 Provided are 45 compounds A-50.001 to A-50.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0311] Table A-51 Provided are 45 compounds A-51.001 to A-51.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0312] Table A-52 Provided are 45 compounds A-52.001 to A-52.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0313] Table A-53 Provided are 45 compounds A-53.001 to A-53.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0314] Table A-54 Provided are 45 compounds A-54.001 to A-54.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0315] Table A-55Provided are 45 compounds A-55.001 to A-55.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0316] Table A-56 Provided are 45 compounds A-56.001 to A-56.045 of formula Iaa, wherein R1 is CH3, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0317] Table A-57 Provided are 45 compounds A-57.001 to A-57.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is 2-pyridyl, and Z1 is as defined in Table Z.

[0318] Table A-58 Provided are 45 compounds A-58.001 to A-58.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl), and Z1 is as defined in Table Z.

[0319] Table A-59 Provided are 45 compounds A-59.001 to A-59.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0320] Table A-60 Provided are 45 compounds A-60.001 to A-60.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3,5-bis(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl), and Z1 is as defined in Table Z.

[0321] Table A-61 Provided are 45 compounds A-61.001 to A-61.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0322] Table A-62 Provided are 45 compounds A-62.001 to A-62.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl) and Z1 is as defined in Table Z.

[0323] Table A-63 Provided are 45 compounds A-63.001 to A-63.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0324] Table A-64 Provided are 45 compounds A-64.001 to A-64.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0325] Table A-65 Provided are 45 compounds A-65.001 to A-65.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is 2-pyridyl, and Z1 is as defined in Table Z.

[0326] Table A-66 Provided are 45 compounds A-66.001 to A-66.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0327] Table A-67 Provided are 45 compounds A-67.001 to A-67.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0328] Table A-68 Provided are 45 compounds A-68.001 to A-68.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethoxy)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0329] Table A-69 Provided are 45 compounds A-69.001 to A-69.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0330] Table A-70Provided are 45 compounds A-70.001 to A-70.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0331] Table A-71 Provided are 45 compounds A-71.001 to A-71.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0332] Table A-72 Provided are 45 compounds A-72.001 to A-72.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0333] Table A-73 Provided are 45 compounds A-73.001 to A-73.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl, and Z1 is as defined in Table Z.

[0334] Table A-74 Provided are 45 compounds A-74.001 to A-74.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridyl) and Z1 is as defined in Table Z.

[0335] Table A-75 Provided are 45 compounds A-75.001 to A-75.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0336] Table A-76 Provided are 45 compounds A-76.001 to A-76.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-bromo-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0337] Table A-77Provided are 45 compounds A-77.001 to A-77.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0338] Table A-78 Provided are 45 compounds A-78.001 to A-78.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0339] Table A-79 Provided are 45 compounds A-79.001 to A-79.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0340] Table A-80 Provided are 45 compounds A-80.001 to A-80.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0341] Table A-81 Provided are 45 compounds A-81.001 to A-81.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0342] Table A-82 Provided are 45 compounds A-82.001 to A-82.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0343] Table A-83 Provided are 45 compounds A-83.001 to A-83.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0344] Table A-84Provided are 45 compounds A-84.001 to A-84.045 of formula Iaa, wherein R1 is cyclopropylmethyl, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0345] Table A-85 Provided are 45 compounds A-85.001 to A-85.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl, and Z1 is as defined in Table Z.

[0346] Table A-86 Provided are 45 compounds A-86.001 to A-86.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0347] Table A-87 Provided are 45 compounds A-87.001 to A-87.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl, and Z1 is as defined in Table Z.

[0348] Table A-88 Provided are 45 compounds A-88.001 to A-88.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2-difluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0349] Table A-89 Provided are 45 compounds A-89.001 to A-89.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is 2-pyridyl and Z1 is as defined in Table Z.

[0350] Table A-90 Provided are 45 compounds A-90.001 to A-90.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromo-2-pyridinyl) and Z1 is as defined in Table Z.

[0351] Table A-91Provided are 45 compounds A-91.001 to A-91.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is pyrimidin-2-yl and Z1 is as defined in Table Z.

[0352] Table A-92 Provided are 45 compounds A-92.001 to A-92.045 of formula Iaa, wherein R1 is H, R2 is [3-(2,2,2-trifluoroethoxy)-5-(trifluoromethyl)phenyl], R4 is (5-bromopyrimidin-2-yl) and Z1 is as defined in Table Z.

[0353] Certain intermediate compounds of formula XV are also available. Tables B-1 to B-21 below illustrate specific compounds of formula XVaa.

[0354]

[0355] Table B-1 Four compounds B-1.001 to B-1.004 of formula XVaa are provided, wherein R1 is H, R2 is [3,5-bis(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0356] Table W :Z1 substituent definition:

[0357] index <![CDATA[Z1]]> 1 F 2 Cl 3 Br 4 I

[0358] Table B-2 Provided are four compounds B-2.001 to B-2.004 of formula XVaa wherein R1 is H, R2 is [3-chloro-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0359] Table B-3 Provided are four compounds B-3.001 to B-3.004 of formula XVaa wherein R1 is H, R2 is [3-chloro-5-(trifluoromethoxy)phenyl] and Z1 is as defined in Table W.

[0360] Table B-4 Provided are four compounds B-4.001 to B-4.004 of formula XVaa wherein R1 is H, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0361] Table B-5 Provided are four compounds B-5.001 to B-5.004 of formula XVaa, wherein R1 is H, R2 is [3-bromo-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0362] Table B-6 Provided are four compounds B-6.001 to B-6.004 of formula XVaa wherein R1 is H, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl] and Z1 is as defined in Table W.

[0363] Table B-7 Provided are four compounds B-7.001 to B-7.004 of formula XVaa wherein R1 is H, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0364] Table B-8 Provided are four compounds B-8.001 to B-8.004 of formula XVaa, wherein R1 is CH3, R2 is [3,5-bis(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0365] Table B-9 Provided are four compounds B-9.001 to B-9.004 of formula XVaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0366] Table B-10 Provided are four compounds B-10.001 to B-10.004 of formula XVaa, wherein R1 is CH3, R2 is [3-chloro-5-(trifluoromethoxy)phenyl] and Z1 is as defined in Table W.

[0367] Table B-11 Provided are four compounds B-11.001 to B-11.004 of formula XVaa, wherein R1 is CH3, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0368] Table B-12 Provided are four compounds B-12.001 to B-12.004 of formula XVaa, wherein R1 is CH3, R2 is [3-bromo-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0369] Table B-13 Provided are four compounds B-13.001 to B-13.004 of formula XVaa, wherein R1 is CH3, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl] and Z1 is as defined in Table W.

[0370] Table B-14Provided are four compounds B-14.001 to B-14.004 of formula XVaa, wherein R1 is CH3, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0371] Table B-15 Provided are four compounds B-15.001 to B-15.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3,5-bis(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0372] Table B-16 Provided are four compounds B-16.001 to B-16.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0373] Table B-17 Provided are four compounds B-17.001 to B-17.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-chloro-5-(trifluoromethoxy)phenyl] and Z1 is as defined in Table W.

[0374] Table B-18 Provided are four compounds B-18.001 to B-18.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0375] Table B-19 Provided are four compounds B-19.001 to B-19.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-bromo-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0376] Table B-20 Provided are four compounds B-20.001 to B-20.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-(trifluoromethyl)-5-(trifluoromethylsulfanyl)phenyl] and Z1 is as defined in Table W.

[0377] Table B-21 Provided are four compounds B-21.001 to B-21.004 of formula XVaa, wherein R1 is cyclopropylmethyl, R2 is [3-(difluoromethoxy)-5-(trifluoromethyl)phenyl] and Z1 is as defined in Table W.

[0378] The compounds of formula I according to the invention are active ingredients of preventive and / or therapeutic value in the field of pest control. Even at low application rates, they have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish, and plants. These active ingredients according to the invention act on all or individual developmental stages of normally sensitive as well as resistant animal pests (such as insects or representatives of the order Acarina). The insecticidal or acaricidal activity of the active ingredients according to the invention can manifest itself directly, i.e., destruction of the pest occurs immediately or only after a certain period of time (e.g., during molting); or indirectly, for example, by reducing egg laying and / or hatching rates.

[0379] Examples of the animal pests mentioned above are:

[0380] from the order Acarina, e.g.

[0381] 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., 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., Rhizoglyphus spp., Sarcoptes spp.), Steneotarsonemus spp., Tarsonemus spp., and Tetranychus spp.;

[0382] From the order Phthirus, e.g.

[0383] Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp., and Phylloxera spp.;

[0384] From the order Coleoptera, e.g.

[0385] Agriotes spp., Amphimallon majale, Anomala orientalis, Anthonomus spp., Aphodius spp., Astylus atromaculatus, Ataenius spp., Atomaria linearis, Chaetocnema tibialis, Cerotomas spp., Conoderus spp., Cosmopolites spp., Cotinis nitida, Curculio spp., Cyclocephalas spp., Dermestes spp., Diabrotica spp.), Argentine beetle (Diloboderus abderus), herbivorous ladybirds (Epilachna spp.), Eremnus species, Heteronychus arator, Hypothenemus hampei, Lagria vilosa, Leptinotarsa ​​decemlineata, Lissorhoptrus spp., Liogenys spp., Maecolaspis spp., Maladera castanea, American leaf beetles (Megascelis spp.), rapeseed beetles (Melighetes aeneus), Melolontha spp., Myochrousarmatus, Orycaephilus spp., Otiorhynchus spp., Phyllophaga spp.), Phlyctinus spp., Popillia spp., Psylliodes spp., Rhyssomatus aubtilis, Rhizopertha spp., Scarabeidae, Sitophilus spp., Sitotroga spp.), Somaticus spp., Cryptorhynchus spp., Sternechus subsignatus, Tenebrio spp., Tribolium spp., and Trogoderma spp.;

[0386] From the order Diptera, e.g.

[0387] Aedes spp., Anopheles spp., Antherigonas occata., Bactrocea oleae, Bibio hortulanus, Bradysia spp., Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Delia spp., Drosophila melanogaster, Fannia spp., Gastrophilus spp., Geomyza tripunctata, Glossina spp.), Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis spp., Riveria quadrifasciata, Scatella spp., Sciara spp., Stomoxys spp., Tabanus spp., Tannia spp.) and Tipula spp.;

[0388] From the order Hemiptera, e.g.

[0389] Acanthocoris scabrator, Acrosternum spp., Adelphocoris lineolatus, Aleurodes spp., Bathycoeliathalassina, Bathycoeliathalassina, Clavigralla tomentosicollis, Creontiades spp., Dichelops furcatus, Edessa spp., Euchistus spp., Eurydema pulchrum, Horcias spp., Brown-winged stink bug, Horcias spp. nobilellus), rice stink bugs, Lygus species, tropical scale bugs, Murgantia histrionic, new long-margined stink bugs, Nesidiocoris tenuis, green stink bugs, Nysius simulans, island stink bugs, skin stink bugs, wall stink bugs, red assassin bugs, cocoa stink bugs, chestnut stink bugs, Scotinophara spp., Thyanta species, Triatominae species, cassava web stink bugs;

[0390] Pea aphid (Acyrthosium pisum), Adalges species, Agallina ensigera, Targuiron vein psyllid, Aleurodicus species, Aleurocanthus species, Sugarcane hole whitefly, Aleurothrixus floccosus, Cabbage whitefly (Aleyrodes brassicae), Cotton leafhopper (Amarasca biguttula), Lemon leafhopper, Kidney shield scale species, Aphididae, Aphid species, Aspidiotus species, Eggplant groove aphid, Potato / tomato psyllid (Bactericera cockerelli), Whitefly species, Brachycaudus species, Cabbage aphid, Cavariella species, Two-tailed aphid (Cavariella aegopodii) Scop.), wax scale species, black-brown round shield scale, orange-brown round shield scale, leafhopper species, large white leafhopper (Cofana spectra), Cryptopterus species, leafhopper species, brown soft scale, corn yellow-winged leafhopper, naked whitefly species, citrus psyllid, wheat aphid, western round tail aphid species, small green leafhopper species, apple aphid, grape leafhopper species, Gascardia species, red eucalyptus psyllid (Glycaspis brimblecombei), cabbage constrictor aphid (Hyadaphis pseudobrassicae), large tail aphid species (Hyalopterus spp.), hyperomyzuspallidus species, lemon green leafhopper (Idioscopus clypealis), African leafhopper, Laodelphax striatellus species, water-hard scale, oyster shield scale species, radish aphid (Lopaphis erysimi), Lyogenys maidis, Aphid species, Cicada species, Metcalfa pruinosa, Aphid, Cicada, Aphid species, Neotoxoptera sp, Nilaparvata species, Nilaparvata spp.), pear green aphid, Odonaspis ruthae, sugarcane cotton aphid, bayberry whitefly, Caulis psyllid, Shield scale species, Gall aphid species, Corn waxhopper, Flathorn planthopper species, Hob wart aphid, Phylloxera species (Phylloxera spp.), Mosella species, Mulberry white scale species, Mealybug species, Cotton blind bug (Pseudatomoscelis seriatus), Psyllid species, Cotton scale (Pulvinaria aethiopica), Toothed scale species, Quesada gigas, Electric leafhopper (Reciliadorsalis), Constrictor aphid species, Black helmet scale species, Banded leafhopper species, Schistosoma species, Wheat aphid species (Sitobion spp.), White-backed planthopper, Spissistilus festinus, Striped planthopper (Tarophagus Proserpina), aphid species, whitefly species, Tridiscus sporoboli, Trionymus spp., African psyllids, scaly scale, flame leafhopper, Zyginidia scutellaris;

[0391] from the order Hymenoptera, e.g.

[0392] Acromyrmex, Arge spp., Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma, Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprions spp., Pogonomyrmex spp., imported fire ants, Solenopsis spp., and Vespa spp.

[0393] From the order Isoptera, e.g.

[0394] Coptotermes spp., Corniternes cumulans, Incisitermes spp., Macrotermes spp., Mastotermes spp., Microtermes spp., Reticulitermes spp.; Tropical fire ants (Solenopsis geminate)

[0395] From the order Lepidoptera, for example,

[0396] Species of the genus Long-winged Roller Moth, species of the genus Brown-banded Roller Moth, species of the genus Clearwing Moth, species of the genus Noctua, cotton leafworm, species of the genus Amylois, species of the genus Mucuna, species of the genus Yellow Roller Moth, species of the genus Argyresthia, species of the genus Banded Roller Moth, species of the genus Spodoptera, species of cotton miner, corn armyworm, powdery moth, peach fruit moth, species of the genus Graminus, species of the genus Color Roller Moth, Chrysoteuchia topiaria, grape fruit moth, species of the genus Leaf Roller, species of the genus Cloud Roller, species of the genus Striped Roller Moth, species of the genus Sheath Moth, Colias lesbia, Cosmophila flava), grass borer species, cabbage borer, apple cyclops, boxwood moth, cyclops species, boxwood moth, stem borer species, Sudan cotton bollworm, Spodoptera species, South American corn seedling borer (Elasmopalpus lignosellus), sweet potato stem borer, mealybug species, leaf cyclops species (Epinotia spp.), salt marsh moth (Etiella zinckinella), flower cyclops species, ring needle cyclops, yellow tussock moth species, root cutter species, Feltia jaculiferia, Grapholita spp., clouded broad-winged cyclops, Heliothis species, cabbage borer, leaf cutter species (Herpetogramma spp.), American white moth, tomato borer, Lasmopalpus lignosellus, spiral leafminer, leafminer species, grape flower moth, Loxostege bifidalis, tussock moth species, miner species, Malacosoma spp., cabbage armyworm, tobacco hornworm, Mythimna spp., Noctuidae species, fall moth species, Orniodes indica, European corn borer, super-small tortoise species, brown tortoise species, small-eyed moth, stem borer, red bell moth, coffee leafminer, one-star armyworm, potato moth, cabbage butterfly, Pieris species, diamondback moth, white nest moth species, leaf moth species, mint ash moth (Rachiplusianu), western bean incense (Richia albicosta), white grain borer species (Scirpophaga spp.), Spodoptera species, Cyprinodon species, Spodoptera species, Cotton leaf roller, Cnaphalocrocis species, Heteroptera species, Trichoplusia species, Tomato leafminer, and Lymantria species;

[0397] From the order Mallophaga, for example,

[0398] Damalina spp. and Trichodectes spp.;

[0399] From the order Orthoptera, for example,

[0400] Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp., Neocurtilla hexadactyla, Periplaneta spp., Scapteriscus spp., and Schistocerca spp.;

[0401] From the order Psocoptera, for example,

[0402] Liposcelis spp.;

[0403] From the order Siphonaptera, for example,

[0404] Ceratophyllus spp., Ctenocephalides spp., and Xenopsylla cheopis;

[0405] From the order Thysanoptera, for example,

[0406] Calliothrips phaseoli, Frankliniella spp., Heliothrips spp., Hercinothrips spp., Parthenothrips spp., Scirtothrips aurantii, Sericothrips variabilis, Taeniothrips spp., Thrips spp.

[0407] From the order of the Thysanura, for example, Lepisma saccharina.

[0408] In another aspect, the present invention may also relate to a method for controlling damage to plants and parts thereof by plant-parasitic nematodes (endoparasitic, semi-endoparasitic and ectoparasitic nematodes), in particular the following plant-parasitic nematodes, such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria and other species of root knot nematodes; cyst-forming nematodes, Globodera rostochiensis and other species of Globodera; Heterodera avenae, Heteroderaglycines, Heterodera exigua and other species of Globodera; schachtii), Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus, and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus, and other Bursaphelenchus species; Ring nematodes, nematodes), Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stemand bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, and other Ditylenchus species; Awl nematodes, Dolichodorus species;Spiral nematodes, Heliocotylenchus multicinctus, and other species of the genus Helicotylenchus; Sheath and sheathoid nematodes, species of the genera Hemicycliophora, and species of the genera Hemicriconemoides; Hirshmanniella species; Lancenematodes, species of the genus Hoploaimus; False rootknot nematodes, species of the genus Nacobbus; Needle nematodes, Longidoruse longatus, and other species of the genus Longidorus; Pin nematodes, species of the genus Pratylenchus; Lesion nematodes. nematodes), Pratylenchus negletus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi, and other Pratylenchus species; Burrowing nematodes, Radopholus similis, and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis, and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus) and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, and other Tylenchorhynchus species;Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant-parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp.

[0409] The compounds of the present invention also have activity against mollusks. Examples include, for example, the Pomacea family; the Arion family (A. ater, A. circumscriptus, A. hortensis, A. rufus); the Bradybaenidae family (Bradybaenidae); fruticum); Cepaea (Cepaea hortensis, C. nemoralis); Ochlodina; Deroceras (D. agrestis, D. empiricorum, D. laeve, D. reticulatum); Discus (D. rotundatus); Euomphalia; Galba (Galba trunculata); Helicelia (H. itala, H. obvia); Helicigona (Helicidae). arbustorum; Helicodiscus; Helix (H. aperta); Limax (L. cinereoniger, L. flavus, L. marginatus, L. maximus, L. tenellus); Lymnaea; Milax (M. gagates, M. marginatus, M. sowerbyi); Opeas; Pomacea (P. canaticulata); Vallonia and Zanitoides.

[0410] The active ingredients according to the invention can be used for controlling, i.e. suppressing or destroying pests of the aforementioned type, which occur in particular on plants, especially on useful and ornamental plants in agriculture, horticulture and forestry, or on organs of these plants, such as fruits, flowers, leaves, stems, tubers or roots, and in some cases even plant organs formed at a later point in time still remain protected against these pests.

[0411] In particular, suitable target crops are cereals such as wheat, barley, rye, oats, rice, corn or sorghum; beets such as sugar beets or fodder beets; fruits such as pome, stone or soft fruit such as apples, pears, plums, peaches, apricots, cherries or berries such as strawberries, raspberries or blackberries; leguminous crops such as beans, lentils, peas or soybeans; oilseed crops such as rapeseed, mustard, olives, sunflowers, coconuts, castor beans, cocoa beans or peanuts; melon crops such as pumpkin, cucumber or melon; fiber plants such as cotton, flax or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes or bell peppers; lauraceae such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper, grapevines, hops, plantaginaceae and latex plants.

[0412] The compositions and / or methods of the present invention may also be used on any ornamental and / or vegetable crop, including flowers, shrubs, broadleaf trees, and evergreen plants.

[0413] For example, the present invention can be used with any of the following ornamental plant species: Ageratum species, Alonsoa species, Anemone species, Anisodontea capsenisis, Anthemis species, Antirrhinum species, Aster species, Begonia species (e.g., Rieger Begonia, Begonia sempervirens, Begonia tubéreux), Bougainvillea species, Brachycome species, Brassica species (ornamentals), Calceolaria species, Capsicum, Catharanthus roseus, Canna species, Centaurea species, Chrysanthemum species, Cineraria species (C. maritime), Coreopsis species, Crassula coccinea, Cupheaignea, Dahlia species, Delphinium species, Dicentra species, Dorotheantus species. spp.), Lisianthus, Forsythia species, Fuchsia species, Geranium gnaphalium, Gerbera species, Globe amaranth, Heliotrope species, Sunflower species, Hibiscus species, Hydrangea species, Hydrangea species, Rhododendron, Impatiens species (African balsam), Amaranth species (Iresines spp.), Kalanchoe species, Lantana, March flower, Lion's ear, Lilium species, Mesembryanthemum species, Physalis species, Monarda species, Dracaena species, Marigold species, Dianthus species (carnation), Canna species, Oxalis species, Daisy species, Pelargonium species (Shieldleaf Pelargonium, Horseshoe Pelargonium), Viola species (Viola tricolor), Petunia species, Phlox species, Plecthranthus species spp.), poinsettia species, creeper species (five-leaf creeper, Parthenocissus quinquefolia), primula species, ranunculus species, azalea species, Rosa species (roses), rudbeckia species, African violet species, salvia species, Scaevola aemola, Schizanthus wisetonensis, sedum species, Solanum species, Surfinia petunia species (Surfinia spp.), marigold species, Nicotiana species, verbena species, zinnia species, and other bedding plants.

