Novel heteroaryl-triazole compounds as pesticides

Abstract

The present invention relates to novel heteroaryl-triazole and heteroaryl-tetrazole compounds of general formula (I) (structural element R 1 , R 2 , R 3 , R 4 and R 5 has the meaning given in the specification), to formulations and compositions containing such compounds and their use in controlling pests such as arthropods and insects in plant protection, and for controlling ectoparasites in animals. [Formula 1] TIFF2022541808000233.tif49140

Description

[Technical field]

[0001] The present invention relates to novel heteroaryl triazole compounds, formulations and compositions containing such compounds, and their use in controlling pests such as arthropods and insects in plant protection and for controlling ectoparasites on animals. [Background technology]

[0002] Certain heteroaryl-triazole compounds have been disclosed for use in controlling ectoparasites in animals in WO2017 / 192385 and for use in controlling pests such as arthropods and insects in the field of plant protection in WO2019 / 170626 and WO2019 / 215198. Furthermore, patent applications WO2019 / 197468, WO2019 / 201835, WO2019 / 202077 and WO2019 / 206799 disclose certain heteroaryl-triazole compounds for use in controlling ectoparasites in animals and for controlling pests such as arthropods and insects in the field of plant protection. WO2020 / 002563, WO2020 / 053364, WO2020 / 053365, WO2020 / 079198 and WO2020 / 094363 all describe azole-amide compounds that can be used as insecticides. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] WO2017 / 192385 [Patent Document 2] WO2019 / 170626 [Patent Document 3] WO2019 / 215198 [Patent Document 4] WO2019 / 197468 [Patent Document 5] WO2019 / 201835 [Patent Document 6] WO2019 / 202077 [Patent Document 7] WO2019 / 206799 [Patent Document 8] WO2020 / 002563 [Patent Document 9] WO2020 / 053364 [Patent Document 10] WO2020 / 053365 [Patent Document 11] WO2020 / 079198 [Patent Document 12] WO2020 / 094363 Summary of the Invention [Problem to be solved by the invention]

[0004] Modern plant protection products and animal ectoparasiticides must meet many requirements, for example, in terms of efficacy, persistence, spectrum and resistance-destroying properties. Questions of toxicity, combinability with other active compounds or formulation auxiliaries become important, as well as questions of the costs required for the synthesis of active compounds. Furthermore, resistance may occur. For all these reasons, the search for new crop protection compositions or animal ectoparasiticides cannot be considered complete, and there is a constant need for new compounds that have improved properties, at least in terms of individual aspects, compared to known compounds.

[0005] The object of the present invention was to provide compounds which in various ways broaden the pesticidal spectrum. [Means for solving the problem]

[0006] The present invention provides a compound of the following general formula (I): [ka]

[0007] In the formula (configuration 1-1), R1 is hydrogen; R 2 is phenyl, where the phenyl is substituted with a total of 1-2 substituents, provided that no such substituents are on either carbon adjacent to the carbon bonded to a C=O, and one substituent is Cyclopropyl, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclopropylsulfonyl, difluoromethylsulfonyl, trifluoroethylsulfonyl, trifluoromethylsulfonyl, 1-cyanocyclopropyl and -SF 5 Selected from group A consisting of: The other substituents are independently selected from group B consisting of chlorine, trifluoromethyl and trifluoromethoxy; or R 2 teeth, thiophene, optionally substituted by one substituent selected from the group consisting of fluorine, chlorine, bromine and trifluoromethyl; or R 2 teeth, a pyrazole optionally substituted by 1 to 2 substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and trifluoromethyl; R 3 is C 1 -C 3 is alkyl; R 4 is pyridine, pyrimidine, or pyrazine, wherein the pyridine, pyrimidine, or pyrazine is optionally substituted by one substituent selected from the group consisting of chlorine and -CN; R 5 is ethyl, n-propyl, iso-propyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, iso-propoxy or halogen.

[0008] The compounds of formula (I) likewise include any diastereomers or enantiomers and E / Z isomers which may exist, as well as the salts and N-oxides of the compounds of formula (I) and their uses for controlling pests.

[0009] Preferred group definitions for the formulae specified above and below are provided below.