[0414] For example, the present invention can be used with any of the following vegetable species: Allium species (garlic, onion, A. oschaninii, leek, shallot, scallion), fennel, celery (Apium graveolus), asparagus, beets (Beta vulgarus), Brassica species (cabbage, Chinese cabbage, turnip), peppers, chickpeas, endive, chicory species (chicory, endive), watermelon, Cucumber species (cucumber, melon), Cucurbita species (zucchini, Indian pumpkin), Cyanara species (artichoke, cardoon), wild carrot, fennel, Hypericum species, lettuce, Lycopersicon species (tomato, cherry tomato), mint species, basil, parsley, Phaseolus species (bean, pea), peas, radish, rhubarb, Rosemary species, sage species, black salsify (Scorzonera spp.), hispanica), eggplant, spinach, new Valerian species (V. eriocarpa), and broad beans.

[0415] Preferred ornamental plant species include African violet, begonia, dahlia, gerbera, hydrangea, verbena, rose, kalanchoe, poinsettia, aster, cornflower, coreopsis, delphinium, monarda, phlox, rudbeckia, sedum, petunia, violet, impatiens, geranium, chrysanthemum, ranunculus, fuchsia, salvia, hydrangea, rosemary, sage, St. John's wort, mint, sweet pepper, tomato, and cucumber.

[0416] The active ingredients according to the invention are particularly suitable for controlling the bean aphid, cucumber leaf beetle, tobacco budworm, peach aphid, diamondback moth and sea moth on cotton, vegetables, corn, rice and soybean crops. The active ingredients according to the invention are also particularly suitable for controlling the cabbage looper (preferably on vegetables), the codling moth (preferably on apples), the green leafhopper (preferably on vegetables, in vineyards), the potato beetle (preferably on potatoes) and the striped stem borer (preferably on rice).

[0417] The compounds of formula I are particularly suitable for controlling:

[0418] - Hemiptera pests, for example one or more of the species Bemisia tabaci, Bean aphid, Green peach aphid, Grain aphid, Brown rice hopper and Euschistus heros (preferably in vegetables, soybean and sugar cane);

[0419] Lepidoptera pests, for example one or more of the species Spodoptera littoralis, Spodoptera frugiperda, Plutella xylostella, Cnaphalocrocis medinalis, Codling moth, Soybean looper, Chilo suppressalis, South American corn borer, Spodoptera sojae and Tomato leafminer (preferably in vegetables and corn);

[0420] Pests from the order Thysanoptera, such as the family Thripidae, for example one or more of Thrips tabaci and Thrips occidentalis (preferably in vegetables); and

[0421] • Soil pests (eg of the order Coleoptera), for example species Diabrotica spp., Cladophora spp. and Colorado potato beetles (preferably in vegetables and corn).

[0422] The term "crops" is to be understood as also including crop plants which have been transformed by the use of recombinant DNA techniques such that they are able to synthesize one or more selectively acting toxins, such as are known, for example, from toxigenic bacteria, in particular those of the genus Bacillus.

[0423] Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, such as insecticidal proteins from Bacillus cereus or Bacillus japonicus; or insecticidal proteins from Bacillus thuringiensis, such as delta-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C, or vegetative insecticidal proteins (Vips), such as Vip1, Vip2, Vip3, or Vip3A; or insecticidal proteins of bacterial colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophila, or Xenorhabdus spp. nematophilus); toxins produced by animals, such as scorpion toxins, spider toxins, bee toxins and other insect-specific neurotoxins; toxins produced by fungi, such as streptomycin, plant lectins, such as pea lectin, barley lectin or snowdrop lectin; agglutinin; protease inhibitors, such as trypsin inhibitor, silk proteinase inhibitor, potato glycoprotein, cystatin, papain inhibitor; ribosome inactivating protein (RIP), such as ricin, maize-RIP, abrin, luffain, saporin or bryophyllin; steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdysteroid inhibitors, HMG-COA-reductase, ion channel blockers, such as sodium channel or calcium channel blockers, juvenile hormone esterase, diuretic hormone receptor, stilbene synthase, bibenzyl synthase, chitinase and glucanase.

[0424] In the context of the present invention, δ-endotoxins (e.g., Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1, or Cry9C) or vegetative insecticidal proteins (Vips) (e.g., Vip1, Vip2, Vip3, or Vip3A) are understood to include, but are not limited to, mixed toxins, truncated toxins, and modified toxins. Mixed toxins are recombinantly produced by combining different domains of those proteins (see, e.g., WO 02 / 15701). Truncated toxins, such as truncated Cry1Ab, are known. In the case of modified toxins, one or more amino acids of a naturally occurring toxin are replaced. In such amino acid replacements, it is preferred that a non-naturally occurring protease recognition sequence be inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G recognition sequence is inserted into the Cry3A toxin (see WO 03 / 018810).

[0425] Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed in, for example, EP-A-0 374 753, WO 93 / 07278, WO 95 / 34656, EP-A-0 427 529, EP-A-451 878 and WO 03 / 052073.

[0426] Methods for preparing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95 / 34656, EP-A-0 367474, EP-A-0 401 979 and WO 90 / 13651.

[0427] The toxins contained in the transgenic plants confer tolerance to harmful insects. Such insects can be found in any insect taxonomic group, but are particularly common among beetles (Coleoptera), two-winged insects (Diptera), and moths (Lepidoptera).

[0428] Transgenic plants containing one or more genes encoding insecticide resistance and expressing one or more toxins are known and some are commercially available. Examples of such plants are: (corn variety expressing Cry1Ab toxin); YieldGard (corn variety expressing Cry3Bb1 toxin); YieldGard (corn varieties expressing Cry1Ab and Cry3Bb1 toxins); (corn variety expressing Cry9C toxin); Herculex (a corn variety expressing the Cry1Fa2 toxin and the enzyme phosphinothricin N-acetyltransferase (PAT) that confers tolerance to the herbicide glufosinate ammonium); NuCOTN (cotton variety expressing Cry1Ac toxin); Bollgard (cotton variety expressing Cry1Ac toxin); Bollgard (cotton varieties expressing Cry1Ac and Cry2Ab toxins); (cotton variety expressing Vip3A and Cry1Ab toxins); (potato variety expressing Cry3A toxin); GT Advantage (GA21 glyphosate tolerance trait), CB Advantage (Bt11 corn borer (CB) trait) and

[0429] Further examples of such genetically modified crops are:

[0430] 1. Bt11 maize, from Syngenta Seeds SAS, Chemin de Hobit 27, F-31 790 St. Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize confers resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) by transgenic expression of a truncated Cry1Ab toxin. Bt11 maize also transgenicly expresses the PAT enzyme to confer tolerance to the herbicide glufosinate ammonium.

[0431] 2. Bt176 maize, from Syngenta Seeds, 27 Rue de Hobbitt, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This genetically modified maize confers resistance to attack by the European corn borer (Ostrinia nubilalis and Sesamia serrata) through transgenic expression of the Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to confer tolerance to the herbicide glufosinate ammonium.

[0432] 3. MIR604 maize, available from Syngenta Seeds, 27 Rue de Hobbit, F-31 790 Saint-Sauveur, France, registration number C / FR / 96 / 05 / 10. This maize plant is rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin G protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03 / 018810.

[0433] 4. MON 863 maize, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / DE / 02 / 9. MON 863 expresses the Cry3Bb1 toxin and confers resistance to certain coleopteran insects.

[0434] 5. IPC 531 cotton, from Monsanto Europe SA, 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C / ES / 96 / 02.

[0435] 6.1507 maize, from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C / NL / 00 / 10. Genetically modified maize expressing the protein Cry1F for resistance to certain lepidopteran insects and the protein PAT for tolerance to the herbicide glufosinate ammonium.

[0436] 7. NK603×MON 810 maize, from Monsanto Europe, 270-272 Avenue Tervuren, B-1150 Brussels, Belgium, registration number C / GB / 02 / M3 / 03. This is a conventionally bred hybrid maize variety, produced by crossing the genetically modified varieties NK603 and MON 810. NK603×MON 810 maize transgenically expresses the protein CP4 EPSPS obtained from the Agrobacterium strain CP4, rendering it herbicide tolerant. (contains glyphosate), and also Cry1Ab toxin obtained from Bacillus thuringiensis subsp. kurstakia, which confers resistance to certain lepidopteran insects, including the European corn borer.

[0437] Transgenic crops of insect-resistant plants are also described in the BATS (Zentrum für Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland) report 2003 ( http: / / bats.ch )middle.

[0438] The term "crop" should be understood to also include crop plants that have been transformed using recombinant DNA technology to enable them to synthesize selectively acting antipathogenic substances, such as, for example, so-called "pathogenesis-related proteins" (PRPs, see, for example, EP-A-0 392 225). Examples of such antipathogenic substances and transgenic plants capable of synthesizing such antipathogenic substances are known, for example, from EP-A-0 392 225, WO 95 / 33818, and EP-A-0 353 191. Methods for producing such transgenic plants are generally known to those skilled in the art and are described, for example, in the publications mentioned above.

[0439] Crops can also be modified to increase resistance to fungal (eg, Fusarium, Anthracnose, or Phytophthora), bacterial (eg, Pseudomonas), or viral (eg, Potato Leaf Roll Virus, Tomato Spotted Wilt Virus, Cucumber Mosaic Virus) pathogens.

[0440] Crops also include those with increased resistance to nematodes, such as Heterodera glycines.

[0441] Crops with tolerance to abiotic stress include those with increased tolerance to drought, high salinity, high temperature, cold, frost or light radiation, for example, through expression of NF-YB or other proteins known in the art.

[0442] Antipathogenic substances that can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers of sodium channels and calcium channels, for example viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; so-called "pathogenesis-related proteins" (PRPs; see, for example, EP-A-0 392 225); antipathogenic substances produced by microorganisms, such as peptide antibiotics or heterocyclic antibiotics (see, for example, WO 95 / 33818) or proteins or polypeptide factors which are involved in plant pathogen defense (so-called "plant disease resistance genes", as described in WO 03 / 000906).

[0443] Other areas of use of the compositions according to the invention are the protection of stored goods and storage rooms and the protection of raw materials such as wood, textiles, floor coverings or buildings, and also in the hygiene sector, in particular the protection of humans, domestic animals and productive livestock from pests of the types mentioned.

[0444] 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 in an animal. The present invention further provides a compound of the first aspect for use in preventing and / or treating a disease transmitted by an ectoparasite.

[0445] The present invention provides the use of the compound of the first aspect for manufacturing a medicament for controlling parasites in or on an animal. The present invention further provides the use of the compound of the first aspect for manufacturing a medicament for controlling ectoparasites of an animal. The present invention further provides the use of the compound of the first aspect for manufacturing a medicament for preventing and / or treating diseases transmitted by ectoparasites.

[0446] The present invention provides a use of the compound of the first aspect in controlling parasites in or on an animal. The present invention further provides a use of the compound of the first aspect in controlling external parasites on an animal.

[0447] When used in the context of parasites in or on animals, the term "control" means reducing the number of pests or parasites, eliminating pests or parasites and / or preventing further infestation by pests or parasites.

[0448] When used in the context of parasites in or on animals, the term "treat" means to inhibit, slow, halt or reverse the progression or severity of existing symptoms or disease.

[0449] The term "prevent" when used in the context of parasites in or on animals means avoiding the development of symptoms or disease in the animal.

[0450] When used in the context of parasites in or on animals, the term "animal" may refer to both mammals and non-mammals, such as birds or fish. In the case of a mammal, it can be a human or a non-human mammal. Non-human mammals include, but are not limited to, livestock animals and pets. Livestock animals include, but are not limited to, cattle, camels, pigs, sheep, goats, and horses. Pets include, but are not limited to, dogs, cats, and rabbits.

[0451] A "parasite" is a harmful organism that lives in or on a host animal and benefits by obtaining nutrients at the host animal's expense. An "endoparasite" is a parasite that lives inside the host animal. An "ectoparasite" is a parasite that lives on the host animal's body. Ectoparasites include, but are not limited to, ticks, insects, and crustaceans (e.g., sea lice). The subclass Ixodida (or Acarina) includes ticks and mites. Ticks include, but are not limited to, members of the genera Rhipicaphalus, such as Rhipicaphalus microplus (Boophilus microplus) and Rhipicephalus sanguineus; Amblyomrna; Dermacentor; Haemaphysalis; Hyalomma; Ixodes; Rhipicentor; Margaropus; Argas; Otobius; and Ornithodoros. Mites include, but are not limited to, members of the genera: Dermestes, such as Dermestes gallinae; Psoralea, such as Psoralea goatii; Cheyletus; Dermatophytes; such as Dermatophytes gallinae; Ortnithonyssus; Demodex, such as Demodex canis; Sarcophagida, such as Sarcophagidae; and Psoralea. Insects include, but are not limited to, members of the orders: Siphonaptera, Diptera, Trichoderma, Lepidoptera, Coleoptera, and Homoptera. Members of Siphonaptera include, but are not limited to, Ctenocephatides cati and Ctenocephatides canis. Members of Diptera include, but are not limited to, species of the genus Musca; skin flies, such as horse flies and sheep flies; biting flies; horseflies, such as species of the genus Tabunus and species of Tabunus; black horn flies, such as blood flies; biting flies; green flies; midges; and mosquitoes. Members of the order Trichoderma include, but are not limited to, blood-sucking lice and chewing lice, such as the wool louse (Bovicola Ovis) and the bovine feather louse.

[0452] The term "effective amount," when used in the context of parasites in or on an animal, refers to an amount or dosage of a compound of the invention, or a salt thereof, which, when administered to an animal in a single dose or multiple doses, provides the desired effect in or on the animal. An effective amount can be readily determined by the attending diagnostician (as one skilled in the art) by using known techniques and by observing results obtained in similar situations. In determining an effective amount, the attending diagnostician considers a number of factors, including, but not limited to: the species of mammal; its size, age, and general health; the parasite to be controlled and the degree of infestation; the specific disease or condition involved; the extent or severity of the disease or condition; the individual's response; the specific compound to be administered; the mode of administration; the bioavailability characteristics of the administered formulation; the dosage regimen selected; the use of concomitant medications; and other relevant circumstances.

[0453] The compounds of the present invention can be given to animals by any route with the desired effect, including but not limited to topical, oral, parenteral and subcutaneous. Topical administration is preferred. Preparations suitable for topical administration include, for example, solutions, emulsions and suspensions, and can be poured, dotted, sprayed, sprayed, or immersed in the form of a spray race. In an alternative, the compounds of the present invention can be given by ear tags or collars.

[0454] The salt forms of the compounds of the present invention include both pharmaceutically acceptable salts and veterinarily acceptable salts, which may be different from agrochemically acceptable salts. Pharmaceutically and veterinarily acceptable salts and common methods for preparing them are well known in the art. See, for example, Gould, PL, "Salt selection for basic drugs", International Journal of Pharmaceutics, 33: 201-217 (1986); Bastin, RJ et al. "Salt Selection and Optimization Procedures for Pharmaceutical New Chemical Entities", Organic Process Research and Development, 4: 427-435 (2000); and Berge, SM et al., "Pharmaceutical Salts", Journal of Pharmaceutical Sciences, 66: 1-19, (1977). It will be appreciated by those skilled in the art that the compound of the present invention easily changes into salt using technology and conditions known to those of ordinary skill in the art, and can be used as salt (such as hydrochloride) to separate.In addition, it will be appreciated by those skilled in the art that the compound of the present invention easily changes into corresponding free alkali, and can be used as corresponding free alkali to separate from corresponding salt.

[0455] The present invention also provides methods for controlling pests (such as mosquitoes and other disease vectors; see also http: / / www.who.int / malaria / vector_control / irs / en / ). In one embodiment, the method for controlling pests comprises applying the composition of the present invention to the target pests, their locus, or a surface or substrate by painting, rolling, spraying, coating, or dipping. By way of example, IRS (indoor residual spraying) application to surfaces (such as walls, ceilings, or floor surfaces) is contemplated by the methods of the present invention. In another embodiment, application of such compositions to substrates such as nonwoven or fabric materials in the form of (or for use in the manufacture of) netting, coverings, bedding, curtains, and tents is contemplated.

[0456] In one embodiment, the method for controlling this type of harmful organism comprises applying the composition of the present invention of pest-killing effective dose to target harmful organism, their place or surface or substrate, so that on this surface or substrate, effective pest-killing activity of retention is provided.Such application can be carried out by brushing, rolling, spraying, coating or dipping pest-killing composition of the present invention.By way of example, the IRS application of surface (such as wall, ceiling or floor surface) has been considered by method of the present invention, so that effective pest-killing activity of retention is provided on this surface.In another embodiment, it has been considered to use this type of composition for the residual control of the harmful organism on substrate, and this substrate is the fabric material of the form (or can be used in the manufacture of these articles) such as being in netting, covering, bedding, curtain and tent.

[0457] The substrate to be treated (including nonwovens, fabrics or nettings) can be made of natural fibers such as cotton, raffia, jute, flax, sisal, burlap or wool, or synthetic fibers such as polyamide, polyester, polypropylene, polyacrylonitrile or the like. Polyester is particularly suitable. Methods for textile treatment are known, for example WO 2008 / 151984, WO 2003 / 034823, US 5631072, WO 2005 / 64072, WO 2006 / 128870, EP 1724392, WO 2005113886 or WO 2007 / 090739.

[0458] A further area of ​​use of the compositions according to the invention is in the field of tree injection / trunk treatment of all ornamental trees as well as all kinds of fruit and nut trees.

[0459] In the field of tree injection / trunk treatment, the compounds according to the invention are particularly suitable for combating wood-boring insects from the orders Lepidoptera and from the orders Coleoptera mentioned above, in particular against the wood-boring insects listed in the following Tables A and B:

[0460] Table A. Examples of economically important exotic wood-boring insects.

[0461]

[0462] Table B. Examples of economically important native wood-boring insects.

[0463]

[0464]

[0465]

[0466]

[0467] The present invention can also be used to control any insect pest that may be present in turfgrass, including, for example, beetles, caterpillars, fire ants, ground pearls, millipedes, woodlice, mites, mole crickets, scale insects, mealybugs, ticks, cicadas, southern wheat stink bugs, and white grubs. The present invention can be used to control insect pests at all stages of their life cycle, including eggs, larvae, nymphs, and adults.

[0468] In particular, the present invention can be used to control insect pests that feed on the roots of turfgrasses, including grubs (such as Cyclocephala spp. (e.g., the marked beetle, C. lurida), Rhizotrogus spp. (e.g., the European beetle, R. majalis), Cotinus spp. (e.g., the Green June beetle, C. nitida), Popillia spp. (e.g., the Japanese beetle, P. japonica), Phyllophaga spp. (e.g., the May / June beetle), Chafer spp. (e.g., the Black turfgrass ataenius, the Black velvet beetle), Maladera spp. (e.g., the Asiatic garden beetle, beetle, chestnut-colored scarab beetle, and Tomarus species), ground pearls (Margarodes spp.), mole crickets (tawny, southern, and short-winged; Scapteriscus spp., Gryllotalpa africana), and leatherjackets (European crane fly, Tipula spp.).

[0469] The present invention can also be used to control insect pests of turfgrass in thatched homes, including armyworms (such as the fall armyworm Spodoptera frugiperda, and the common armyworm Pseudaletia unipuncta), cutworms, weevils (Sphenophorus spp., such as S. venatus verstitus and S. parvulus), and grass borers (such as Crambus spp. and the tropical grass borer, Herpetogramma phaeopteralis).

[0470] The present invention can also be used to control insect pests in turfgrasses that live above ground and feed on turfgrass leaves, including wheat stink bugs (such as the southern wheat stink bug, Blissus insularis), Bermudagrass mite (Eriophyes cynodoniensis), Grass mealybug (Antonina graminis), Propsapia bicincta, leafhoppers, cutworms (Noctuidae), and Schizaphis graminis.

[0471] The present invention can also be used to control other pests in turfgrass, such as introduced fire ants (Solenopsis invicta) that create nests in lawns.

[0472] In the hygiene sector, the compositions according to the invention are effective against ectoparasites such as hard ticks, soft ticks, scabies, autumn mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, bird lice and fleas.

[0473] Examples of such parasites are:

[0474] From the order of the Pediculus: Haemaphysalis spp., Linognathus spp., Pediculus hominis spp., and Phtirus spp., Phitirus spp.

[0475] From the order Trichophagus: Felicola species, Brachypelago species, Ducklingia species, Cattlelicia species, Werneckiella species, Lepikentron species, Cattlelicia species, Trichopelago species and Felicola species (Felicola spp.).

[0476] From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp. spp.), Musca spp., Hydrotaea spp., Biting flies spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp. spp.) and Melophagus spp.

[0477] From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllum spp.

[0478] From the order of the Heteropterida, for example, Cimex spp., Triatominae spp., Panstrongylus spp.

[0479] From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattelagermanica and Supella spp.

[0480] Subclass Acaria (family Acarida) and orders Meta-stigmata and Meso-stigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyommas spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp. spp.), Sternostoma spp., and Varroa spp.

[0481] From the orders Actinedida (Prostigmata) and Acaridida (Astigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp. spp.), Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcooptes spp., Notoedress spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes spp.

[0482] The compositions according to the invention are also suitable for protecting materials in the case of, for example, wood, textiles, plastics, adhesives, glues, paints, paper and card, leather, floor coverings and construction from infestation by insects.

[0483] The compositions according to the invention can be used, for example, against the following pests: beetles, such as the American house beetle, the hairy green tiger beetle, the furniture beetle, the death beetle, Ptilinuspecticornis, Dendrobium pertinex, the fine-toothed fork-tailed beetle, Priobiumcarpini, the brown powder beetle, the African powder beetle, the southern powder beetle, the flat-stomached beetle, the soft-haired powder beetle, the flat-legged powder beetle, the scale-haired powder beetle, the wood beetle, the wood beetle, the black beetle, the red-bellied oak beetle, the brown heteroptera beetle, the double-spined beetle and the bamboo beetle, and also members of the Hymenoptera, such as the blue-black wood beetle, the giant wood beetle, the Taiga wood beetle and Urocerus The compounds of formulae I and I'a or their salts are particularly suitable for controlling one or more pests selected from the following families: Noctuidae, Plutella xylostellae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Psoraciformes, Meloidogyne, and Heteroderae. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in Tables A-1 to A-92 and Table P") controls one or more pests selected from the following families: Noctuidae, Plutellae, Chrysomelidae, Thripidae, Pentatomidae, Tortricidae, Delphacidae, Aphididae, Noctuidae, Spodoptera, Meloidogyne, and Heteroderae.

[0484] The compounds of formula I and I'a or their salts are particularly suitable for controlling one or more pests selected from the following genera: Spodoptera species, Diamondback moth species, Flower Thrips species, Thrips species, American stink bug species, Cydia species, Brown rice hopper species, Myzus persicae species, Aphis species, Rootworm species, Aphis species, Spodoptera species and Grass borer species. In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in Tables A-1 to A-92 and Table P") controls one or more pests selected from the following genera: Spodoptera species, Diamondback moth species, Flower Thrips species, Thrips species, American stink bug species, Cydia species, Brown rice hopper species, Myzus persicae species, Aphis species, Rootworm species, Aphis species, Spodoptera species and Grass borer species.

[0485] The compounds of formula I and I'a or their salts are particularly useful for controlling one or more of the following: Spodoptera littoralis, Plutella xylostella, Western flower thrips, Thrips tabaci, American stink bug, codling moth, brown rice hopper, peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer.

[0486] In a preferred embodiment of each aspect, compound TX (wherein the abbreviation "TX" means "a compound selected from the compounds defined in Tables A-1 to A-92 and Table P") controls one or more of the following: Spodoptera littoralis, diamondback moth, western flower thrips, tabaci thrips, hero American stink bug, codling moth, brown rice hopper, green peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer, such as Spodoptera littoralis+TX, diamondback moth+TX; western flower thrips+TX, tabaci thrips+TX, hero American stink bug+TX, codling moth+TX, brown rice hopper+TX, green peach aphid+TX, soybean looper+TX, bean aphid+TX, cucumber leaf beetle+TX, cereal aphid+TX, and striped stem borer+TX.

[0487] In an embodiment of each aspect, a compound selected from the compounds defined in Tables A-1 to A-92 and Table P is suitable for controlling Spodoptera littoralis, Plutella xylostella, western flower thrips, tabaci thrips, American stink bug, codling moth, brown rice hopper, green peach aphid, soybean looper, bean aphid, cucumber leaf beetle, cereal aphid, and striped stem borer on cotton, vegetables, corn, corn, rice and soybean crops.

[0488] In an embodiment, a compound selected from the compounds defined in Tables A-1 to A-92 and Table P is suitable for controlling Mamestra (preferably on vegetables), Codling moth (preferably on apples), Empoasca (preferably on vegetables, vineyards), Leptinotarsa ​​(preferably on potatoes) and Chilo suppressalis (preferably on rice).

[0489] The compounds according to the present invention may have any number of benefits, including, among others, favorable levels of biological activity for protecting plants against insects or superior properties for use as agrochemical active ingredients (e.g., higher biological activity, favorable activity spectrum, increased safety (against non-target organisms above and below ground, such as fish, birds, and bees), improved physico-chemical properties, or increased biodegradability). In particular, it has been unexpectedly discovered that certain compounds of Formula I can exhibit favorable safety profiles relative to non-target arthropods, particularly pollinators such as honey bees, solitary bees, and bumblebees. Most particularly, relative to the Italian honey bee (Apis mellifera).

[0490] The compounds according to the invention can be used as pesticides in unmodified form, but they are generally formulated into compositions in various ways using formulation adjuvants such as carriers, solvents, and surfactants. These formulations can be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifiable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or a water-miscible organic solvent as a carrier), impregnated polymer films, or in other known forms, for example, from the Manual on Development and Use of FAO and WHO Specifications for Pesticides, United Nations, 1st edition, second revision (2010). Such formulations can be used directly or diluted before use. Dilution can be performed with, for example, water, liquid fertilizers, micronutrients, biological organisms, oils or solvents.

[0491] These formulations can be prepared, for example, by mixing the active ingredient with a formulation adjuvant to obtain a composition in the form of a finely divided solid, granules, solution, dispersion or emulsion. The active ingredients can also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of plant or animal origin, modified oils of plant or animal origin, organic solvents, water, surfactants or combinations thereof.

[0492] These active ingredients can also be contained in very fine microcapsules. Microcapsules contain active ingredients in porous carriers. This allows the active ingredients to be released (e.g., slowly released) into the environment in controlled amounts. Microcapsules typically have a diameter of from 0.1 to 500 microns. The amount of active ingredient they contain is approximately from 25% to 95% of the capsule weight by weight. These active ingredients can be in the form of a holistic solid, in the form of fine particles in a solid or liquid dispersion, or in the form of a suitable solution. The encapsulated membrane can include, for example, natural or synthetic rubber, cellulose, styrene / butadiene copolymer, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane, or chemically modified polymers and starch xanthate, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules can be formed, in which the active ingredient is contained in the form of finely dispersed particles in a solid matrix of a base material, but these microcapsules themselves are not wrapped.

[0493] Formulation adjuvants suitable for preparing the compositions according to the invention are known per se. As liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetates, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol rosinate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethyl Formamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, dipropylene glycol, alkyl pyrrolidone, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, α-pinene, d-limonene, ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, acetic acid glyceryl, diacetic acid glyceryl, triacetic acid glyceryl, decaglycerol Hexadecane, Hexanediol, Isoamyl Acetate, Isobornyl Acetate, Isooctane, Isophorone, Cumene, Isopropyl Myristate, Lactic Acid, Laurylamine, Mesityl Oxide, Methoxypropanol, Methyl Isoamyl Ketone, Methyl Isobutyl Ketone, Methyl Laurate, Methyl Caprylate, Methyl Oleate, Methylene Chloride, m-Xylene, n-Hexane, n-Octylamine, Octadecanoic Acid, Octylamine Acetate, Oleic Acid, Oleylamine, o-Xylene, Phenol, Polyethylene Glycol, Propionic Acid, Propyl Lactate , propylene carbonate, propylene glycol, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, etc.

[0494] Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soy flour, pumice, wood flour, ground walnut shells, lignin, and similar substances.

[0495] Many surface-active substances can be used advantageously in both solid and liquid formulations, especially those which can be diluted with a carrier before use. Surface-active substances can be anionic, cationic, nonionic or polymeric and they can act as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, such as calcium dodecylbenzenesulfonate; alkylphenol / alkylene oxide addition products, such as ethoxylated nonylphenol; alcohol / alkylene oxide addition products, such as ethoxylated tridecanol; soaps, such as sodium stearate; salts of alkylnaphthalenesulfonates, such as sodium dibutylnaphthalenesulfonate; salts of dialkylsulfosuccinates, such as sodium di(2-ethylhexyl)sulfosuccinate; sorbitol esters, such as sorbitol oleate; quaternary ammoniums, such as dodecyltrimethylammonium chloride; polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphates; as well as other substances, such as described in: McCutcheon's Detergents and Emulsifiers Annual, MC Publishing Company (MC Publishing Company). Corp., Ridgewood New Jersey (1981).

[0496] Other adjuvants that can be used in pesticidal formulations include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or change the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, antifreeze agents, microbicides, and liquid and solid fertilizers.

[0497] The composition according to the invention may comprise an additive comprising an oil of plant or animal origin, a mineral oil, an alkyl ester of such an oil or a mixture of such an oil and an oil derivative. The amount of the oil additive in the composition according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray tank in the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral oil or an oil of plant origin, such as rapeseed oil, olive oil or sunflower oil; emulsified vegetable oils; alkyl esters of oils of plant origin, such as methyl derivatives; or oils of animal origin, such as fish oil or tallow. Preferred oil additives include C8-C 22 Alkyl esters of fatty acids, especially C 12 -C 18Methyl derivatives of fatty acids, such as the methyl esters of lauric, palmitic, and oleic acids (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from the Compendium of Herbicide Adjuvants, 10th edition, Southern Illinois University, 2010.

[0498] These compositions of the invention generally comprise from 0.1% to 99% by weight, in particular from 0.1% to 95% by weight, of a compound of the invention and from 1% to 99.9% by weight of a formulation adjuvant, which preferably includes from 0 to 25% by weight of a surfactant. While commercial products may preferably be formulated as concentrates, the end user will generally use dilute formulations.

[0499] The application rate varies within wide limits and depends on the nature of the soil, the application method, the crop plants, the harmful organisms to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the time of application, and the target crop. In general, the compound can be applied at a rate of from 1 l / ha to 2000 l / ha, in particular from 10 l / ha to 1000 l / ha.

[0500] A preferred formulation may have the following composition (wt %):

[0501] Emulsifiable concentrates :

[0502] Active ingredient: 1% to 95%, preferably 60% to 90%

[0503] Surfactant: 1% to 30%, preferably 5% to 20%

[0504] Liquid carrier: 1% to 80%, preferably 1% to 35%

[0505] Dust agent :

[0506] Active ingredient: 0.1% to 10%, preferably 0.1% to 5%

[0507] Solid carrier: 99.9% to 90%, preferably 99.9% to 99%

[0508] Suspension concentrate:

[0509] Active ingredient: 5% to 75%, preferably 10% to 50%

[0510] Water: 94% to 24%, preferably 88% to 30%

[0511] Surfactant: 1% to 40%, preferably 2% to 30%

[0512] wettable powder :

[0513] Active ingredient: 0.5% to 90%, preferably 1% to 80%

[0514] Surfactants: 0.5% to 20%, preferably 1% to 15%

[0515] Solid carrier: 5% to 95%, preferably 15% to 90%

[0516] Granules:

[0517] Active ingredient: 0.1% to 30%, preferably 0.1% to 15%

[0518] Solid carrier: 99.5% to 70%, preferably 97% to 85%

[0519] The following examples further illustrate (but do not limit) the present invention.

[0520] <![CDATA[ wettable powder ]]> a) b) c) Active ingredient 25％ 50％ 75％ Sodium lignin sulfonate 5％ 5％ - Sodium lauryl sulfate 3％ - 5％ Sodium diisobutylnaphthalenesulfonate - 6％ 10％ Phenol polyglycol ether (7-8 mol of ethylene oxide) - 2％ - Highly dispersed silicic acid 5％ 10％ 10％ Kaolin 62％ 27％ -

[0521] The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain wettable powders which can be diluted with water to give a suspension of the desired concentration.

[0522] <![CDATA[ Powder for dry seed treatment ]]> a) b) c) Active ingredient 25％ 50％ 75％ Light mineral oil 5％ 5％ 5％ Highly dispersed silicic acid 5％ 5％ - Kaolin 65％ 40％ - talc - 20％

[0523] The combination is thoroughly mixed with adjuvants and the mixture is thoroughly ground in a suitable grinder to obtain a dust that can be used directly for seed treatment.

[0524]

[0525]

[0526] Emulsions of any desired dilution which can be used in plant protection can be obtained from these concentrates by dilution with water.

[0527] <![CDATA[ Dust powder ]]> a) b) c) Active ingredient 5％ 6％ 4％ talc 95％ - - Kaolin - 94％ - Mineral fillers - - 96％

[0528] Ready-to-use dusts are obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such dusts can also be used for dry seed dressing of seeds.

[0529] <![CDATA[ Extruder pellets ]]> Active ingredient 15％ Sodium lignin sulfonate 2％ Carboxymethyl cellulose 1％ Kaolin 82％

[0530] The combination is mixed with the adjuvants and ground, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

[0531] <![CDATA[ Coated granules ]]> Active ingredient 8％ Polyethylene glycol (molecular weight 200) 3％ Kaolin 89％

[0532] This finely ground combination is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

[0533] Suspension concentrates

[0534] Active ingredient 40％ Propylene glycol 10％ Nonylphenol polyglycol ether (15 mol of ethylene oxide) 6％ Sodium lignin sulfonate 10％ Carboxymethyl cellulose 1％ Silicone oil (in the form of a 75% emulsion in water) 1％ water 32％

[0535] The finely ground combination is intimately mixed with an adjuvant to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0536] Flowable concentrate for seed treatment

[0537]

[0538] The finely ground combination is intimately mixed with an adjuvant to give a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation materials can be treated and protected against microbial infestation by spraying, pouring or immersion.

[0539] Extended-release capsule suspension

[0540] 28 parts of the combination are mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of a defoamer, and 51.6 parts of water until the desired particle size is reached. To this emulsion, 2.8 parts of a mixture of 1,6-hexanediamine in 5.3 parts of water are added. The mixture is stirred until polymerization is complete. The resulting capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the medium capsules is 8 to 15 microns. The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for this purpose.

[0541] Formulation types include emulsion concentrates (EC), suspension concentrates (SC), suspoemulsions (SE), capsule suspensions (CS), water-dispersible granules (WG), emulsifiable granules (EG), emulsions, water-in-oil emulsions (EO), oil-in-water emulsions (EW), microemulsions (ME), oil dispersions (OD), oil suspensions (OF), oil-soluble concentrates (OL), soluble concentrates (SL), ultra-low volume suspensions (SU), ultra-low volume concentrates (UL), finished drug (TK), dispersible concentrates (DC), wettable powders (WP), soluble granules (SG), or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

[0542] Preparation example:

[0543] "Mp" means melting point in °C. Free radicals represent methyl groups. Recorded on a Brucker 400 MHz spectrometer 1 H NMR measurements, chemical shifts are given in ppm relative to TMS standards. Spectra were measured in deuterated solvents as specified. The following methods were used to characterize these compounds. Characteristic LCMS values ​​obtained for each compound are the retention time ("Rt", reported in minutes) and the measured molecular ion (M+H) + .

[0544] LCMS method:

[0545] Spectra were recorded on a mass spectrometer from Waters (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 Da to 900 Da) and an Acquity UPLC from Waters: binary pump, heated column compartment, diode array detector and ELSD detector. Column: Waters UPLC HSS T3, 1.8 μm, 30 x 2.1 mm, temperature: 60°C, DAD wavelength range (nm): 210 to 500, solvent gradient: A = water + 5% MeOH + 0.05% HCOOH, B = acetonitrile + 0.05% HCOOH; gradient: 10%-100% B in 1.2 min; flow rate (ml / min) 0.85

[0546] Example 1: N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)-1,2,4-triazol-3-yl)ethyl Preparation of methyl)benzamide (Compound P3)

[0547]

[0548] Step A: Preparation of 2-(methylamino)propionamide

[0549]

[0550] To a solution of 2-bromopropionamide (10 g, 65.8 mmol) in acetonitrile was added potassium carbonate (27.5 g, 197.4 mmol) and a 2M solution of methylamine in THF (66 mL, 131.6 mmol). The resulting suspension was stirred at 80 ° C for 16 hours, filtered and concentrated in vacuo. The residue was dissolved in ethyl acetate (100 mL), washed sequentially with water and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give 2-(methylamino)propionamide as white crystals.

[0551] 1 H-NMR (400MHz, CDCl3): δ=3.06 (q, J=7.0Hz, 1H), 2.42 (s, 3H), 1.32 (d, J=7.0Hz, 3H) ppm.

[0552] Step B: Preparation of N-(2-amino-1-methyl-2-oxo-ethyl)-N-methyl-3,5-bis(trifluoromethyl)benzamide preparation

[0553]

[0554] A solution of 2-(methylamino)propionamide (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 at 0° C. and treated dropwise with a 50% solution of 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphaninane-2,4,6-trioxide (T3P) in ethyl acetate (47 mL, 79 mmol). The resulting orange solution was stirred at room temperature for 45 minutes and then concentrated in vacuo. The residue was dissolved in methyl tert-butyl ether (200 mL) and washed with water (2×30 mL), 2 M 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 directly without further purification in the next step.

[0555] 1H-NMR (400MHz, CDCl3): 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).

[0556] Step C: N-[2-[Dimethylaminomethyleneamino]-1-methyl-2-oxo-ethyl]-N-methyl-3,5-dioxo- Preparation of (trifluoromethyl)benzamide

[0557]

[0558] 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 four hours 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.

[0559] LCMS: R t 0.89, m / z=398 (M+H + ).

[0560] Step D: N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide Preparation

[0561]

[0562] 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 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 hours and then concentrated in vacuo. Purification by silica gel chromatography (eluting with ethyl acetate in cyclohexane) gave N-methyl-N-[1-(1H-1,2,4-triazol-5-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0563] LCMS: R t 0.86, m / z=367 (M+H + ).

[0564] Step E: N-[1-(3-Bromo-1H-1,2,4-triazol-5-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzyl Preparation of amide (I6)

[0565]

[0566] To N- methyl -N- [1- (1H-1,2,4- triazole -5- bases) ethyl] -3,5- bis (trifluoromethyl) benzamide (0.95g, 2.6mmol) in dichloromethane (30mL) solution of 2M aqueous solution (3.9mL, 7.8mmol) and benzyltrimethylammonium tribromide (1.1g, 2.9mmol) in dichloromethane (10mL) is added. The reaction mixture is stirred for 45 minutes and then carefully quenched with 2M HCl aqueous solution. The organic phase is separated, dried over sodium sulfate, filtered and concentrated in vacuo to obtain N- [1- (3- bromo- 1H-1,2,4- triazole -5- bases) ethyl] -N- methyl -3,5- bis (trifluoromethyl) benzamide as a yellow solid.

[0567] LCMS: R t 0.98, m / z=445,447(M+H + ).

[0568] Step F: N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)-1,2,4-triazol-3-yl)ethyl Preparation of methyl)benzamide (Compound P3)

[0569]

[0570] 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 and then stirred at room temperature for 30 minutes. To this mixture was added a solution of 2-bromopyrimidine (0.60 g, 3.8 mmol) in dry DMF (2.0 mL) and the reaction was stirred at room temperature for 1 hour and then heated to 120° C. for 15 hours. The reaction mixture was taken up in ethyl acetate and washed with water (5 x 5 mL), washed once with brine, dried over anhydrous MgSO , 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.

[0571] LCMS: R t 1.05, m / z=525 (M+H + ).

[0572] Example 2: N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-dimethoxy- Preparation of (trifluoromethyl)benzamide (Compound P2)

[0573]

[0574] Step A: Preparation of ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propionate

[0575]

[0576] At 0 ℃, to the stirring solution of 3,5-bis (trifluoromethyl) benzoic acid (10.0g, 38.7mmol) in dichloromethane (10.0mL), SOCl (9.21g, 77.5mmol) was added, and the resulting mixture was stirred at room temperature for 2 hours. Then the mixture was concentrated in vacuo, and the residue obtained was added to the stirring solution of ethyl alanine (5.44g, 46.5mmol) in pyridine (100mL) at 0 ℃. The reaction mixture was stirred at room temperature for 2 hours. After the reaction was completed, the mixture was diluted with water, and extracted with ethyl acetate (10ml x 2). The organic phase merged was washed with 2N HCl and salt water successively, through Na SO Drying and vacuum concentration. By silica gel chromatography (eluting with ethyl acetate in cyclohexane) purification of crude product, ethyl 2-[[3,5-bis (trifluoromethyl) benzoyl] amino] propionic ester is obtained.

[0577] LCMS: R t 1.06, m / z=358 ​​(M+H + ).

[0578] Step B: Preparation of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propionic acid

[0579]

[0580] To a stirred solution of ethyl 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propanoate (5.00 g, 14.0 mmol) in THF:HO (1:1, 50 mL) was added LiOH.HO (1.76 g, 42.0 mmol) at 0°C and the resulting mixture was stirred at room temperature for 2 hours. 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.

[0581] LCMS: R t 0.91, m / z=330 (M+H + ).

[0582] Step C: N-[1-[5-(methoxymethyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-diol Preparation of (trifluoromethyl)benzamide (Compound P2)

[0583]

[0584] To a stirred solution of 2-[[3,5-bis(trifluoromethyl)benzoyl]amino]propionic 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, and 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 and then cooled at room temperature. Ethyl acetate (25 mL) was added, and the organic layer was washed with a saturated bicarbonate sol and then with water. Drying over Na2SO4 and concentration in vacuo gave the crude product, which was purified by silica gel chromatography (eluting 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).

[0585] LCMS: R t 0.92, m / z=475(M+H + ); Mp: 155℃-160℃; 1 H NMR

[0586] (400MHz, CDCl3): δ8.92 (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.

[0587] Example 3: N-methyl-N-[1-(5-phenyl-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(triazol-3-yl)ethyl Preparation of (4-fluoromethyl)benzamide (Compound P6)

[0588]

[0589] 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(PPh3)4 (13 mg, 0.011 mmol) and aqueous potassium carbonate (2 M, 0.17 mmol). The resulting mixture was stirred at reflux for 1 hour. After that, LCMS indicated complete conversion. The mixture was added to the reaction mixture and the solvent was removed by vacuum concentration. The crude product was purified by silica gel chromatography (eluting 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).