[0010] The present invention further comprises: (Configuration 1-2): R 1 is hydrogen; R 2 is phenyl, wherein the phenyl is substituted with a total of 1-2 substituents, provided that no such substituents are on the carbon adjacent to any carbon bonded to C=O, and one substituent is Methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclopropylsulfonyl, difluoromethylsulfonyl, trifluoroethylsulfonyl, trifluoromethylsulfonyl and -SF 5 and cyclopropyl, wherein said cyclopropyl is optionally substituted by 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl and trifluoromethyl; The other substituents are independently selected from group B consisting of fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy and cyclopropyl, said cyclopropyl being optionally substituted by 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl and trifluoromethyl; or R 2 but, thiophene, optionally substituted by one substituent selected from the group consisting of fluorine, chlorine, bromine and trifluoromethyl; or R 2 but, a pyrazole optionally substituted by 1 to 2 substituents selected from the group consisting of fluorine, chlorine, bromine, methyl and trifluoromethyl; R 3 But, C 1 -C 3 is alkyl; R 4is pyridine, pyrimidine or pyrazine, wherein the pyridine, pyrimidine or pyrazine is optionally substituted by one substituent selected from the group consisting of chlorine and -CN; R 5 is ethyl, n-propyl, iso-propyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, iso-propoxy or halogen.

[0011] The preferred one (Configuration 2-1) is R 1 is hydrogen; R 2 is 3-chloro-5-cyclopropylphenyl, 3-chloro-5-methylsulfonylphenyl, 5-chloro-3-thienyl, 3-chloro-5-(2,2,2-trifluoroethylsulfonyl)phenyl, 3-chloro-5-isopropylsulfonylphenyl, 3-cyclopropylsulfonyl-5-(trifluoromethyl)phenyl, 3-chloro-5-ethylsulfonylphenyl, 3-chloro-5-cyclopropylsulfonylphenyl, 3-ethylsulfonyl-5-(trifluoromethyl)phenyl, 3-cyclopropyl-5-(trifluoromethoxy)phenyl, 3-chloro-5-(difluoromethylsulfonyl)phenyl, 3-methylsulfonyl-5-(trifluoromethyl)phenyl, 1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl, 3-chloro-5-(pentafluoro-λ6-sulfanyl)phenyl, 3-chloro-5-(1-cyanocyclopropyl)phenyl, or 3-chloro-5-(trifluoromethylsulfonyl)phenyl; R 3 is methyl; R 4 is 5-cyanopyridin-2-yl, pyrimidin-2-yl, 5-chloropyrimidin-2-yl or 5-chloropyridin-2-yl; R 5 is ethyl, n-propyl, iso-propyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, iso-propoxy, iodine, bromine or chlorine.

[0012] The preferred one (Configuration 2-2) is: R 1 is hydrogen; R 2 3-chloro-5-cyclopropylphenyl, 3-chloro-5-methylsulfonylphenyl, 5-chloro-3-thienyl, 3-chloro-5-(2,2,2-trifluoroethylsulfonyl)phenyl, 3-chloro-5-isopropylsulfonylphenyl, 3-cyclopropylsulfonyl-5-(trifluoromethyl)phenyl, 3-chloro-5-ethylsulfonylphenyl, 3-chloro-5-cyclopropylsulfonylphenyl, 3-ethylsulfonyl-5-(trifluoromethyl)phenyl, 3-cyclopropyl-5-(trifluoromethoxy)phenyl, 3-chloro-5-(difluoromethylsulfonyl)phenyl, 3-methylsulfonyl-5-(trifluoromethyl)phenyl, 1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl, 3-chloro-5-(pentafluoro-λ6-sulfanyl)phenyl, 3-chloro-5-(1-cyanocyclopropyl)phenyl, 3-chloro-5-(trifluoromethylsulfonyl)phenyl, nyl)phenyl, 3-bromo-5-[1-(trifluoromethyl)cyclopropyl]phenyl, 3-cyclopropyl-5-methylsulfonylphenyl, 3-(difluoromethyl)-5-methylsulfonylphenyl, 3-cyclopropyl-5-cyclopropylsulfonylphenyl, 3-fluoro-5-methylsulfonylphenyl, 3-(difluoromethoxy)-5-methylsulfonylphenyl, 3-methylsulfonyl-5-(trifluoromethoxy)phenyl, 3-cyclopropyl-5-(difluoromethyl)phenyl, 3-bromo-5-(1-fluorocyclopropyl)phenyl, 3-bromo-5-(2,2-difluorocyclopropyl)phenyl, 3-cyclopropyl-5-(difluoromethoxy)phenyl, 3-cyclopropylsulfonyl-5-(difluoromethoxy)phenyl, 3-cyclopropylsulfonyl-5-(trifluoromethoxy)phenyl, or 3-cyclopropylsulfonyl-5-(difluoromethyl)phenyl; R 3 is methyl; R4 is 5-cyanopyridin-2-yl, pyrimidin-2-yl, 5-chloropyrimidin-2-yl or 5-chloropyridin-2-yl; R 5 There are also compounds of formula (I) wherein is ethyl, n-propyl, iso-propyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, iso-propoxy, iodine, bromine or chlorine.