[0590] LCMS: R t 1.15, m / z=521(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0591] 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. Example 4: N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5- Preparation of bis(trifluoromethyl)benzamide (Compound P15).

[0592]

[0593] Step A: N-[1-[5-(benzhydrylamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P22).

[0594]

[0595] To 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 benzophenone imine (71 mg, 0.38 mmol), xantphos (23 mg, 0.038 mmol), Pd2(dba)3(PPh3)4 (18 mg, 0.019 mmol) and cesium carbonate (19 mg, 0.57 mmol). The resulting mixture was stirred at reflux for 18 hours. After that, LCMS showed complete conversion. The mixture was added to the reaction mixture and the solvent was removed in vacuo. The crude product was purified by silica gel chromatography (eluting with ethyl acetate in cyclohexane) to give N-[1-[5-(benzylideneamino)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P22) as a gum.

[0596] LCMS: R t 1.19, m / z=624 (M+H + ).

[0597] Step B: N-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(triazol-3-yl)-1,2,4-triazol-3-yl)-1,2,4-triazol-3-yl)-ethyl Preparation of (4-fluoromethyl)benzamide (Compound P7).

[0598]

[0599] To a stirred solution of N-[1-[5-(benzylideneamino)-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 aqueous HCl (2N, 0.20 mL, 0.41 mmol), and the resulting mixture was stirred at room temperature for 1 hour. Ethyl acetate (20 mL) was added, and the organic layer was washed with a bicarbonate saturated sol, and then washed with water. It was dried over Na2SO4 and concentrated in vacuo to give a crude product, which was purified by silica gel chromatography (eluted with ethyl acetate / hexane) 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 brown solid.

[0600] LCMS: R t 0.88, m / z=460(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0601] 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

[0602] 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)

[0603]

[0604] To a cooled suspension of 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 CuCl2·2H2O (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 hours. Water was added and the formed precipitate was filtered off. Purification by silica gel chromatography (eluting with ethyl acetate / hexane) gave N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-N-methyl-3,5-bis(trifluoromethyl)benzamide (Compound P15).

[0605] LCMS: R t 1.05, m / z=479(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0606] 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

[0607] Example 5: N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]- Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P1)

[0608]

[0609] Step A: Methyl 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2, Preparation of 4-triazole-3-carboxylate

[0610]

[0611] In a high-pressure metal reactor, triethylamine (35.6 μL, 255 μmol) and [1,3-bis(diphenylphosphino)propane]dichloropalladium(ii) (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 10 bar carbon monoxide atmosphere. 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. The crude material was purified by flash chromatography on silica gel (eluting with methanol in dichloromethane) to give the desired product.

[0612] LCMS: R t 0.99, m / z=489(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0613] δ=8.98(d, J=4.77 Hz, 2H),8.26(s, 2H),7.98(s, 1H),7.76(br d, J=7.34 Hz, 1H),7.50(t, J=4.77 Hz, 1H),6.54(quintet, J=7.06 Hz, 1H),4.02(s, 3H),1.82-1.75(m, 3H)ppm.

[0614] Step B: 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-trifluoromethylbenzoyl]amino]ethyl Preparation of oxazole-3-carboxamide (Compound P37)

[0615]

[0616] Lanthanum (III) trifluoromethanesulfonate (4.2 mg, 7.2 μmol) was added 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. The reaction mixture was heated to 70 ° C and stirred for 2 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. 5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide (compound P37) was obtained by precipitation in diethyl ether as a white solid.

[0617] LCMS: R t 0.88, m / z=474(M+H +); 1 H NMR (400 MHz, methanol-d4)

[0618] 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.

[0619] Step C: (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-(dimethylamino)- Preparation of 1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide

[0620]

[0621] 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-methylamine (0.062 mL, 0.465 mmol) at room temperature. The reaction mixture was heated to 100° C. and stirred for 2 hours. 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.

[0622] 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.

[0623] Step D: (NE)-5-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-N-[(hydroxyamino) Preparation of [methyl]-1-pyrimidin-2-yl-1,2,4-triazole-3-carboxamide

[0624]

[0625] To a solution of hydroxylamine hydrochloride (24.6 mg, 0.355 mmol) in acetic acid (1.25 mL) was added sodium hydroxide (1 N in water, 0.355 mL, 0.355 mmol) dropwise. Since the reaction was slightly exothermic, 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 hour and then concentrated under reduced pressure to give (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.

[0626] LCMS: R t 0.93, m / z=517 (M+H + ).

[0627] Step E: N-[1-[5-(1,2,4-oxadiazol-5-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]- Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P1)

[0628]

[0629] 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 acetic acid (0.79 mL) dropwise at room temperature. The reaction mixture was heated to 90 ° C and stirred for 2 hours. 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. The crude material was purified by reverse phase chromatography (eluting with acetonitrile in water) to give N-[1-[5-(1,2,4-oxadiazole-5-yl)-2-pyrimidin-2-yl-1,2,4-triazole-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (Compound P1) as a beige solid.

[0630] LCMS: R t 1.01, m / z=499 (M+H + ).

[0631] 1H-NMR (400MHz, CDCl3): 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

[0632] Example 6: N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]- Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P30)

[0633]

[0634] Step A: N-[1-[5-(hydrazinecarbonyl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)-1,2,4-triazol-3-yl]ethyl Preparation of methyl)benzamide

[0635]

[0636] 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) was added hydrazine hydrate (35%, 52 μL, 0.37 mmol) at room temperature. The reaction mixture was heated to 60 ° C and stirred for 1 hour. 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.

[0637] LCMS: R t 0.87, m / z=489 (M+H + ).

[0638] Step B: N-[1-[5-(1,3,4-oxadiazol-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]- Preparation of 3,5-bis(trifluoromethyl)benzamide (Compound P30)

[0639]

[0640] At room temperature, to a mixture of N-[1-[5-(hydrazine carbonyl)-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), p-toluenesulfonic acid (17 mg, 0.098 mmol) was added. The reaction mixture was heated to 140 ° C and stirred for 5 hours. After cooling to room temperature, the reaction mixture was concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain N-[1-[5-(1,3,4-oxadiazole-2-yl)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl] ethyl]-3,5-bis(trifluoromethyl)benzamide (compound P30) as a white solid.

[0641] LCMS: R t 0.95, m / z=499 (M+H + ).

[0642] 1 H-NMR (400MHz, DMSO-d6): δ=9.72(br d,J=6.60Hz,1H),9.48(s,1H),9.06(d,J=4.77Hz,2H),8.43(s,2H),8.32(s,1H),7.75-7.70(m,1H),6.11(s,1H),1.75(d,J=6.97Hz,3H)ppm.

[0643] Example 7: N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-difluoromethanesulfonyl Preparation of (trifluoromethyl)benzamide (Compound P28)

[0644]

[0645] Step A: Preparation of 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine

[0646]

[0647] 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 hour. After cooling to room temperature, methanol (8.1 mL) was added and the reaction was heated to 60°C and stirred for 14 hours. After cooling to room temperature, the suspension was filtered through celite and the filtrate was concentrated to give O-methyl N-propionylthiocarbamate.

[0648] A mixture of O-methyl N-propionylthiocarbamate (7.0 g, 48 mmol) and 2-hydrazinopyrimidine (CAS 7504-94-1, 8.1 g, 71 mmol) in dry ethanol (95 mL) was heated to 90 ° C and stirred for 4 hours. After cooling to room temperature, the reaction mixture was filtered and concentrated under reduced pressure. The crude material was purified by silica gel flash chromatography (isopropanol in chloroform) to obtain 2-(5-ethyl-3-methoxy-1,2,4-triazol-1-yl)pyrimidine.

[0649] LCMS: R t 0.62, m / z=206(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0650] 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.

[0651] Step B: Preparation of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine

[0652]

[0653] A mixture of 2- (5- ethyl -3- methoxy -1,2,4- triazole -1- bases) 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 light for 30 minutes. The reaction mixture was concentrated under reduced pressure. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain 2- [5- (1- bromoethyl) -3- methoxy -1,2,4- triazole -1- bases] pyrimidine as a yellow solid.

[0654] LCMS: R t 0.75, m / z=284,286(M+H + ); 1 H-NMR (400 MHz,

[0655] 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.

[0656] Step C: Preparation of 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine; hydrobromide salt

[0657]

[0658] A solution of 2-[5-(1-bromoethyl)-3-methoxy-1,2,4-triazol-1-yl]pyrimidine (2.1 g, 7.4 mmol) in aqueous ammonia (7 M in methanol, 110 mL) was stirred at room temperature for 40 hours. The reaction mixture was concentrated under reduced pressure. Trituration with diethyl ether gave 1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine; hydrobromide salt, which was used without further purification.

[0659] LCMS: R t 0.18, m / z=221(M+H + ).

[0660] Step D: N-[1-(5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethyl)-1 ... Preparation of 4-(2-amino-4-methyl)benzamide

[0661]

[0662] To 1- (5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl) ethylamine; 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 ° C -5 ° C. The reaction mixture was stirred at room temperature for 1 hour. After concentration under reduced pressure, the crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to obtain N- [1- (5-methoxy-2-pyrimidin-2-yl-1,2,4-triazol-3-yl) ethyl] -3,5-bis (trifluoromethyl) benzamide as a yellow solid.

[0663] LCMS: R t 0.99, m / z=461(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0664] 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, CDCl3) δ = -62.86 (s, 6F) ppm.

[0665] Step E: N-[1-(5-oxo-2-pyrimidin-2-yl-1H-1,2,4-triazol-3-yl)ethyl]-3,5-bis(trifluoromethane Preparation of 4-(2-amino-4-methyl)benzamide (Compound P26)

[0666]

[0667] 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 solution, 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.

[0668] LCMS: R t 0.92, m / z=447(M+H + ); 1 H-NMR (400 MHz,

[0669] 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; 19 F NMR (377MHz, DMSO-d6): δ = -61.30 (s, 6F) ppm.

[0670] Step F: N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-difluoromethanesulfonyl Preparation of (trifluoromethyl)benzamide

[0671]

[0672] 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 hours. After cooling at 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. The crude material was purified by flash chromatography on silica gel (ethyl acetate in cyclohexane) to give N-[1-[5-(difluoromethoxy)-2-pyrimidin-2-yl-1,2,4-triazol-3-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide.

[0673] LCMS: R t 1.07, m / z=497(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0674] 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,CHF2),6.47(dd,J=8.25,6.79Hz,1H),1.76(d,J=6.60Hz,3H)ppm; 19 F-NMR (377MHz, CDCl3): δ = -61.30 (s, 6F), -86.16 (d, 2F) ppm.

[0675] Example 8: N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl Preparation of [3,5-bis(trifluoromethyl)benzamide (Compound P19)]

[0676]

[0677] Step A: N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfanyl)-1,2,4-triazol-3-yl]ethyl Preparation of [3,5-bis(trifluoromethyl)benzamide (P20)]

[0678]

[0679] 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 trifluoromethylthiol(2,2-bipyridyl)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. The crude material was purified first by flash chromatography on silica gel (ethyl acetate in cyclohexane) and then by reverse phase chromatography (acetonitrile in water) to give 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.

[0680] LCMS: R t 1.15, m / z=545(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0681] 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, CDCl3): δ=-39.77 (s, 3F), -63.02 (s, 6F).

[0682] Step B: N-methyl-N-[1-[2-pyrimidin-2-yl-5-(trifluoromethylsulfonyl)-1,2,4-triazol-3-yl]ethyl Preparation of [3,5-bis(trifluoromethyl)benzamide (Compound P19)]

[0683]

[0684] 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-chloroperoxybenzoic 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 a saturated aqueous solution of sodium bicarbonate. 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 obtain 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.

[0685] LCMS: R t 1.17, m / z=577 (M+H + ).

[0686] Example 9: N-[(1S)-1-[2-pyrimidin-2-yl-5-(trifluoromethoxy)-1,2,4-triazol-3-yl]ethyl]-3, Preparation of 5-bis(trifluoromethyl)benzamide (Compound P23)

[0687]

[0688] 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 were added 1-(trifluoromethoxy)pyridine-4-carbonitrile; 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonamide (0.200 g, 0.424 mmol) and tris(2,2'-bipyridyl)ruthenium(II)hexafluorophosphate (0.018 g, 0.021 mmol). The reaction mixture was stirred at room temperature for 2 hours under irradiation with 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.

[0689] LCMS: R t 1.10, m / z=515(M+H + ); 1 H-NMR (400MHz, CDCl3):

[0690] 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.

[0691] Table P: Examples of compounds of formula I

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698]

[0699]

[0700]

[0701]

[0702] Table I: Intermediate Table:

[0703]

[0704]

[0705] By adding other insecticides, acaricides and / or fungicidal active ingredients, the activity of the composition according to the present invention can be significantly widened and adapted to prevailing conditions. Mixtures of compounds of Formula I with other insecticides, acaricides and / or fungicidal active ingredients can also have other unexpected advantages, which can also be described as synergistic in a wider sense. For example, better tolerance of plants, reduced phytotoxicity, insects can be controlled at their different developmental stages, or better behavior during their production (e.g., during grinding or mixing, during their storage or during their use).

[0706] Suitable active ingredients to be added here are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenol derivatives, thioureas, juvenile hormones, formamidines, benzophenone derivatives, ureas, pyrrole derivatives, carbamates, pyrethroids, chlorinated hydrocarbons, acylureas, pyridylmethyleneamino derivatives, macrolides, neonicotinoids and Bacillus thuringiensis preparations.

[0707] Preference is given to the following mixtures of a compound of formula I with an active ingredient (wherein the abbreviation "TX" stands for "a compound selected from the group consisting of the compounds defined in Tables A-1 to A-92 and Table P"):

[0708] Adjuvant, the adjuvant is selected from the group consisting of: petroleum (alias) (628) + TX,

[0709] Insect control active substances, the insect control active substances are selected from Abamectin + TX, Acetoquin + TX, Acetamiprid + TX, Acetaminophen + TX, Acynonapyr + TX, Biprofen + TX, Afolan + TX, Coumarin + TX, Allethrin + TX, α-Cypermethrin + TX, Alpha-Cypermethrin + TX, Sulfamycin + TX, Mefenamic Acid + TX, Azofenbrit + TX, Triazoline + TX, Dimethoate + TX, Benzophenone + TX, Benzpyrimoxan + TX , β-cyfluthrin + TX, β-cypermethrin + TX, bifenazate + TX, bifenthrin + TX, binacarb + TX, bio-allethrin + TX, bio-allethrin S)-cyclopentyl isomer + TX, bio-resmethrin + TX, bistrifluan + TX, brofenoxam (Broflanilide) + TX, bromothrin + TX, bromophos-ethyl + TX, buprofezin + TX, butacarb + TX, cadusafos + TX, carbaryl + TX, butacarb + TX, batan + TX,CAS No.: 1472050-04-6+TX, CAS No.: 1632218-00-8+TX, CAS No.: 1808115-49-2+TX, CAS No.: 2032403-97-5+TX, CAS No.: 2044701-44-0+TX, CAS No.: 2128706-05-6+TX, CAS No.: 2249718-27-0+TX, chlorantraniliprole+TX, chlordane+TX, chlorfenapyr+TX, chlorpropamide+TX, chlorfenapyr+TX, chlorfenapyr+TX, chlorfenapyr+TX, clenpyrine+TX, chlorfenapyr+TX, clothianidin+TX, 2-chlorophenyl N-methylcarbamate (CPMC)+TX, benzonitrile+TX, cyantraniliprole+TX , cyclobromofenapyr + TX, pyrethroids + TX, cycloxanil + TX, cytoxanil + TX, cyetpyrafen + TX, cytoxanil (Cyetpyrafen or Etpyrafen) + TX, cyflumetofen + TX, cyhalodiamide + TX, cyhalothrin + TX, cypermethrin + TX, cypermethrin + TX, cyromazine + TX, deltamethrin + TX, cyper ... +TX, vegetable and fruit phosphorus +TX, emamectin +TX, dextromethorphan +TX, ε-momfluorothrin +TX, ε-methofluthrin +TX, cypermethrin +TX, ethion +TX, ethiprole +TX, ethofenprox +TX, etoxazole +TX, fenamiphos +TX, fenfluramide +TX, fenapyr +TX, fenitrothion +TX, fumarate +TX, fenthiocarb +TX, fenoxycarb +TX, cypermethrin +TX, fenpyroxymate +TX, fensulfuron +TX, fenthion +TX, fenthion +TX, cypermethrin +TX, fipronil +TX, flometoquin +TX, flonicamid +TX, pyrimidifen Ester + TX, Fluazaindolizine + TX, Fluazifop + TX, Flubendiamide + TX, Flucythrin + TX, Flucitrinate + TX, Flufenacet + TX, Flucythrin + TX, Fluthiazolin + TX, Flumethrin + TX, Flufenacet + TX, Flupyrimin + TX, Fluralaner + TX, Fluvalinate + TX, Flucitrinate + TX, Flufenacet + TX, Flucythrin + TX, Flumethrin + TX, Flupyrimin + TX, Fluralaner + TX, Fluxametamide + TX, Fosthiazol + TX, γ-Cyhalothrin + TX, Gossyplure,TM+TX, pyramid +TX, chlorfenapyr +TX, halofenprox +TX, Heptafluthrin +TX, hexythiazox +TX, hydrazone +TX, Imicyafos +TX, imidacloprid +TX, imiprodinil +TX, indoxacarb +TX, iodomethane +TX, iprodione +TX, Isocycloseram +TX, Isosulfuron +TX, Ivermectin +TX, κ-bifenthrin +TX, κ-tefluthrin +TX, λ-cyhalothrin +TX, lepidomectin +TX, chlorfenapyr +TX, metaflumizone +TX, metaldehyde +TX, metamifent +TX, methomyl +TX, methoxyfenozide +TX, methoxybenzyl Flumethrin + TX, Metformin + TX, Zikewei + TX, Cypermethrin + TX, Momfluorothrin + TX, Methionin + TX, Nitenpyram + TX, Nithiothiazide + TX, Oxydemeton + TX, Oxamyl + TX, Oxazosufyl + TX, Parathion-ethyl + TX, Permethrin + TX, Phenothrin + TX, Phosphamidon + TX, Piperonyl butoxide + TX, Pirimicarb + TX, Pyrimidophos-ethyl + TX, Polyhedrosis virus + TX, Promethrin + TX, Profenofos + TX, Profenofos + TX, Profluthrin + TX, Propargite + TX, Afenacet + TX, Propoxur + TX, Prothiophos + TX, Protrifenbute + TX, Pyril Pyflubumide + TX, Pymetrozine + TX, Pyraclofos + TX, Pyrafluprole + TX, Pyridaben + TX, Pyridalyl + TX, Pyrifluquinazon + TX, Pyrimethoxam + TX, Pyrimostrobin + TX, Pyrafluprid + TX, Pyriproxyfen + TX, Resmethrin + TX, Sarolaner + TX, Selamectin + TX, Silafluthrin + TX, Spinetoram + TX, Spinosad + TX, Spirodiclofen + TX, Spiromesifen + TX, Spiropyrid + TX, Spiropyrid + TX, Spiropidion + TX, Spirotetramat + TX, Sulfonamidin + TX, Tebufenozide + TX, Tebufenpyrad + TX, Tebupirimiphos + TX, Tefluthrin + TX, Temephos + TX, Tetrachloraniliprole + TX, tetrachlorfon + TX, tetramethrin + TX, tetrafluthrin + TX, acaricide + TX, flucyramid + TX, θ-cypermethrin + TX, thiacloprid + TX, thiamethoxam + TX, thiocarb + TX, thiodicarb + TX, long-lasting carboxylic acid + TX, methyl benzylphos + TX, thiophanate + TX, tioxazafen + TX, tolfenpyrad + TX, toxaphene + TX, tralomethrin + TX, transfluthrin + TX, triazophos + TX, trichlorfon + TX,Chlorpyrifos+TX, trichlorfon+TX, triflumezopyrim+TX, Tyclopyrazoflor+TX, ζ-cypermethrin+TX, seaweed extract and fermentation products derived from sugar acyl+TX, seaweed extract and fermentation products derived from sugar acyl (containing urea+TX, amino acids+TX, potassium and molybdenum, and EDTA-chelated manganese)+TX, seaweed extract and fermented plant products+TX, seaweed extract and fermented plant products (containing plant hormones+TX, vitamins+TX, EDTA-chelated copper+TX, zinc+TX, and iron+TX), azadirachtin+TX, Bacillus aizawai+TX, Bacillus chitinosporus AQ746 (NRRL Accession No. B-21 618)+TX, Bacillus firmus+TX, Bacillus kurstak Kurstaki) + TX, Bacillus mycoides AQ726 (NRRL Accession No. B-21664) + TX, Bacillus pumilus (NRRL Accession No. B-30087) + TX, Bacillus pumilus AQ717 (NRRL Accession No. B-21662) + TX, Bacillus species AQ178 (ATCC Accession No. 53522) + TX, Bacillus species AQ175 (ATCC Accession No. 55608) + TX, Bacillus species AQ177 (ATCC Accession No. 55609) + TX, unspecified Bacillus subtilis + TX, Bacillus subtilis AQ153 (ATCC Accession No. 55614) +TX, Bacillus subtilis AQ30002 (NRRL Accession No. B-50421) +TX, Bacillus subtilis AQ30004 (NRRL Accession No. B-50455) +TX, Bacillus subtilis AQ713 (NRRL Accession No. B-21661) +TX, Bacillus subtilis AQ743 (NRRL Accession No. B-21665) +TX, Bacillus thuringiensis AQ52 (NRRL Accession No. B-21619) +TX, Bacillus thuringiensis BD#32 (NRRL Accession No. B-21530) +TX, Bacillus thuringiensis subsp. Kurstaki BMP 123+TX, Beauveria bassiana+TX, D-limonene+TX, Granulovirus+TX, Harpin+TX, Helicoverpa armigera nuclear polyhedrosis virus+TX, Helicoverpa tatarinowii nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Helicoverpa virescens nuclear polyhedrosis virus+TX, Metarhizium species+TX, Muscodor albus 620 (NRRL registration number 30547)+TX, Muscodor roseus A3-5 (NRRL registration number 30548)+TX, Neem-based products+TX,Paecilomyces fumosorum + TX, Paecilomyces lilacinus + TX, Pasteuria szabalensis + TX, Pasteuria penetranta + TX, Pasteuria mycoides + TX, Pasteuria thornei + TX, Pasteuria thunbergii + TX, p-cymene + TX, Plutella xylostella granulosis virus + TX, Plutella xylostella nuclear polyhedrosis virus + TX, polyhedrosis virus + TX, pyrethrum + TX, QRD 420 (terpenoid blend) + TX, QRD 452 (terpenoid blend) + TX, QRD 460 (terpenoid blend) + TX, Quillaja sapodilla + TX, Rhodococcus sphaeroides AQ719 (NRRL Accession No. B-21663) + TX, Spodoptera frugiperda nuclear polyhedrosis virus + TX, Streptomyces flavus (NRRL Accession No. 30232) + TX, Streptomyces species (NRRL Accession No. B-30145) + TX, terpenoid blend + TX, and Verticillium species,

[0710] an algaecide selected from the group consisting of bethoxazin [CCN] + TX, copper dioctanoate (IUPAC name) (170) + TX, copper sulfate (172) + TX, cybutryne [CCN] + TX, dichlone (1052) + TX, dichlorophen (232) + TX, endoxan (295) + TX, fentin (347) + TX, slaked lime [CCN] + TX, nabam (566) + TX, quinoclamine (714) + TX, quinonamid (1379) + TX, simazine (730) + TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347) + TX,

[0711] An anthelmintic selected from the group consisting of: avermectin (1) + TX, clefonate (1011) + TX, doramectin (alias) [CCN] + TX, emamectin (291) + TX, emamectin benzoate (291) + TX, eprinomectin (alias) [CCN] + TX, ivermectin (alias) [CCN] + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, piperazine [CCN] + TX, selamectin (alias) [CCN] + TX, spinosad (737) and thiophanate (1435) + TX,

[0712] Avicide selected from the group consisting of chloralose (127) + TX, endrin (1122) + TX, fenthion (346) + TX, pyridin-4-amine (IUPAC name) (23) and strychnine (745) + TX,

[0713] Bactericide, the bactericide is selected from the group consisting of: 1-hydroxy-1H-pyridine-2-thione (IUPAC name) (1222) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, 8-hydroxyquinoline sulfate (446) + TX, bronopol (97) + TX, copper dioctanoate (IUPAC name) (170) + TX, copper hydroxide (IUPAC name) (169) + TX, cresol [CCN] + TX, dichlorophen (232) + TX, dipyrithione (1105) + TX, dodesine (1112) + TX, fenaminosulf (1144) + TX, formaldehyde (404) + TX, mercury + Fen (alias) [CCN] + TX, kasugamycin (483) + TX, kasugamycin hydrochloride hydrate (483) + TX, nickel bis(dimethyldithiocarbamate) (IUPAC name) (1308) + TX, nitrapyrin (580) + TX, octhilinone (590) + TX, oxolinic acid (606) + TX, oxytetracycline (611) + TX, potassium hydroxyquinoline sulfate (446) + TX, probenazole (658) + TX, streptomycin (744) + TX, streptomycin sesquisulfate (744) + TX, chlorpheniramine (766) + TX, and thimerosal (alias) [CCN] + TX,

[0714] Biological agent, the biological agent is selected from the group consisting of: GV of cotton brown banded moth (alias) (12) + TX, Radiation-forming soil bacteria (alias) (13) + TX, Amblyseius spp. (alias) (19) + TX, Spodoptera exigua NPV (alias) (28) + TX, Anagrus atomus (alias) (29) + TX, Aphelinus abdominalis (alias) (33) + TX, Aphidius colemani (alias) (34) + TX, Aphidoletes aphidimyza (alias) (35) + TX, Spodoptera exigua NPV (alias) (38) + TX, Bacillus firmus (alias) (48) + TX, Bacillus sphaericus (alias) Neide)(scientific name)(49)+TX、Bacillus thuringiensisBerliner)(scientific name)(51)+TX、Bacillus thuringiensissubsp.aizawai)(scientific name)(51)+TX、Bacillus thuringiensissubsp.israelensis)(scientific name)(51)+TX、Bacillus thuringiensissubsp.japonensis)(scientific name)(51)+TX、Bacillus thuringiensissubsp.kurstaki)(scientific name)(51)+TX、Bacillus thuringiensissubsp.tenebrionis (scientific name) (51) + TX, Beauveria bassiana (alias) (53) + TX, Beauveria brongniartii (alias) (54) + TX, Chrysoperla carnea (alias) (151) + TX, Cryptolaemus montrouzieri (alias) (178) + TX, Codling moth GV (alias) (191) + TX, Dacnusa sibirica (alias) (212) + TX, Diglyphus isaea (alias) (254) + TX, Eretmocerus sibirica (scientific name) (293) + TX, Eretmocerus sibirica (alias) eremicus) (alias) (300) + TX, Spodoptera exigua NPV (alias) (431) + TX, Heterorhabditis bacteriophora and H. megidis (alias) (433) + TX, Hippodamia convergens (alias) (442) + TX, Leptomastix dactylopii (alias) (488) + TX, Macrolophus caliginosus (alias) (491) + TX, Spodoptera exigua NPV (alias) (494) + TX, Metaphycus helvolus (alias) (522) + TX, Metarhizium anisopliae var.acridum)(scientific name)(523)+TX, Metarhizium anisopliae var.anisopliae)(scientific name)(523)+TX, Neodiprion sertifer NPV and Neodiprion sertifer (Neodiprion sertifer) NPV.lecontei)NPV (alias) (575) + TX, Paecilomyces species (alias) (596) + TX, Paecilomyces fumosoroseus (alias) (613) + TX, Phytoseiulus persimilis (alias) (644) + TX, Spodoptera exigua multicapsid nuclear polyhedrosisvirus (scientific name) (741) + TX, Steinernema bibionis (alias) (742) + TX, Steinernema carpocapsae (alias) (742) + TX, Steinernema glaseri (alias) (742) + TX, Steinernema riobrave) (alias) (742) + TX, Steinernema riobravis (alias) (742) + TX, Steinernema capterisci (alias) (742) + TX, Steinernema spp. (alias) (742) + TX, Trichogramma spp. (alias) (826) + TX, Typhlodromus occidentalis (alias) (844) and Verticillium lecanii (alias) (848) + TX,.

[0715] Soil disinfectant selected from the group consisting of iodomethane (IUPAC name) (542) and bromomethane (537) + TX,

[0716] A chemical sterilant selected from the group consisting of: apholanate [CCN] + TX, bis(aziridine) methylaminophosphine sulfide (bisazir) (alias) [CCN] + TX, busulfan (alias) [CCN] + TX, diflubenzuron (250) + TX, dimatif (alias) [CCN] + TX, hemel [CCN] + TX, hempa [CCN] + TX, metepa [CCN] + TX, methiotepa [CCN] + TX, methyl apholanate [CCN] + TX, methyl thiote ... apholate) [CCN] + TX, morzid [CCN] + TX, penfluron (alias) [CCN] + TX, tepa [CCN] + TX, thiohempa (alias) [CCN] + TX, thiohexamethylenetepa (alias) [CCN] + TX, trotamide (alias) [CCN] and urethaneimide (alias) [CCN] + TX,

[0717] Insect pheromone, the insect pheromone is selected from the group consisting of: (E)-dec-5-en-1-yl acetate and (E)-dec-5-en-1-ol (IUPAC name) (222) + TX, (E)-tridec-4-en-1-yl acetate (IUPAC name) (829) + TX, (E)-6-methylhept-2-en-4-ol (IUPAC name) (541) + TX, (E,Z)-tetradec-4,10-dien-1-yl acetate (IUPAC name) (779) + TX, (Z)-dodec-7-en-1-yl acetate (IUPAC name) (285) + TX, (Z)-hexadecan-11-enal (IUPAC name) (436) + TX, (Z)-hexadecan-11-en-1-yl acetate (IUPAC name) (437) +TX, (Z)-hexadec-13-en-11-yn-1-yl acetate (IUPAC name) (438) +TX, (Z)-eicos-13-en-10-one (IUPAC name) (448) +TX, (Z)-tetradec-7-en-1-al (IUPAC name) (782) +TX, (Z)-tetradec-9-en-1-ol (IUPAC name) (783) +TX, (Z)-tetradec-9-en-1-yl acetate (IUPAC name) (784) +TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate (IUPAC name) (283) +TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate (IUPAC name) (780) +TX, (9Z,12E)-tetradec-9,12-Dien-1-yl acetate (IUPAC name) (781) + TX, 14-methyloctadec-1-ene (IUPAC name) (545) + TX, 4-methylnonan-5-ol and 4-methylnonan-5-one (IUPAC name) (544) + TX, alpha-multistriatin (alias) [CCN] + TX, western pine beetle gathering pheromone (brevicomin) (alias) [CCN] + TX, codlelure (alias) [CCN] + TX, codlemon mone)(alias)(167)+TX、cuelure)(alias)(179)+TX、disparlure)(277)+TX、1-dodecane-8-en-1-yl acetate(IUPAC name)(286)+TX、1-dodecane-9-en-1-yl acetate(IUPAC name)(287)+TX、10-10-dien-1-yl acetate(IUPAC name)(284)+TX、dominicalure(alias)[CCN]+TX、ethyl 4-methyloctanoate(IUPAC name) C name) (317) + TX, eugenol (alias) [CCN] + TX, southern pine beetle gathering pheromone (frontalin) (alias) [CCN] + TX, gossyplure (alias) (420) + TX, grandlure (421) + TX, grandlure I (alias) (421) + TX, grandlure II (alias) (421) + TX, grandlure III (alias) (421) + TX, grandlure IV (alias) (421) + TX, hexalure )[CCN]+TX、ipsdienol(alias)[CCN]+TX、ipsenol(alias)[CCN]+TX、japonilure(alias)(481)+TX、lineatin(alias)[CCN]+TX、litlure(alias)[CCN]+TX、looplure(alias)[CCN]+TX、medlure[CCN]+TX、megatomoic acid(alias)[CCN]+TX、methyl eugenol(alias)(540)+TX、muscalure(563)+TX、octadeca-2,13-dien-1-yl acetate(IUPAC name)(588)+TX、octadeca-3,13-Dien-1-yl acetate (IUPAC name) (589) + TX, orfralure (alias) [CCN] + TX, oryctalure (alias) (317) + TX, ostramone (alias) [CCN] + TX, siglure [CCN] + TX, sordidin (alias) (736) + TX, sulcatol )(Other name)[CCN]+TX, tetradec-11-en-1-yl acetate (IUPAC name) (785)+TX, Mediterranean fruit fly attractant (839)+TX, Mediterranean fruit fly attractant A (Other name) (839)+TX, Mediterranean fruit fly attractant B1 (Other name) (839)+TX, Mediterranean fruit fly attractant B2 (Other name) (839)+TX, Mediterranean fruit fly attractant C (Other name) (839) and trunc-call (Other name)[CCN]+TX,

[0718] An insect repellent selected from the group consisting of 2-(octylthio)ethanol (IUPAC name) (591) + TX, butopyronoxyl (933) + TX, butoxy(polypropylene glycol) (936) + TX, dibutyl adipate (IUPAC name) (1046) + TX, dibutyl phthalate (1047) + TX, dibutyl succinate (IUPAC name) (1048) + TX, DEET [CCN] + TX, dimethyl carbate) [CCN] + TX, dimethyl phthalate [CCN] + TX, ethyl hexanediol (1137) + TX, hexylurea [CCN] + TX, methoquin-butyl (1276) + TX, methyl neodecylamide [CCN] + TX, oxamate [CCN] and picaridin [CCN] + TX,

[0719] Molluscicide selected from the group consisting of: di(tributyltin) oxide (IUPAC name) (913) + TX, bromoacetamide [CCN] + TX, calcium arsenate [CCN] + TX, cloethocarb (999) + TX, copper acetyl arsenite [CCN] + TX, copper sulfate (172) + TX, triphenyltin (347) + TX, iron phosphate (IUPAC name) (352) + TX, metaldehyde (518) + TX, methiocarb (530) + TX, niclosamide (576) + TX, niclosamide-ethanolamine (57 6)+TX, pentachlorophenol (623)+TX, sodium pentachlorophenoxide (623)+TX, tazimcarb (1412)+TX, thiodicarb (799)+TX, tributyltin oxide (913)+TX, trifenmorph (1454)+TX, trimethacarb (840)+TX, triphenyltin acetate (IUPAC name) (347) and triphenyltin hydroxide (IUPAC name) (347)+TX, pyriprole [394730-71-3]+TX,

[0720] A nematicide selected from the group consisting of: AKD-3088 (compound code) + TX, 1,2-dibromo-3-chloropropane (IUPAC / Chemical Abstracts name) (1045) + TX, 1,2-dichloropropane (IUPAC / Chemical Abstracts name) (1062) + TX, 1,2-dichloropropane and 1,3-dichloropropene (IUPAC name) (1063) + TX, 1,3-dichloropropene (233) + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide (IUPAC / Chemical Abstracts name) Abstract name) (1065) + TX, 3-(4-chlorophenyl)-5-methylrhodanine (IUPAC name) (980) + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid (IUPAC name) (1286) + TX, 6-isopentenylaminopurine (alias) (210) + TX, avermectin (1) + TX, acetofenamide [CCN] + TX, cotton bell carb (15) + TX, aldicarb (16) + TX, aldicarb (863) + TX, AZ60541 (compound code) + TX, benclothiazol [CCN] + TX, benomyl (62) + TX, butylpyridabenz (alias) + TX, cadastrephos (109) + TX, carbofuran (118) + TX, carbon disulfide (945) + TX, carbosulfan (119) + TX, chloropicrin (141) + TX, chlorpyrifos (145) + TX, chlorpyrifos (999) + TX, cytokinin (alias) (210) + TX 、Dazomethane (216) + TX、DBCP (1045) + TX、DCIP (218) + TX、diamidafos (1044) + TX、diclofos (1051) + TX、dicliphos (alias) + TX、dimethoate (262) + TX、doramectin (alias) [CCN] + TX、emamectin (291) + TX、emamectin benzoate (291) + TX、eprinomectin (alias) [CCN] + TX、ethoxyphos (312) + TX, ethylene dibromide (316) + TX, chlorpyrifos (326) + TX, fenpyrad (alias) + TX, fenthiophos (1158) + TX, thiazolin (408) + TX, butythiophos (1196) + TX, furfural (alias) [CCN] + TX, GY-81 (development code) (423) + TX, thiophene [CCN] + TX, iodomethane (IUPAC name) (542) + TX, isamidofos (1230) + TX , chlorfenapyr (1231) + TX, ivermectin (alias) [CCN] + TX, kinetin (alias) (210) + TX, methyl azomethine (1258) + TX, metamizole (519) + TX, metamizole potassium salt (alias) (519) + TX, metamizole sodium salt (519) + TX, methyl bromide (537) + TX, methyl isothiocyanate (543) + TX, milbemycin oxime (alias) [CCN] + TX, moxidectin (alias) [CCN] + TX, Myrotheciumverrucaria) combination (alias) (565) + TX, NC-184 (compound code) + TX, oxamyl (602) + TX, phorate (636) + TX, phosphamidon (639) + TX, phosphamidon [CCN] + TX, clomiphene (alias) + TX, selamectin (alias) [CCN] + TX, spinosad (737) + TX, terbufos (alias) + TX, terbufos (773) + TX, tetrachlorothiophene (I UPAC / Chemical Abstracts Name) (1422) + TX, thiafenox (alias) + TX, thiophos (1434) + TX, triazophos (820) + TX, triazocarb (alias) + TX, dimethylol [CCN] + TX, YI-5302 (compound code) and zeatin (alias) (210) + TX, fluensulfone [318290-98-1] + TX, fluopyram + TX

[0721] A nitrification inhibitor selected from the group consisting of potassium ethylxanthate [CCN] and nitrapyrin (580) + TX,

[0722] A plant activator selected from the group consisting of acibenzolar (6) + TX, acibenzolar-S-methyl (6) + TX, probenazole (658) and Reynoutria sachalinensis extract (alias) (720) + TX,

[0723] Rodenticide, the rodenticide is selected from the group consisting of: 2-isovaleryl indane-1,3-dione (IUPAC name) (1246) + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide (IUPAC name) (748) + TX, α-chlorohydrin [CCN] + TX, aluminum phosphide (640) + TX, antoconazole (880) + TX, arsenic trioxide (882) + TX, barium carbonate (891) + TX, dithiocarbamide (912) + TX, brodifacoum (89) + TX, bromodisulfuron (89) + TX, Diclofenac (91) + TX, Bromodimethalin (92) + TX, Calcium Cyanide (444) + TX, Chloralose (127) + TX, Chlorodipine (140) + TX, Cholecalciferol (alias) (850) + TX, Chlorodimethalin (1004) + TX, Cholecalciferol (1005) + TX, Cytodextrin (175) + TX, Cytodextrin (1009) + TX, Cytodextrin (246) + TX, Cytodextrin (249) + TX, Diclofenac (273) + TX, Calcifedol (301) + TX, Fluorine Felocell (357) + TX, fluoroacetamide (379) + TX, flufenacet (1183) + TX, flufenacet 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, fosfomycin (1318) + TX, fosfomycin (13 36)+TX, phosphine (IUPAC name) (640)+TX, phosphorus [CCN]+TX, warfarin (1341)+TX, potassium arsenite [CCN]+TX, warfarin (1371)+TX, scilla glycoside (1390)+TX, sodium arsenite [CCN]+TX, sodium cyanide (444)+TX, sodium fluoroacetate (735)+TX, strychnine (745)+TX, thallium sulfate [CCN]+TX, warfarin (851) and zinc phosphide (640)+TX,

[0724] A synergist selected from the group consisting of 2-(2-butoxyethoxy)ethyl piperate (IUPAC name) (934) + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone (IUPAC name) (903) + TX, farnesol with nerolidol (alias) (324) + TX, MB-599 (research code) (498) + TX, MGK264 (research code) (296) + TX, piperonyl butoxide (649) + TX, piprotal (1343) + TX, propyl isomer (1358) + TX, S421 (research code) (724) + TX, sesamex (1393) + TX, sesasmolin (1394) and sulfoxide (1406) + TX,

[0725] An animal repellent selected from the group consisting of anthraquinone (32) + TX, chloralose (127) + TX, copper cyclohexane [CCN] + TX, copper oxychloride (171) + TX, diazinon (227) + TX, dicyclopentadiene (chemical name) (1069) + TX, guazatine (422) + TX, guazatine acetate (422) + TX, methiocarb (530) + TX, pyridin-4-amine (IUPAC name) (23) + TX, salamine (804) + TX, trimethacarb (840) + TX, zinc cyclohexane [CCN] and ziram (856) + TX,

[0726] A virucide selected from the group consisting of: imipenem (also known as CCN) and ribavirin (also known as CCN) + TX,

[0727] A wound protective agent selected from the group consisting of mercuric oxide (512) + TX, octhilinone (590) and thiophanate-methyl (802) + TX,