[0013] In a further preferred embodiment, the present invention provides a compound comprising R 3 C 1 -C 3 With respect to compounds of formula (I') in which alkyl, particularly preferably Me, [ka]

[0014] During the ceremony, Structural element R 1 , R 2 , R 4 and R 5 has the meaning of being provided in the configuration (1-1) or the configuration (2-1) or the configuration (1-2) or the configuration (2-2).

[0015] In a further preferred embodiment, the present invention provides a compound comprising R 3 C 1 -C 3 With respect to compounds of formula (I″) in which alkyl, particularly preferably Me, [ka]

[0016] During the ceremony, Structural element R 2 , R 4 and R 5 has the meaning of being provided in the configuration (1-1) or the configuration (2-1) or the configuration (1-2) or the configuration (2-2).

[0017] According to a further aspect, the present invention encompasses intermediate compounds useful in the preparation of compounds of general formula (I) above.

[0018] In particular, the present invention encompasses intermediate compounds of general formula (e): [ka]

[0019] During the ceremony, Structural element R 3 , R 4 and R 5 has the meaning given in the structure (1-1) or the structure (2-1) or the structure (1-2) or the structure (2-2), for example the free amine in the case of the intermediate compounds INT-1 to INT-8, INT-10 to INT-12, INT-18, INT-20, INT-22, INT-24, INT-25 and INT-26, their salts and amine hydrochlorides: INT-1: 6-[5-[(1S)-1-aminoethyl]-3-ethyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile hydrochloride, INT-2: 6-[5-[(1S)-1-aminoethyl]-3-isopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-3: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile hydrochloride, INT-4: 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-5: 6-[5-[(1S)-1-aminoethyl]-3-methoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-6: 6-[5-[(1S)-1-aminoethyl]-3-ethoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-7: 6-[5-[(1S)-1-aminoethyl]-3-isopropoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-8: (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride, INT-10: 1-[3-chloro-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl]ethanamine, INT-11: 1-[3-bromo-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl]ethanamine, INT-12: 1-[3-iodo-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-5-yl]ethanamine, INT-18: (1S)-1-[1-(5-chloropyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethanamine, INT-20: (1S)-1-[1-(5-chloropyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride, INT-22: (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethanamine, INT-24: 6-[5-(1-aminoethyl)-3-iodo-1H-1,2,4-triazol-1-yl]nicotinonitrile, INT-25: 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, INT-26: 6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile Includes.

[0020] The invention also encompasses the intermediates 3-chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (INT-9), 3-cyclopropyl-5-(difluoromethyl)benzoic acid (INT-13), 3-cyclopropyl-5-iodobenzoic acid (INT-14), 3-chloro-5-[(difluoromethyl)sulfonyl]benzoic acid (INT-16), 3-cyano-5-cyclopropylbenzoic acid (INT-15), 3-cyclopropyl-5-methylsulfonyl-benzoic acid (INT-17), 3-cyclopropyl-5-cyclopropylsulfonyl-benzoic acid (INT-19) and 3-fluoro-5-methylsulfonyl-benzoic acid (INT-21) and salts thereof.

[0021] The present invention also includes an intermediate compound represented by the following general formula (yf′): [ka]

[0022] During the ceremony, E' is hydrogen, chlorine or -CN and A is N or CH, including salts thereof. Preferred is the hydrochloride salt, e.g. INT-23: 5-[(1S)-1-aminoethyl]-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-3-amine hydrochloride.

[0023] The compounds of formula (I), depending on the nature of the substituents, may also be in the form of stereoisomers, i.e. in the form of geometric and / or optical isomers or isomeric mixtures of various compositions. Although only the compounds of formula (I) discussed herein, the invention provides both the pure stereoisomers and any desired mixtures of these isomers.