[0728] Biologically active substances, the biologically active substances are selected from 1,1-bis(4-chlorophenyl)-2-ethoxyethanol+TX, 2,4-dichlorophenylbenzenesulfonate+TX, 2-fluoro-N-methyl-N-1-naphthylacetamide+TX, 4-chlorophenylphenyl sulfone+TX, acetofenapyr+TX, aldicarb+TX, sagofos+TX, fomanphos+TX, amitriptyline+TX, amitriptyline hydrogen oxalate+TX, amitraz+TX, cypermethrin+TX, arsenic trioxide+TX, azobenzene+TX, azophos+TX, benomyl+TX, benoxafos+TX, benzyl benzoate+TX, bixafenthion+TX, bromethrin+TX, bromothiophene+TX, bromophos +TX, bromopyralid +TX, buprofen +TX, butamethoxam +TX, butamethoxam +TX, butylpyridaben +TX, calcium polysulfide +TX, octachlorocamphene +TX, chlormethoxam +TX, trithion +TX, cypermethrin +TX, cypermethrin +TX, cypermethrin +TX, chlordimeform +TX, chlordimeform hydrochloride +TX, chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, dimethoate +TX, ethyl chlorfenapyr +TX, chlormebuform (chloromebuform) +TX, chlorfenapyr +TX, propyl chlorfenapyr +TX, chlorfenapyr +TX, chlorfenapyr +TX, guaiac I +TX, guaiac II +TX, guaiac +TX, closantel +TX, coumaphos +TX, crotamiton +TX, Toxop+TX, Thiamin+TX, Fructofos+TX, DCPM+TX, DDT+TX, Dinophos+TX, Dinophos-O+TX, Dinophos-S+TX, Demeton-methyl+TX, Demeton-O+TX, Demeton-O-methyl+TX, Demeton-S+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Demeton-S-methyl+TX, Dimethoate+TX, Dichlorvos+TX, Dichlorvos+TX, Dichlorvos+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate+TX, Dimethoate-4+TX, Dimethoate -6+TX, anthelmintic+TX, nitropentyl+TX, nitrobenzene acaricide+TX, nitrobutyl+TX, dithiophos+TX, sulfodiphenyl+TX, disulfiram+TX, DNOC+TX, dofenapyn+TX, doramectin+TX, fenoxaphos+TX, eprinomectin+TX, thiophos+TX, ethiprox+TX, anti-mite+TX, fenbutatin+TX, fenthiocarb+TX, fenpyrad+TX, fenpyroximate+TX, anthracene+TX, fentrifanil+TX, fluazifop+TX, flufenoxuron+TX, diflubenzuron+TX, fluazifop+TX, FMC 1137+TX, fluazifop+TX, fluazifop hydrochloride+TX, formparanate+TX, γ-HCH+TX, fruit green +TX,Benzylfen + TX, hexadecylcyclopropanecarboxylate + TX, isocarbophos + TX, jasmonate I + TX, jasmonate II + TX, iodonium + TX, lindane + TX, propanil + TX, cypermethrin + TX, dithiophos + TX, methylthiophene + TX, cypermethrin + TX, methylbromide + TX, methicillin + TX, chlorpyrifos + TX, milbemycin + TX, propylamine + TX, monocrotophos + TX, maoguo + TX, moxidectin + TX, naled + TX, 4-chloro-2-(2-chloro-2-methyl-propyl)-5-[(6-iodo-3-pyridyl)methoxy]pyridazin-3-one + TX, fluazifop + TX, nikkomycin + TX, penbufenac + TX, penbufenac 1:1 zinc chloride complex +TX, omethoate +TX, isothiophos +TX, sulfone +TX, pp'-DDT +TX, parathion +TX, permethrin +TX, fenthion +TX, phosalone +TX, thiophanate +TX, phosphamidon +TX, polychloroterpenes +TX, polynactins +TX, prochlorperazine +TX, cypermethrin +TX, propoxur +TX, ethidium +TX, pyrethrin I +TX, pyrethrin II +TX, pyrethrin +TX, pyrimethanthiophos +TX, pyrimithiophos +TX, quinalphos +TX, quintiofos +TX, R-1 492+TX, glyphosate+TX, rotenone+TX, octamidine+TX, clomartin+TX, selamectin+TX, threon+TX, SSI-121+TX, sulfilam+TX, sulfluramid+TX, sulfotep+TX, sulfur+TX, fluazifop+TX, τ-fluvalinate+TX, TEPP+TX, terbucarb+TX, tetrachlorvinphos+TX, thiafenox+TX, thiafenox+TX, pyrimidine+TX, long-lasting cypermethrin+TX, methyl sulfophos+TX, chlorpyrifos+TX, thiamethoxam ... TX, vaniliprole + TX, bethoxazin + TX, copper dioctanoate + TX, copper sulfate + TX, cybutryne + TX, dichloronaphthoquinone + TX, dichlorophen + TX, endoxan + TX, triphenyltin + TX, slaked lime + TX, sodium mancozeb + TX, quinone + TX, quinone + TX, simazine + TX, triphenyltin acetate + TX, triphenyltin hydroxide + TX, fusulin + TX, piperazine + TX, thiophanate + TX, chloralose + TX, fenthion + TX, pyridin-4-amine + TX, strychnine + TX, 1-hydroxy-1H-pyridine-2-thione + TX, 4-(quinoxalin-2-ylamino)benzenesulfonamide + TX,8-Hydroxyquinoline sulfate + TX, bronopol + TX, copper hydroxide + TX, cresol + TX, dispyrithione + TX, dodesine + TX, sodium disulfide + TX, formaldehyde + TX, mercurophen + TX, kasugamycin + TX, kasugamycin hydrochloride hydrate + TX, nickel bis(dimethyldithiocarbamate) + TX, trichloromethylpyridine + TX, octhilone + TX, oxolinic acid + TX, oxytetracycline + TX, potassium hydroxyquinoline sulfate + TX, thiabendazole + TX, streptomycin + TX, streptomycin sesquisulfate + TX, chlorothiazol + TX, thimerosal + TX, cotton brown-banded tormenter GV + TX, Agrobacterium radiobacterium + TX, Amblyseius spp. + TX, celery budworm NPV + TX, Anagrus atomus + TX, Aphelinus abdominalis + TX, cotton aphid parasitoid (Aphidius colemani+TX, Aphidoletes aphidimyza+TX, Spodoptera alfalfa NPV+TX, Bacillus sphaericus Neide+TX, Beauveria brongniartii+TX, Chrysoperla carnea+TX, Cryptolaemus montrouzieri+TX, Codling moth GV+TX, Dacnusasibirica+TX, Diglyphus isaea+TX, Eretmocerus eremicus+TX, Heterorhabditis bacteriophora and H.megidis+TX, Hippodamia convergens)+TX, citrus powdery scale parasitoid (Leptomastix dactylopii)+TX, blind bug (Macrolophus caliginosus)+TX, cabbage looper NPV+TX, yellow broad-stalked jumping wasp (Metaphycus helvolus)+TX, yellow green green anisopliae (Metarhizium anisopliae var. acridum)+TX, scarab green anisopliae microspore variant (Metarhizium anisopliae var. anisopliae)+TX, European new pine sawfly (Neodiprion sertifer) NPV and red-headed new pine sawfly (N. lecontei) NPV+TX, small flower stink bug species+TX,Paecilomyces fumosoroseus+TX, Phytoseiulus persimilis+TX, Steinernema bibionis+TX, Steinernema carpocapsae+TX, Steinernema glaseri+TX, Steinernema riobrave+TX, Steinernema riobravis+TX, Steinernema scapterisci+TX, Steinernema spp.+TX, Trichogramma species+TX, Typhlodromus occidentalis)+TX, Verticillium lecanii+TX, apholonate+TX, bis(aziridine) methylaminophosphine sulfide (bisazir)+TX, busulfan+TX, dimatif+TX, hemelamine+TX, hempa+TX, metepa+TX, methiotepa+TX, methyl apholonate Apholate) + TX, Morzid + TX, Penfluron + TX, Tepa + TX, Thiohempa + TX, Thiohempa + TX, Tritamide + TX, Urethaneimine + TX, (E)-Deca-5-en-1-yl acetate and (E)-Deca-5-en-1-ol + TX, (E)-Tridec-4-en-1-yl acetate + TX, (E)-6-Methylhept-2-en-4-ol + TX, (E,Z)-Tetradec-4,10-dien-1-yl acetate + TX, (Z)-Dodec-7-en-1-yl acetate + TX, (Z)-Hexadec-11-enal + TX, (Z)-hexadec-11-en-1-yl acetate + TX, (Z)-hexadec-13-en-11-yn-1-yl acetate + TX, (Z)-eicos-13-en-10-one + TX, (Z)-tetradec-7-en-1-al + TX, (Z)-tetradec-9-en-1-ol + TX, (Z)-tetradec-9-en-1-yl acetate + TX, (7E,9Z)-dodec-7,9-dien-1-yl acetate + TX, (9Z,11E)-tetradec-9,11-dien-1-yl acetate + TX, (9Z,12E)-tetradec-9,12-dien-1-yl acetate + TX, 14-methyloctadec-1-ene + TX,4-Methylnonan-5-ol and 4-methylnonan-5-one + TX, α-polystyrene + TX, western pine beetle gathering pheromone + TX, codlelure + TX, codlemone + TX, cuelure + TX, epoxy nonadecane + 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, southern pine beetle gathering pheromone (frontalin )+TX, grandlure+TX, grandlure mixture I+TX, grandlure mixture II+TX, grandlure mixture III+TX, grandlure mixture IV+TX, hexalure+TX, ipsdienol+TX, ipsenol+TX, japonilure+TX, lineatin+TX, litlure+TX, looplure+TX, medlure+TX, megatomoic acid+TX, methyl eugenol) + TX, muscalure + TX, octadec-2,13-dien-1-yl acetate + TX, octadec-3,13-dien-1-yl acetate + TX, orfralure + TX, oryctalure + TX, ostramone + TX, siglure + TX, sordidin + TX, sulcatol + TX, tetradec-11-en-1-yl acetate Ester + TX, Mediterranean fruit fly attractant (trimedlure) + TX, Mediterranean fruit fly attractant A + TX, Mediterranean fruit fly attractant B1 + TX, Mediterranean fruit fly attractant B2 + TX, Mediterranean fruit fly attractant C + TX, trunc-call + TX, 2-(octylthio)ethanol + TX, butopyronoxyl + TX, butoxy (polypropylene glycol) + TX, dibutyl adipate + TX, dibutyl phthalate + TX, dibutyl succinate + TX, DEET + TX, dimethyl carbate + TX, dimethyl phthalate + TX, ethyl hexanediol + TX, hexamide + TX, methoquin-butyl + TX, methylneodecanamide + TX, oxamate + TX,Picaridin + TX, 1-dichloro-1-nitroethane + TX, 1,1-dichloro-2,2-di(4-ethylphenyl)ethane + TX, 1,2-dichloropropane and 1,3-dichloropropylene + TX, 1-bromo-2-chloroethane + TX, 2,2,2-trichloro-1-(3,4-dichlorophenyl)ethyl acetate + TX, 2,2-dichlorovinyl 2-ethylsulfinylethyl methyl phosphate + TX, 2-(1,3-dithiolan-2-yl)phenyl dimethylcarbamate + TX, 2-(2-butoxyethoxy)ethyl thiocyanate + TX, 2-(4,5-dimethyl-1,3-dioxolan-2-yl)phenylmethylcarbamate + TX, 2-(4-chloro-3, 5-xylyloxy)ethanol+TX, 2-chlorovinyl diethyl phosphate+TX, 2-imidazolidinone+TX, 2-isovaleryl indane-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-phenylpyrazol-5-yldimethylcarbamate+TX, 4-methyl(prop-2-ynyl)amino-3,5-xylylmethylcarbamate+TX, 5,5-dimethyl-3-oxocyclohex-1-enyldimethylcarbamate+TX, acethion+TX, acrylonitrile+TX, aldrin+TX, alomycin+TX, chlorpyrifos+TX, α-decaprylamide Chemical + TX, aluminum phosphide + TX, cypermethrin + TX, neonicotinoid + TX, ethyl methidathion + TX, methyl pyrifos + TX, Bacillus thuringiensis δ-endotoxin + TX, barium hexafluorosilicate + TX, barium polysulfide + TX, cypermethrin + TX, Bayer 22 / 190 + TX, Bayer 22408 + TX, β-cyfluthrin + TX, β-cypermethrin + TX, bioethanomethrin + TX, biopermethrin + TX, bis(2-chloroethyl) ether + TX, borax + TX, bromopheniramine + TX, bromo-DDT + TX, hexacarb + TX, cypermethrin + TX, butathiofos + TX, Butyl phosphate + TX, calcium arsenate + TX, calcium cyanide + TX, carbon disulfide + TX, carbon tetrachloride + TX, badan hydrochloride + TX, cevadine + TX, bornyl + TX, chlordane + TX, chlordecone + TX, chloroform + TX, chloropicrin + TX, chloraniloxime + TX, chlorprazophos + TX, cis-resmethrin + TX, cis-resmethrin + TX, clocythrin (alias) + TX, copper acetylarensite + TX, copper arsenate + TX, copper oleate + TX, coumithoate + TX, cryolite + TX,CS 708+TX, benzonitrile+TX, cypermethrin+TX, cypermethrin+TX, cypermethrin+TX, d-methrin+TX, DAEP+TX, dazomethon+TX, decarbofuran+TX, diamidafos+TX, isochlorvinphos+TX, dimethophos+TX, dicresyl+TX, cypermethrin+TX, dieldrin+TX, diethyl 5-methylpyrazol-3-yl phosphate+TX, dior+TX, tetrafluthrin+TX, demaquinetosulfuron+TX, pyrethrin+TX, methylchlorfenapyr+TX, difenocarb+TX, propanol+TX, pentotropol+TX, dinoseb+TX, fenpyroxene+TX, vesiculophos+TX, thiopyrafos+TX, DSP+TX, ecdysterone+TX, EI 1642+TX, EMPC+TX, EPBP+TX, etaphos+TX, ethiobencarb+TX, ethyl formate+TX, dibromoethane+TX, dichloroethane+TX, ethylene oxide+TX, EXD+TX, ethiobencarb+TX, fenitrothion+TX, fenoxacrim+TX, cypermethrin+TX, fenthion+TX, ethylfenthion+TX, flucofuron+TX, butylfenthion+TX, phosphamidon +TX, butanethion+TX, furathiocarb+TX, pyrethroid+TX, biguanide salt+TX, biguanide acetate+TX, sodium tetrathiocarbonate+TX, halfenprox+TX, HCH+TX, HEOD+TX, heptachlor+TX, cypermethrin+TX, HHDN+TX, hydrogen cyanide+TX, quinolincarb+TX, IPSP+TX, chlorfenapyr+TX, carbofuran+TX, isodrin+TX, isofenphos+TX, transplanting spirit+TX, rice blasting spirit+TX, oxathiophos+TX , juvenile hormone I + TX, juvenile hormone II + TX, juvenile hormone III + TX, chlorpentyl + TX, methoprene + TX, lead arsenate + TX, bromophenylphos + TX, acetamiprid + TX, thiamethoxam + TX, m-isopropyl methylcarbamate + TX, magnesium phosphide + TX, phosphazide + TX, methyl azoxystrobin + TX, thiamethoxam + TX, mercurous chloride + TX, methyl sulfoxide + TX, metamizole + TX, metamizole potassium salt + TX, metamizole sodium salt + TX, methylsulfonyl fluoride + TX, butylphos + TX, methoxy Prilin + TX, methoxychlor + TX, methoxychlor + TX, methyl isothiocyanate + TX, methyl chloroform + TX, dichloromethane + TX, oxadiazine + TX, mirex + TX, napeptide + TX, naphthalene + TX, NC-170 + TX, nicotine + TX, nicotine sulfate + TX, nithiazine + TX, pronicotine + TX, O-5-dichloro-4-iodophenyl O-ethylethyl phosphonothioate + TX, O,O-diethyl O-4-methyl-2-oxo-2H-benzopyran-7-ylphosphonothioate + TX,O,O-diethyl O-6-methyl-2-propylpyrimidin-4-ylphosphonothioate + TX, O,O,O',O'-tetrapropyl dithiopyrophosphate + TX, oleic acid + TX, p-dichlorobenzene + TX, methyl parathion + TX, pentachlorophenol + TX, pentachlorophenyl laurate + TX, PH 60-38+TX, fenthion+TX, parachlorothion+TX, phosphine+TX, methyl phoxim+TX, methamidophos+TX, polychlorinated dicyclopentadiene isomers+TX, potassium arsenite+TX, potassium thiocyanate+TX, precocious plant I+TX, precocious plant II+TX, precocious plant III+TX, amidopyrimidin+TX, profluthrin+TX, fenvalerate+TX, prothiophos+TX, pyraclostrobin+TX, anti-pyrethroid+TX, quassia extract+TX, quinalphos-methyl+TX, oxazolidinone+TX, iodophos-amide+TX, resmethrin+TX, rotenone+TX, thiamethoxam+TX, ryanodine+TX, Anodine + TX, sabadilla + TX, octamethrin + TX, clostridium + TX, SI-0009 + TX, thiamethoxam + TX, sodium arsenite + TX, sodium cyanide + TX, sodium fluoride + TX, sodium hexafluorosilicate + TX, sodium pentachlorophenol + TX, sodium selenate + TX, sodium thiocyanate + TX, sulcofuron + TX, sulcofuron-sodium + TX, sulfuryl fluoride + TX, thiopromide + TX, tar + TX, thiabendazim + TX, TDE + TX, butylpyrimidinphos + TX, dimethoate + TX, cypermethrin + TX, tetrachlorobenzene Ethane + TX, thiochlorvos + TX, cyclopentane + TX, cyclopentane oxalate + TX, cypermethrin + TX, cypermethrin sodium + TX, tralomethrin + TX, permethrin + TX, trichlormetaphos-3 + TX, chlorpyrifos + TX, cyclohexanil + TX, tolprocarb + TX, chlorpyrifos-butyl + TX, methoprene + TX, veratridine + TX, veratridine + TX, XMC + TX, zetamethrin + TX, zinc phosphide + TX, tolfenphos + TX, and cypermethrin + TX, tetrafluthrin + TX X, bis(tributyltin) oxide + TX, bromoacetamide + TX, ferric phosphate + TX, niclosamide-ethanolamine + TX, tributyltin oxide + TX, pyromorph + TX, snail killer + TX, 1,2-dibromo-3-chloropropane + TX, 1,3-dichloropropylene + TX, 3,4-dichlorotetrahydrothiophene 1,1-dioxide + TX, 3-(4-chlorophenyl)-5-methylrhodanine + TX, 5-methyl-6-thioxo-1,3,5-thiadiazin-3-yl acetic acid + TX, 6-isopentenylaminopurine + TX, benclothiaz + TX, cytokinin + TX, DCIP + TX, furfural + TX,Isamidofos + TX, kinetin + TX, verrucous myristic fungus combination + TX, tetrachlorothiophene + TX, xylenol + TX, zeatin + TX, potassium ethylxanthate + TX, acibenzolar + TX, acibenzolar-S-methyl + TX, Reynoutria sachalinensis extract + TX, α-chlorohydrin + TX, antoclopramide + TX, barium carbonate + TX, bifenthionine + TX, brodifacoum + TX, brodifacoum + TX, brofenthionine + TX, chlorofacitin + TX, cholecalciferol + TX, chlorfenapyr ... Pyridine + TX, flurbiprofen hydrochloride + TX, warfarin + TX, fosfomycin + TX, phosphorus + TX, warfarin + TX, warfarin + TX, scilla glycoside + TX, sodium fluoroacetate + TX, thallium sulfate + TX, warfarin + TX, 2-(2-butoxyethoxy)ethyl piperate + TX, 5-(1,3-benzodioxol-5-yl)-3-hexylcyclohex-2-enone + TX, farnesol with nerolidol + TX, synergistic acetyl ether + TX, MGK 264 + TX, synergistic butoxide + TX, synergistic aldehyde + TX, synergistic ester (propyl isomer)+TX, S421+TX, enhanced powder+TX, sesasmolin+TX, sulfoxide+TX, anthraquinone+TX, copper cyclohexane+TX, copper oxychloride+TX, dicyclopentadiene+TX, salam+TX, zinc cyclohexane+TX, zinc ziram+TX, imipenem+TX, ribavirin+TX, mercuric oxide+TX, thiophanate-methyl+TX, azaconazole+TX, bifenthionol+TX, fuconazole+TX, cyproconazole+TX, difenoconazole+TX, diniconazole+TX, epoxiconazole+TX, fenbuconazole+TX, fluquinconazole+TX, flusilazole+TX, flutriafol+TX, furopyram+TX, hexaconazole+TX, imazalil+TX, imidazole+TX, ipconazole+TX, metconazole+TX, myclobutrazol+TX, paclobutrazol +TX, blastifen +TX, penconazole +TX, prothioconazole +TX, pyrifenox +TX, prochloraz +TX, propiconazole +TX, pyraconazole +TX, simeconazole +TX, tebuconazole +TX, fluconazole +TX, triadimefon +TX, triadimenol +TX, triflumizole +TX, triticonazole +TX, pyrimidine +TX, chlorfenapyr +TX, flufenapyr +TX, bupirimate +TX, dimethirimol +TX, ethirimol +TX, dodecamorph +TX, fenpropidine +TX, fenpropimorph +TX, spiroxamorph +TX, tridecamorph +TX,Cyprodinil + TX, pyraclostrobin + TX, pyrimethanil + TX; fenpiclonil + TX, fludioxonil + TX, benalaxyl + TX, furalaxyl + TX, metalaxyl + TX, R-metalaxyl + TX; furamide + TX; oxadixyl + TX, carbendazim + TX, debacarb + TX, chlorpyrifos + TX, thiabendazole + TX, chlozolinate + TX, dichlozoline + TX, myclozoline + TX, procymidone + TX, Vinclozoline + TX, boscalid + TX, carboxin + TX, furamide + TX, flutolanil + TX, mefenamic acid + TX, oxycarboxin + TX, penthiopyrad + TX, thiofuran + TX, dodine + TX, biguanide + TX, azoxystrobin + TX, enestroburin + TX, enestroburin + TX, flutoxanil + TX, fluoxastrobin + TX, kresoxim-methyl + TX, oxazolidinone + TX, trifloxystrobin + TX, trifloxystrobin + TX, picoxystrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, pyraclostrobin + TX, ferbam + TX, mancozeb + TX, maneb + ​​TX, maneb + ​​TX, maneb + ​​TX, methyl propineb + ​​TX, maneb + ​​TX, captol + TX, captan + TX, pyraclostrobin + TX, folpet + TX, tolylfluanid + TX, Bordeaux mixture + TX, copper oxide + TX, mancozeb + TX, quinoline copper + TX, phthalostrobin + TX, kefansan + TX, pyraclostrobin + TX, chlorpyrifos + TX, tolclofos-methyl + TX, captol + TX, benzathiapiprolin + TX, blasticidin + TX, chloroneb + ​​TX, chlorothalonil + TX, cyfluanid + TX, diclofenac + TX ocymet)+TX, diclomezine+TX, dicloran+TX, diethofencarb+TX, dimethomorph+TX, flumorph+TX, dithianon+TX, ethaboxam+TX, etridiazole+TX, famoxadone+TX, fenamidone+TX, fenoxanil+TX, ferimzone+TX, fluazinam+TX, fluopicolide+TX,Flusulfamide + TX, flupyraclostrobin + TX, fenhexamid + TX, fosetyl-aluminium + TX, hymexazol + TX, propineb + ​​TX, cyazofamid + TX, methasulfocarb + TX, mefenoxam + TX, pencycuron + TX, phthalide + TX, polyoxins + TX, propamocarb + TX, pyrimidine + TX, proquinazid + TX, pyroquilon n)+TX, pyriofenone+TX, quinoxyfen+TX, pentachloronitrobenzene+TX, thiazolamide+TX, triazoxide+TX, tricyclazole+TX, triamcinol+TX, validamycin+TX, valeramide+TX, zoxamide+TX, mandipropamid+TX, isopyrazam+TX, sedaxane+TX, benzovinflumizone+TX, fluopyram+TX, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (3',4',5'-trifluoro-biphenyl-2-yl)-amide +TX, isoflurane+TX, isothiopyram+TX, dipymetitrone+TX, 6-ethyl-5,7-dioxo-pyrrolo[4,5][1,4]dithia[1,2-c]isothiazole-3-carbonitrile+TX, 2-(difluoromethyl)-N-[3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide+TX, 4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile+TX, (R)-3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro- phenyl)-2,5-dimethyl-pyrazol-3-amine+TX, 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine+TX, fluindapyr+TX, Jiaxiangjunzhi+TX, lvbenmixianan+TX, dichlobentiazox+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-quinolinyl)oxy]phenyl]propan-2-ol+TX,Oxathiapiprolin + TX, N-[6-[[[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid tert-butyl ester + TX, pyraziflumid + TX, inpyrfluxam + TX, trolprocarb + TX, clofoconazole + TX, ipfentrifluconazole + TX, 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dimethyl-indan-4-yl]pyridine-3-carboxamide + TX, N'-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[4 -(4,5-dichlorothiazol-2-yl)oxy-2,5-dimethyl-phenyl]-N-ethyl-N-methyl-formamidine + TX, [2-[3-[2-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidinyl]thiazol-4-yl]-4,5-dihydroisoxazol-5-yl]-3-chloro-phenyl] methanesulfonate + TX, N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridinyl]carbamic acid but-3-ynyl ester + TX, N-[[5-[4-(2,4-dimethylphenyl)triazol-2-yl]-2-methyl-phenyl]methyl]carbamic acid methyl + TX, 3-chloro-6-methyl-5- Phenyl-4-(2,4,6-trifluorophenyl)pyridazine+TX, pyridachlometyl+TX, 3-(difluoromethyl)-1-methyl-N-[1,1,3-trimethylindan-4-yl]pyrazole-4-carboxamide+TX, 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one+TX, 1-methyl-4-[3-methyl-2-[[2-methyl-4-(3,4,5-trimethylpyrazol-1-yl)phenoxy]methyl]phenyl]tetrazol-5-one+TX, aminopyrifen+TX, pyraclostrobin+TX, indazolesulfam+TX, fluopicolide+TX, (Z,2E)- 5-[1-(4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine+TX, florylpicoxamid+TX, fenpicoxamid+TX, isobutylethoxyquinoline+TX, ipflufenoquin+TX, quinofumelin+TX, isopropylthiopyrad+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)-1-methyl-pyrazole-4-carboxamide+TX, benzthiopyrad+TX,Cyanostrobin + TX, 5-amino-1,3,4-thiadiazole-2-thiol zinc salt (2:1) + TX, fluopyram + TX, fluthiazolinone + TX, fluopyram + TX, pyrapropoyne + TX, picarbutrazox + TX, 2-(difluoromethyl)-N-(3-ethyl-1,1-dimethyl-indan-4-yl)pyridine-3-carboxamide + TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide + TX, 4-[[6-[2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(1,2,4-triazol-1-yl)-1- )propyl]-3-pyridyl]oxy]benzonitrile+TX, metyltetraprole+TX, 2-(difluoromethyl)-N-((3R)-1,1,3-trimethylindan-4-yl)pyridine-3-carboxamide+TX, α-(1,1-dimethylethyl)-α-[4'-(trifluoromethoxy)[1,1'-diphenyl]-4-yl]-5-pyrimidinemethanol+TX, fluoxapiprolin+TX, enoxastrobin+TX, 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-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile + TX, trinexapac-ethyl + TX, syringostyrin + TX, zhongshengmycin + TX, thiophanate-methyl + TX, zinc thiazole + TX, amectotractin + TX, iprodione + TX, (N-methoxy-N-[[4-[5-(trifluoromethyl) )-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide+TX, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX,3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea+TX, N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide+TX, 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one a mixture of 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one+TX, ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrazole-4-carboxylate+TX, and N,N-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-1,2,4-triazol-3-amine+TX), wherein the compound other than TX in the mixture can be WO 2 2017 / 055473, WO 2017 / 055469, 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 (the 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 (the 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 (the compound can be prepared by the method described in WO2016 / 156290), 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile + TX (the compound can be prepared by the method described in WO 2016 / 156290), 2-amino-6-methyl-pyridine-3-carboxylic acid (4-phenoxyphenyl) methyl ester + TX (the compound can be prepared by the method described in WO 2014 / 006945), 2,6-dimethyl-1H,5H-[1,4]dithia[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone+TX (this compound can be prepared by the method described in WO 2011 / 138281), N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX, N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide+TX,

[0729] (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamine + TX (the compound can be prepared by the method described in WO 2018 / 153707), N'-(2-chloro-5-methyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine + TX, N'-[2-chloro-4-(2-fluorophenoxy)-5-methyl-phenyl]-N-ethyl-N-methyl-formamidine + TX (the compound can 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 (the compound can be prepared by the method described in WO2014 / 095675),

[0730] Microbial agents, including: Acinetobacter lwoffii + TX, Acremonium fungi + TX + TX, Cephalosporium acremonium + TX + TX, Acremonium diospyri + TX, Acremonium obclavatum + TX, and AdoxGV +TX, Agrobacterium radioactive strain K84 +TX, Alternaria +TX, Alternaria cassiae +TX, Alternaria destruens +TX, Powdery mildew +TX, Aspergillus flavus AF36 +TX, Aspergillus flavus NRRL 21882 +TX, Aspergillus species +TX, Aureobasidium pullulans +TX, Azospirillum +TX, ( +TX、TAZO )+TX, nitrogen-fixing bacteria+TX, Azotobacter chroocuccum +TX, nitrogen-fixing bacteria cysts (BionaturalBlooming )+TX, Bacillus amyloliquefaciens+TX, Bacillus cereus+TX, Bacillus chitinosporus strain CM-1+TX, Bacillus chitinosporus strain AQ746+TX, Bacillus licheniformis strain HB-2 (Biostart TM )+TX, Bacillus licheniformis strain 3086 ( +TX、Green )+TX, Bacillus circulans+TX, Bacillus firmus ( +TX、BioNem- +TX, )+TX, Bacillus firmus strain I-1582+TX, Bacillus macerans+TX, Bacillus marismortui+TX, Bacillus megaterium+TX, Bacillus mycoides strain AQ726+TX, Milky Spore )+TX, Bacillus pumilus species+TX, Bacillus pumilus strain GB34 (Yield )+TX, Bacillus pumilus strain AQ717+TX, Bacillus pumilus strain QST 2808( +TX, Ballad )+TX, Bacillus spahericus +TX, Bacillus species +TX, Bacillus species strain AQ175 +TX, Bacillus species strain AQ177 +TX, Bacillus species strain AQ178 +TX, Bacillus subtilis strain QST 713 ( +TX, +TX, )+TX, Bacillus subtilis strain QST 714 +TX, Bacillus subtilis strain AQ153+TX, Bacillus subtilis strain AQ743+TX, Bacillus subtilis strain QST3002+TX, Bacillus subtilis strain QST3004+TX, Bacillus subtilis variant strain FZB24 ( +TX, )+TX, Bacillus thuringiensis Cry 2Ae+TX, Bacillus thuringiensis Cry1Ab+TX, Bacillus thuringiensis Aizawai GC 91 +TX, Bacillus thuringiensis israelensis ( +TX, +TX, )+TX, Bacillus thuringiensis kurstaki ( +TX, +TX, +TX, +TX, Scutella +TX, Turilav +TX, +TX、Dipel +TX, +TX, )+TX, Bacillus thuringiensis Kurstak BMP 123 +TX, Bacillus thuringiensis Kurstak HD-1 (Bioprotec-CAF / )+TX, Bacillus thuringiensis strain BD#32+TX, Bacillus thuringiensis strain AQ52+TX, Bacillus thuringiensis var.aizawai ( +TX, )+TX, bacteria spp. +TX, +TX, )+TX, Clavipactermichiganensis phage +TX, +TX, Beauveria bassiana ( +TX, Brocaril )+TX, Beauveria bassiana GHA (Mycotrol +TX, Mycotrol +TX, )+TX, Beauveria brongniartii ( +TX, Schweizer +TX, )+TX, Beauveria spp.+TX, Botrytis cineria+TX, Bradyrhizobium japonicum +TX, Brevibacillus brevis +TX, Bacillus thuringiensis tenebrionis +TX, BtBooster+TX, Burkholderia cepacia ( +TX, +TX、Blue )+TX, Burkholderiagladii+TX, Burkholderia gladioli+TX, Burkholderia spp.+TX, Canadian thistle fungus (CBH Canadian )+TX, Candida butyri+TX, Candida famata+TX, Candida fructus+TX, Candida glabrata+TX, Candida guilliermondii+TX, Candida melibiosica+TX, Candida oleophila strain O+TX, Candida parapsilosis+TX, Candida pelliculosa+TX, Candida pulcherrima+TX, Candida reukaufii+TX, Candida saitoana( +TX, )+TX, Candida sake+TX, Candida spp.+TX, Candida tenius+TX, Cedecea dravisae+TX, Cellulomonas flavigena+TX, Chaetomium cochliodes +TX, Chaetomium globosum +TX, Chromobacterium subtsugae strain PRAA4-1T +TX, Cladosporium cladosporioides +TX, Cladosporium oxysporum +TX, Cladosporium chlorocephalum +TX, Cladosporium spp. +TX, Cladosporium tenuissimum +TX, Clonostachys rosea +TX, Colletotrichum acutatum +TX, Coniothyrium minitans (Cotans )+TX, Coniothyrium spp.+TX, Cryptococcus albidus +TX, Cryptococcus humicola +TX, Cryptococcus infirmo-miniatus +TX, Cryptococcus laurentii +TX, Cryptophlebia leucotreta granulovirus +TX, Cupriavidus campinensis+TX, Cydia pomonella granulovirus +TX, codling moth granulosis virus ( +TX, Madex +TX, Madex Max / )+TX、Cylindrobasidium laeve +TX, Cylindrocladium +TX, Debaryomyceshansenii +TX, Drechslera hawaiinensis +TX, Enterobacter cloacae +TX, Enterobacteriaceae +TX, Entomophtora virulenta +TX, Epicoccum nigrum +TX, Epicoccum purpurascens +TX, Epicoccum species +TX, Filobasidium floriforme +TX, Fusarium acuminate +TX, Fusarium chrysosporium +TX, Fusarium oxysporum ( / Biofox )+TX, Fusarium spp.+TX, Fusarium spp.+TX, Galactomyces geotrichum+TX, Gliocladium catenulatum ( +TX, )+TX, Gliocladium roseum+TX, Gliocladium species +TX, Gliocladium virens +TX, granulovirus +TX, Halobacillus halophilus +TX, Halobacillus litoralis +TX, Halobacillus trueperi +TX, Halomonas species +TX, Halomonas subglaciescola +TX, Halovibrio variabilis +TX, Hansenula vitis +TX, Helicoverpa armigera nuclear polyhedrosis virus +TX, Spodoptera nucleus polyhedrosis virus +TX, isoflavone-formononetin +TX, Kloeckneria citrifolia +TX, Kloeckneria species +TX, Lagenidium giganteum +TX, Lecanicillium longisporum +TX, Lecanicillium muscarium +TX, Lymantria dispar nuclear polyhedrosis virus +TX, Halococcus halophilus +TX, Meira geulakonigii +TX, Metarhizium anisopliae +TX, Metarhizium anisopliae (Destruxin )+TX, Metschnikowia fruticola +TX, Metschnikowia pulcherrima+TX, Microdochium dimerum +TX, Micromonospora coerulea +TX, Microsphaeropsis ochracea +TX, Muscodor albus 620 +TX, Muscodor roseus strain A3-5+TX, Mycorrhizae spp. ( +TX、Root )+TX, Myrotheca verrucosa strain AARC-0255 +TX、BROS +TX, Ophiostoma piliferum strain D97 +TX, Paecilomyces farinosus +TX, Paecilomyces fumosorum +TX, )+TX, Paecilomyces lilacinus (Biostat )+TX, Paecilomyces lilacinus strain 251 (MeloCon )+TX, Paenibacillus polymyxa+TX, Pantoea agglomerans (BlightBan )+TX, Pantoea species+TX, Pasteurella species +TX, Pasteuria nishizawae+TX, Penicillium chrysogenum+TX, Penicillium billai ( +TX, )+TX, Penicillium breviscompactum+TX, Penicillium spp.+TX, Penicillium chrysogenum+TX, Penicillium purpurogenum+TX, Penicillium species+TX, Penicillium viridiflorum+TX, Phlebiopsis gigantean +TX, phosphate-solubilizing bacteria +TX, Cryptophyton+TX, Phytophthora palmatum +TX, Pichia anomala +TX, Pichia guilermondii +TX, Pichia membranaceus +TX, Pichia nail +TX, Pichia stipitis +TX, Pseudomonas aeruginosa +TX, Pseudomonas aureofasciens (Spot-Less )+TX, Pseudomonas cepacia+TX, Pseudomonas chlororaphis +TX, Pseudomonas corrugate +TX, Pseudomonas fluorescens strain A506 (BlightBan )+TX, Pseudomonas putida+TX, Pseudomonas reactans+TX, Pseudomonas species+TX, Pseudomonas syringae +TX, Pseudomonas aureus +TX, Pseudomonas fluorescens +TX, Pseudozyma flocculosa strain PF-A22 UL (Sporodex )+TX、Puccinia canaliculata+TX、Puccinia thlaspeos(Wood )+TX、Pythium oligandrum+TX、Pythium oligandrum +TX, )+TX, Pythium+TX, Rhanella aquatilis+TX, Rhanella spp.+TX, Rhizobia ( +TX, )+TX, Rhizoctonia+TX, Rhodococcus globerulus strain AQ719+TX, Rhodosporidiumdiobovatum+TX, Rhodosporidium toruloides+TX, Rhodotorula spp.+TX, Rhodotorula glutinis+TX, Rhodotorula graminis+TX, Rhodotorula mucilagnosa+TX, Rhodotorula rubra+TX, Saccharomyces cerevisiae+TX, Salinococcus roseus+TX, Sclerotinia minor+TX, Sclerotinia minor +TX, Scytalidium spp.+TX, Scytalidium uredinicola+TX, Spodoptera exigua nuclear polyhedrosisvirus ( +TX, )+TX, Serratia marcescens+TX, Serratia plymuthica+TX, Serratia spp.+TX, Sordaria fimicola+TX, Spodoptera littoralis nuclear polyhedrovirus +TX, Sporobolomyces roseus +TX, Stenotrophomonas maltophilia +TX, Streptomyces ahygroscopicus +TX, Streptomyces albaduncus +TX, Streptomyces exfoliates +TX, Streptomyces galbus +TX, Streptomyces griseoplanus +TX, Streptomyces griseoviridis +TX, Streptomyces lydicus +TX, Streptomyces lydicus WYEC-108 +TX, Streptomyces violaceus +TX, Tilletiopsis minor +TX, Tilletiopsis spp. +TX, Trichoderma asperellum (T34 )+TX, Trichoderma gamsii +TX, Trichoderma atroviride +TX, Trichoderma hamatum TH 382+TX, Trichoderma harzianum rifai +TX, Trichoderma harzianum T-22 ( +TX, PlantShield +TX, +TX, )+TX, Trichoderma harzianum T-39 +TX, Trichoderma mainhamatum +TX, Trichoderma koningii +TX, Trichoderma spp. LC 52 +TX, Trichoderma lignorum +TX, Trichoderma longibrachiatum +TX, Trichoderma polysporum +TX, Trichoderma taxi +TX, Trichoderma virens +TX, Trichoderma virens (formerly known as Gliocladium virens GL-21) +TX, Trichoderma viride +TX, Trichoderma viride strain ICC 080 +TX, Trichosporon pullulans +TX, Trichosporon spp. +TX, Trichothecium spp. +TX, Trichothecium roseum +TX, Typhula phacorrhiza strain 94670 +TX, Typhula phacorrhiza strain 94671 +TX, Ulocladium atrum +TX, Ulocladium oudemansii +TX, Ustilago maydis +TX, various bacteria and supplemented micronutrients (Natural )+TX, various fungi (Millennium )+TX, Verticillium chlamydosporium+TX, Verticillium lecanii ( +TX, )+TX、Vip3Aa20 +TX, Virgibaclillus marismortui +TX, Xanthomonas campestris pv.Poae +TX, Xenorhabdus burnetii +TX, Xenorhabdus nematophila;

[0731] Plant extracts, including pine oil +TX, Azadirachtin (Plasma Neem +TX, +TX, +TX, +TX, plant IGR ( +TX, )+TX, canola oil (Lilly Miller )+TX, Chenopodium ambrosioides near ambrosioides +TX, chrysanthemum extract +TX, neem oil extract +TX, Labiatae essential oil +TX, clove-rosemary-peppermint and thyme oil extracts (Garden insect )+TX, betaine +TX, garlic +TX, lemongrass oil +TX, neem oil +TX, catnip (Nepeta cataria) (catnip oil) +TX, Nepeta catarina +TX, nicotine +TX, oregano oil +TX, Pedaliaceae oil +TX, Pyrethrum+TX, Soapbark Tree (Quillaja saponaria) +TX, Reynoutria sachalinensis ( +TX, )+TX, rotenone (Eco )+TX, Rutaceae plant extract +TX, soybean oil (Ortho )+TX, tea tree oil (Timorex )+TX, thyme oil+TX, MMF+TX, +TX, Rosemary-Sesame-Peppermint-Thyme and Cinnamon Extract Blend (EF )+TX, clove-rosemary and peppermint extract mixture (EF )+TX, Clove-Peppermint-Garlic Oil and Mint Blend (Soil )+TX, kaolin +TX, storage glucan of brown algae

[0732] Pheromones, including: 3M Sprayable Blackheaded Fireworm )+TX, codling moth pheromone (Paramount dispenser-(CM) / Isomate )+TX, Grape Leaf Roller Pheromone (3MMEC-GBM Sprayable )+TX, leaf roller pheromone (3M MECLR Sprayable )+TX, housefly pheromone (Muscamone)(Snip7Fly +TX、Starbar Premium Fly )+TX, 3M oriental fruit moth sprayable )+TX, Peachtree Borer pheromone +TX, Tomato Pinworm Pheromone (3M Sprayable )+TX, Entostat powder (from palm tree extract) (Exosex )+TX、(E+TX,Z+TX,Z)-3+TX,8+TX,11-tetradecatriene acetate+TX、(Z+TX,Z+TX,E)-7+TX,11+TX,13-hexadecatrienal+TX、(E+TX,Z)-7+TX,9-dodecadien-1-yl acetate+TX、2-methyl-1-butanol+TX、calcium acetate+TX、 +TX, +TX, +TX, Lavandulyl senecioate;

[0733] Macrobial agents, including: Aphidius ervi + TX, Aphidius ervi +TX, Acerophagus papaya+TX, Coccinella bispot +TX, Coccinella bispotata +TX, Coccinella bispotata +TX, Ageniaspis citricola+TX, Amblyseius andersoni ( +TX, )+TX, Amblyseius californicus ( +TX, )+TX, Amblyseius cucumber mite ( +TX, Bugline )+TX, Pseudo-Amblyseius +TX, Bugline +TX, )+TX, Amblyseius osbornei +TX, Amitus hesperidum +TX, Anagrus atomus +TX, Anagyrus fusciventris +TX, Anagyrus kamali +TX, Anagyrus loecki +TX, Anagyrus pseudococci +TX, Red wax scale flat-horned jumping wasp (Anicetus benefices) +TX, Golden wasp (Anisopteromalus calandrae) +TX, Woodland flower stink bug (Anthocoris nemoralis) +TX, Short-spur Aphid Wasp ( +TX, )+TX, Aphelinus asychis+TX, Aphidius colemani +TX, Alphididae +TX, tobacco aphid wasp+TX, peach red aphid wasp +TX, aphid-eating gall midge +TX, aphid-eating gall midge +TX, Lingnan yellow aphid wasp +TX, Indian yellow aphid wasp +TX, Aprostocetus hagenowii +TX, Atheta coriaria +TX, Bombus species +TX, European bumblebee (Natupol )+TX, European Bumblebee ( +TX, )+TX, Cephalonomiastephanoderis+TX, Black-backed Ladybird (Chilocorus nigritus)+TX, Common Lacewing (Chrysoperlacarnea) +TX, Common Lacewing +TX, Chrysoperlarufilabris+TX, Cirrospilus ingenuus+TX, Cirrospilusquadristriatus+TX, Citrostichus phyllocnistoides+TX, Closterocerus chamaeleon+TX, Closterocerus species+TX, Coccidoxenoides perminutus +TX, Coccophagus cowperi+TX, Coccophagus lycimnia+TX, Coccophagus lutescens+TX, Coccophagus rapae+TX, Coccophagus moniliformis+TX, Coccophagus spp. +TX, )+TX、Japanese square-headed beetle+TX、Siberian jawed braconid wasp+TX、Siberian jawed braconid wasp +TX, Pea leafminer +TX, small black ladybug (Delphastuscatalinae) +TX, Delphastus pusillus+TX, Diachasmimorpha krausii+TX, Long-tailed fly miner+TX, Diaparsis jucunda+TX, Diaphorencyrtusaligarhensis+TX, Pea leafminer+TX, Pea leafminer +TX, )+TX, Siberian Braconid Wasp ( +TX, )+TX、Species of the genus Encarsia+TX、Aphididae+TX、Encarsiae +TX, +TX, )+TX, Eretmocerus eremicus +TX, Encarsia guadeloupae +TX, Encarsia haitiensis +TX, Slender Hoverfly +TX, Eretmoceris siphonini+TX, Eretmoceruscalifornicus+TX, Eretmocerus eremicus( +TX, Eretline )+TX, Eretmocerus eremicus +TX, Heinrich's aphid wasp+TX, Monterey's aphid wasp ( +TX, Eretline )+TX, Eretmocerus siphonini+TX, Four-spotted Ladybird (Exochomus quadripustulatus)+TX, Feltiella acarisuga +TX, Acarina +TX, Alishan fly miner +TX, Fopiusceratitivorus +TX, Wirless )+TX, thrips slender waist +TX, Galendromus occidentalis +TX, Goniozus legneri +TX, Echinops serratus +TX, Harmonia axyridis +TX, Heterorhabditis species (Lawn )+TX, Heterorhabditis elegans (NemaShield +TX, +TX, +TX, +TX, +TX, +TX, +TX, )+TX, Heterorhabditis megidis (Nemasys +TX, BioNem +TX、Exhibitline +TX, )+TX, Hippodamia convergens+TX, Hypoaspis aculeifer ( +TX, )+TX、Hypoaspis miles(Hypoline +TX, )+TX, black branch gall wasp+TX, Lecanoideus floccissimus+TX, Lemophagus errabundus+TX, tri-colored beautiful jumping wasp (Leptomastidea abnormis)+TX, orange flour scale parasitic wasp (Leptomastix dactylopii) +TX, Leptomastix epona+TX, Lindorus lophanthae+TX, Lipolexis oregmae+TX, Greenfly +TX, tea-footed aphid wasp+TX, blind bug (Macrolophus caliginosus) ( +TX、Macroline +TX, )+TX, Mesoseiulus longipes+TX, Metaphycus flavus+TX, Metaphycus lounsburyi+TX, and Metaphycus hornbeam +TX, Microterys flavus +TX, Muscidifuraxraptorellus and Spalangia cameroni +TX, Neodryinus typhlocybae+TX, Neodryinus californicus+TX, Neodryinus typhlocybae cucumber +TX, Neoseiulus fallacis+TX, Nesideocoris tenuis( +TX, )+TX, Bronze Blackfly +TX, Orius insidiosus( +TX, Oriline )+TX, Orius laevigatus ( +TX, Oriline )+TX、Oriline )+TX, small black flower stink bug +TX, Pauesia juniperorum+TX, Pediobius foveolatus+TX, Phasmarhabditis hermaphrodita +TX, Phymastichus coffea+TX, Phytoseiulusmacropilus+TX, Phytoseiulus Chileanus ( +TX、Phytoline )+TX, Cypripedium scaly-bellied +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, Australian ladybird+TX, Rumina decollate+TX, Semielacherpetiolatus+TX, Aphid +TX, Steinernema carinata (Nematac +TX, +TX, BioNem +TX, +TX, +TX, )+TX, Nematode +TX, Nemasys +TX, BioNem +TX, +TX, +TX, +TX、Exhibitline +TX, +TX, )+TX, Steinernemakraussei (Nemasys +TX, BioNem +TX、Exhibitline )+TX, Steinernema riobrave ( +TX, )+TX, Steinernema scapterisci (Nematac )+TX, Steinernematid species+TX, Steinernematid species (Guardian )+TX, Deep-point mite-feeding ladybug +TX, bright-bellied enameled wasp+TX, Tetrastichus setifer+TX, Thropobiussemiluteus+TX, Chinese long-tailed wasp (Torymus sinensis)+TX, Tricholine )+TX, Trichogrammatid wasp +TX, Trichogramma spleniformis +TX, Trichogramma microplus +TX, Trichogramma ostriniae +TX, Trichogramma platneri +TX, Trichogramma septorum +TX, Xanthopimpla stemmator; and

[0734] Other biological agents, including: abscisic acid + TX, +TX, Chondrostereum purpureum (Chontrol )+TX, Colletotrichum gloeosporioides +TX, copper octanoate +TX, Delta trap (Trapline )+TX, Erwinia amylovora (Harpin) ( +TX、Ni-HIBIT Gold )+TX, iron phosphate +TX, Funnel trap (Trapline )+TX、 +TX, Grower's +TX, Homo-brassonolide +TX, Ferric Phosphate (LillyMiller Worry Free Ferramol Slug & Snail )+TX、MCP hail trap(MCP hail trap)(Trapline )+TX, weevils and parasitic wasps (Microctonus hyperodae)+TX, soybean reddish brown necrosis pathogen (Mycoleptodiscus terrestris) +TX, +TX, +TX, +TX, Pheromone trap (Thripline )+TX, potassium bicarbonate +TX, fatty acid potassium salt +TX, potassium silicate solution +TX, potassium iodide + potassium thiocyanate +TX, +TX, Spider Venom +TX, Locust Microsporidia (Nosema locustae) (Semaspore Organic Grasshopper )+TX, Sticky trap (Trapline +TX, Rebell )+TX and trap (Takitrapline y+ )+TX.

[0735] References in brackets after the active ingredient, e.g. [3878-19-1] refer to Chemical Abstracts Registry Numbers. The mixed partners described above are known. In the case where the active ingredients are included in "The Pesticide Manual" [The Pesticide Manual - A World Compendium; 13th edition; Editor: CDSTomLin; The British Crop Protection Council]], they are described therein by the entry number given above in parentheses for the specific compound; e.g. the compound "abamectin" is described by entry number (1). In the case where "[CCN]" is added above to a specific compound, the compound in question is included in the "Compendium of Pesticide Common Names", which can be found on the Internet [A.Wood; Compendium of Pesticide Common Names , 1995-2004]; for example, the compound "acetoprolin" is described on the Internet at http: / / www.alanwood.net / pesticides / acetoprole.html middle.

[0736] Most of the active ingredients mentioned above are referred to above by their so-called "common names," with the relevant "ISO common name" or another "common name" being used in individual cases. If a name is not a "common name," the kind of name used is replaced by the name given in parentheses for the specific compound; in this case, the IUPAC name, IUPAC / Chemical Abstracts name, "Chemical Name," "Traditional Name," "Compound Name," or "Research Code" is used, or if neither one of those names nor the "common name" is used, the "synonym" is used. "CAS Registry Number" means the Chemical Abstracts Registry Number.

[0737] Active ingredient mixtures of a compound of formula I selected from the compounds defined in Tables A-1 to A-92 and Table P and the above-mentioned active ingredients comprise a compound selected from Tables A-1 to A-92 and Table P and the above-mentioned active ingredient, preferably in a mixing ratio of from 100:1 to 1:6000, especially from 50:1 to 1:50, more especially in a ratio of from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 and 1:5, particularly preferably in a ratio of from 2:1 to 1:2, and a ratio of from 4:1 to 2:1 is likewise preferred, especially in a ratio of 1:1, or 5:1, 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 2:35, or 4:35, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

[0738] The mixtures as described above may be used in a method for controlling pests which comprises applying a composition comprising a mixture as described above to the pests or their environment, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body.

[0739] 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 active ingredients as described above can be applied, for example, in a single "ready-to-use" form, in a combined spray mixture (the mixture is composed of separate formulations of these single active ingredient components, such as a "tank mix"), and in combination with these single active ingredients when applied in a sequential manner (i.e., one after another within a reasonably 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 as described above is not critical for practicing the present invention.

[0740] The compositions according to the invention may also contain other solid or liquid adjuvants, such as stabilizers, for example non-epoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soybean oil), defoamers (for example silicone oils), preservatives, viscosity regulators, adhesives and / or tackifiers, fertilizers or other active ingredients for achieving specific effects, such as bactericides, fungicides, nematicides, plant activators, molluscicides or herbicides.

[0741] The compositions according to the invention are prepared in a manner known per se, in the absence of auxiliaries, for example by grinding, screening and / or compressing the solid active ingredient; and in the presence of at least one auxiliary, for example by intimately mixing the active ingredient with one or more auxiliary agents and / or grinding the active ingredient with one or more auxiliary agents. These methods for preparing the compositions and the use of compound I for preparing these compositions are also subject matter of the present invention.

[0742] Methods of applying these compositions, i.e., methods for controlling the aforementioned types of pests, such as spraying, atomizing, dusting, brushing, seed dressing, broadcasting or pouring (which are selected to suit the intended purpose of the prevailing situation), and the use of these compositions for controlling the aforementioned types of pests are further subjects of the present invention. Typical concentration rates are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. The application rates per hectare are generally between 1 g and 2000 g of active ingredient per hectare, in particular between 10 g / ha and 1000 g / ha, preferably between 10 g / ha and 600 g / ha.

[0743] In the field of crop protection, the preferred method of application is application to the leaves of the plants (foliar application), the frequency and rate of application possibly being selected to suit the risk of infestation by the pest in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by saturating the locus of the plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of rice crops, such granules can be metered into flooded rice fields.

[0744] The compound with formula I of the present invention and composition thereof are also suitable for the protection of plant propagation materials (such as seed, as fruit, tuber or grain, or nursery plants), to resist the harmful organism of above-mentioned type.Can be used before planting, this propagation material is processed, for example, can be processed before sowing, seed.Alternatively, this compound can be applied to seed grain (coating), and this is by being immersed in liquid composition by grain or by using solid composition layer and realize.Also may use these compositions when this propagation material is planted in the place of application, for example, these compositions are applied to seed furrow during sowing.These treatment methods for plant propagation materials and the plant propagation materials so processed are other themes of the present invention.Typical treatment ratio will depend on plant to be controlled and harmful organism / fungus, and usually between 1 gram to 200 grams of every 100kg seed, preferably between 5 grams to 150 grams of every 100kg seed, as between 10 grams to 100 grams of every 100kg seed.

[0745] The term seed includes all kinds of seeds and plant propagules including but not limited to true seeds, seed pieces, suckers, kernels, bulbs, fruits, tubers, grains, rhizomes, cuttings, cuttings and the like and in preferred embodiments means true seeds.

[0746] The present invention also includes seeds coated or treated with a compound of formula I or seeds containing a compound of formula I. Although more or less of the component can penetrate into the seed material, depending on the method of application, the term "coating or treatment and / or containing" generally refers to when applied, in most cases, the active ingredient is on the surface of the seed. When the seed product is (re)planted, it can absorb the active ingredient. In an embodiment, the present invention makes it possible to obtain plant propagation materials having a compound of formula I adhered thereto. In addition, the composition comprising the plant propagation material treated with a compound of formula I can be obtained.

[0747] Seed treatment includes all applicable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. Seed treatment with the compound of Formula I can be carried out by any known method and used, such as before sowing seeds or in the sowing / planting process, seed spraying or dusting.

[0748] The compounds of the present invention may be distinguished from other similar compounds by greater efficacy and / or different pest control at lower application rates, which can be determined by one skilled in the art using experimental procedures, using lower concentrations (if necessary) such as 10 ppm, 5 ppm, 2 ppm, 1 ppm or 0.2 ppm, or lower application rates such as 300, 200 or 100 mg of AI / m 2 Greater efficacy may be observed through increased safety (against non-target organisms above and below ground (such as fish, birds and bees), improved physico-chemical properties or increased biodegradability.

[0749] Biological examples:

[0750] The following examples are used to illustrate the present invention. Certain compounds of the present invention may differ from known compounds in that they exhibit greater efficacy at low application rates, which can be demonstrated by one skilled in the art using the experimental procedures outlined in the examples, using lower application rates (if necessary), for example, 50 ppm, 24 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

[0751] Example B1: Diabrotica balteata (corn rootworm)

[0752] Corn sprouts placed on the agar layer in 24-well microtiter plates were treated with an aqueous test solution prepared from a 10,000ppm DMSO stock solution by spraying. After drying, the plates were infested with L2 larvae (6 to 10 / well). After infestation for 4 days, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0753] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0754] 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

[0755] Example B2: Euschistus heros (Neotropical brown stink bug)

[0756] Soybean leaves on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaves were infested with N2 nymphs. After 5 days of infestation, the samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0757] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0758] P1, P2, P3, P7, P11, P12, P16, P17, P18, P22, P25, P29, P32, P33, P37, P38

[0759] Example B3: Frankliniella occidentalis (Western flower thrips): feeding / contact activity

[0760] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 μL DMSO stock solution. After drying, the leaf discs were infested with a mixed-age population of flower thrips. Seven days after infestation, the samples were evaluated for mortality.

[0761] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0762] P1, P4, P12, P16, P28, P37

[0763] Example B4: Chilosuppressalis (Striped rice stemborer)

[0764] 24 hole microtiter plates with artificial feed are handled by pipetting with the aqueous test solution prepared from 10 '000ppm DMSO stock solution.After drying, plate is infested (6-8 only / hole) with L2 stage larvae.After infesting 6 days, compared to untreated sample, these samples are assessed for mortality rate, antifeedant effect and growth inhibition.When at least one in these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, the control of test sample to Chilo suppressalis was realized.

[0765] The following compounds produced at least 80% control in at least one of the categories (mortality, antifeedant effect, or growth inhibition) at a 200 ppm application rate:

[0766] P1, P3, P4, P8, P11, P12, P14, P19, P21, P25, P27, P28, P29, P30, P31, P32, P33, P34, P35, P36, P37

[0767] Example B5: Plutellaxylostella (Diamondback moth)

[0768] 24-well microtiter plates with artificial diet were treated by pipetting with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, Plutella xylostella eggs were pipetted through a plastic template onto gel blotting paper and the plate was sealed with it. After 8 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.

[0769] The following compounds gave an effect of at least 80% in at least one of the two categories (mortality or growth inhibition) at an application rate of 200 ppm:

[0770] 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

[0771] Example B6: Myzus persicae (Green peach aphid): Feeding / contact activity

[0772] Sunflower leaf disks were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf disks were infested with a population of mixed-age aphids. After 6 days of infestation, the samples were evaluated for mortality.

[0773] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0774] P3, P4, P7, P11, P12, P16, P17, P18, P21, P22

[0775] Example B7: Myzus persicae (Green peach aphid): Systemic activity

[0776] The roots of pea seedlings infested with a population of mixed-age aphids were placed directly into an aqueous test solution prepared from a 10,000 DMSO stock solution. Six days after the seedlings were placed in the test solution, the samples were evaluated for mortality.

[0777] The following compounds produced at least 80% mortality at a test rate of 24 ppm:

[0778] P2, P12, P16, P17, P21

[0779] Example B8: Myzus persicae (Green peach aphid): Intrinsic activity

[0780] The test compound prepared from 10,000ppm DMSO stock solution is applied to 24-well microtiter plates by pipette and mixed with sucrose solution. Use the parafilm (Parafilm) sealing plate of stretching. The plastic template with 24 holes is placed on the plate, and the pea seedlings infected are directly placed on the parafilm. The plate infected with gel blotting paper and another plastic template is then inverted. After infecting for 5 days, these samples are evaluated for mortality.

[0781] The following compounds produced at least 80% mortality at a test rate of 12 ppm:

[0782] P2, P3, P4, P7, P11, P12, P16, P17, P18, P21, P22, P28, P30, P31, P32, P34, P36, P37, P38

[0783] Example B9: Spodopteralittoralis (Egyptian cotton leafworm)

[0784] The cotton leaf disk is placed on the agar in the 24 hole microtiter plates and sprayed with the aqueous test solution prepared from 10 '000ppm DMSO stock solution.After drying, the leaf disk is infested with five L1 stage larvae. After infesting 3 days, compared to untreated sample, these samples are assessed at mortality rate, antifeedant effect and growth inhibition.When at least one in these classifications (mortality rate, antifeedant effect and growth inhibition) was higher than untreated sample, realized the control of test sample to Spodoptera littoralis.

[0785] The following compounds produced at least 80% control in at least one of the categories (mortality, antifeedant effect, or growth inhibition) at a 200 ppm application rate:

[0786] 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

[0787] Example B10: Spodoptera littoralis (Egyptian cotton leafworm)

[0788] Test compound is applied to 24 orifice plates and mixed with agar with a pipette from 10,000ppm DMSO stock solution. Lettuce seeds are placed on agar and sealed this multi-well plate with another plate that also comprises agar. After 7 days, root has absorbed compound and lettuce growth has entered the cover plate. Then, these lettuce leaves are cut into the cover plate. Spodoptera ova is pipetted through plastic templates on moist gel blotting paper and with its sealed cover plate. After infecting 6 days, compared to untreated sample, these samples are assessed for mortality rate, antifeedant effect and growth inhibition.

[0789] The following compounds gave at least 80% efficacy in at least one of the three categories (mortality, feed refusal, or growth inhibition) at a test rate of 12.5 ppm:

[0790] P3, P15, P32

[0791] Example B11: Tetranychus urticae (Two-spotted spider mite): feeding / contact activity

[0792] Bean leaf discs on agar in 24-well microtiter plates were sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed age mite population. Eight days after infestation, these samples were evaluated for mortality of the mixed population (mobile platform).

[0793] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0794] P36

[0795] Example B12: Thrips tabaci (Onion Thrips): Feeding / Contact Activity

[0796] Sunflower leaf discs were placed on agar in 24-well microtiter plates and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf discs were infested with a mixed-age population of thrips. After 6 days of infestation, these samples were evaluated for mortality.

[0797] The following compounds produced at least 80% mortality at an application rate of 200 ppm:

[0798] P5, P7, P17, P18, P22

[0799] Example B13: Myzus persicae (Green peach aphid)

[0800] The test compound prepared from 10,000ppm DMSO stock solution is applied to 96 well microtiter plates and mixed with sucrose solution by liquid handling robot. Parafilm is stretched on 96 well microtiter plates, and the plastic template with 96 holes is placed on this plate. Aphids are sieved into the hole directly on this parafilm. With gel blotting card and second plastic template sealing through the plate of infestation, and then inverted. After infesting 5 days, these samples are assessed for mortality rate.

[0801] The following compounds produced at least 80% mortality at an application rate of 50 ppm:

[0802] P2, P3, P5, P7, P11, P12, P14, P15, P16, P17, P18, P21, P22, P30, P32, P33, P37, P38

[0803] Example B14: Plutellaxylostella (Diamondback Moth)

[0804] The aqueous test solution prepared from 10,000ppm DMSO stock solution was used to process 96 microtiter plates containing artificial feeds by a liquid handling robot. After drying, eggs (approximately 30 per well) were infested on the mesh lid that was suspended above the feed. These eggs were hatched and the L1 larvae moved downward to the feed. After infecting for 9 days, these samples were assessed for mortality.

[0805] The following compounds gave an average mortality of at least 80% at an application rate of 500 ppm:

[0806] P2, P3, P5, P6, P7, P9, P15, P16, P17, P18, P20, P22, P24, P25, P30, P31, P32, P33, P38.

Claims

1. Compound of Formula II in R1 is cyclopropyl -CH2-, CH≡CCH2-, hydrogen or methyl; R3 is methyl; R4 is pyridine or pyrimidine, wherein the pyridine or pyrimidine is optionally substituted with a halogen; and Z1 is halogen, CN, amino, NH2C(O), (C1-C3 alkyl)amino, di(C1-C3 alkyl)amino, hydroxy, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C4 haloalkylsulfanyl, C1-C4 haloalkylsulfonyl, C1-C3 alkoxy-C1-C3 alkyl, C1-C3 alkoxy-C1-C3 alkoxy, (C1-C3 alkyl)NHC(O), (C1-C3 alkyl)2NC(O), (C1-C3 alkyl)C(O)NH, (C1-C3 alkyl)C(O), oxadiazolyl, diphenylmethanimine, C1-C3 haloalkoxy, or phenyl; and Its N-oxide or agrochemically acceptable salt.

2. The compound according to claim 1, wherein R1 is cyclopropyl-CH2-, hydrogen or methyl.

3. The compound according to claim 1, wherein R1 is hydrogen or methyl.

4. The compound according to claim 1, wherein R4 is selected from J1 and J3 5. The compound of claim 1, wherein Z1 is trifluoromethoxy, 2,2-difluoroethoxy, difluoromethoxy, chloro, fluoro, amino, 2,2,2-trifluoroethoxy, bromo or iodo. The compound according to claim 1 , wherein Z 1 is chloro, fluoro, bromo or iodo.

7. A process for preparing a compound of formula II as defined in any one of claims 1 to 6, comprising reacting a compound of formula VI in the presence of a suitable base wherein R3, R4 and Z1 are as defined in any one of claims 1 to 5, and the compound of formula VIII wherein R1 is as defined in any one of claims 1 to 5, reacting.

8. The process according to claim 7, wherein the compound of formula II is further reacted with a carboxylic acid derivative of formula III Wherein R2 is Y1, Y3, Y5 or Y 11 one Thus providing a compound of formula I wherein R1, R3, R4, and Z1 are as described in any one of claims 1-5.

9. The method according to claim 8, wherein the compound of formula III is first activated to a compound of formula IIIa in the presence of a base according to the following scheme: Where X0 is selected from and halogens, Subsequent reaction with a compound of formula II provides a compound of formula I.

Images