[0024] According to the invention, however, it is preferred to use the optically active stereoisomeric forms of the compounds of formula (I) and their salts.

[0025] The present invention therefore relates to both the pure enantiomers and diastereomers and to mixtures thereof for controlling pests, including arthropods, especially insects.

[0026] Where appropriate, the compounds of formula (I) may exist in various polymorphic forms or as mixtures of various polymorphic forms. Both pure polymorphs and polymorphic mixtures are provided by the present invention and may be used in accordance with the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] definition Those of ordinary skill in the art will appreciate that unless expressly stated otherwise, the terms "a" or "an" when used in this application can mean "one," "one or more," or "at least one," depending on the context.

[0028] In all structures depicted herein, including ring systems and groups, adjacent atoms may not be -OO- or -OS-.

[0029] Structures with variable numbers of possible carbon atoms (C atoms) are referred to in this application as C 炭素原子の下限 -C 炭素原子の上限 Structure (C LL -C UL The alkyl group may be more specifically defined by its structure, for example, C 3 -C 10 It corresponds to an alkyl. Ring structures consisting of carbon atoms and heteroatoms are sometimes called "LL- to UL-membered" structures. An example of a six-membered ring structure is toluene (a six-membered ring structure substituted with methyl groups).

[0030] A generic term for a substituent, e.g. C LL -C UL The alkyl group may be, for example, C LL -C UL Cycloalkyl-C LL -C ULWhen it is at the end of a compound substituent, such as an alkyl group, it is not necessary to use the compound as the starting component of the compound substituent, e.g., C LL -C UL Cycloalkyl refers to the latter substituent, e.g., C LL -C UL All generic terms used in this application for chemical groups, ring systems and cyclic groups include "C LL ~C UL " or "LL-~UL-member" to specify more specifically. 。 In the definitions of the symbols given in the formula above, collective terms are used which generally represent the following substituents:

[0031] Halogen relates to elements of the seventh main group, preferably fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine and bromine, even more preferably fluorine and chlorine.

[0032] Examples of heteroatoms are N, O, S, P, B, Si. Preferably, the term "heteroatom" relates to N, S and O.

[0033] According to the present invention, "alkyl" by itself or as part of a chemical group represents a straight or branched hydrocarbon, preferably having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2-dimethylpropyl, 1,3-dimethylbutyl, 1,4-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl and 2-ethylbutyl. Preference is also given to alkyl having 1 to 4 carbon atoms, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl. The alkyl of the present invention may be substituted with one or more identical or different groups.

[0034] According to the present invention, "alkenyl" by itself or as part of a chemical group preferably represents a straight or branched hydrocarbon having 2 to 6 carbon atoms and at least one double bond, such as, for example, vinyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-3-butenyl, -2-pentenyl, 4-methyl-2-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3- Dimethyl-2-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl. Preferred are also alkenyls having 2 to 4 carbon atoms, in particular 2-propenyl, 2-butenyl or 1-methyl-2-propenyl. The alkenyls of the present invention may be substituted with one or more identical or different groups.

[0035] According to the present invention, "alkynyl" by itself or as part of a chemical group preferably represents a straight or branched hydrocarbon having 2 to 6 carbon atoms and at least one triple bond, such as, for example, 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1-methyl-2-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 2-hex ... yl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl and 2,5-hexadiynyl. Preferred are also alkynyls having 2 to 4 carbon atoms, in particular, for example, ethynyl, 2-propynyl or 2-butynyl-2-propenyl. The alkynyls of the present invention may be substituted with one or more identical or different groups.

[0036] According to the present invention, "cycloalkyl" by itself or as part of a chemical group represents a monocyclic, bicyclic or tricyclic hydrocarbon, preferably having 3 to 10 carbons, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl. Preference is also given to alkenyl having 3, 4, 5, 6 or 7 carbon atoms, in particular cyclopropyl or cyclobutyl. Cycloalkyl according to the present invention may be substituted with one or more identical or different groups.

[0037] According to the present invention, "alkylcycloalkyl" preferably represents a monocyclic, bicyclic or tricyclic alkylcycloalkyl having 4 to 10 or 4 to 7 carbon atoms, such as methylcyclopropyl, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is also given to alkylcycloalkyl having 4, 5 or 7 carbon atoms, in particular ethylcyclopropyl or 4-methylcyclohexyl. The alkylcycloalkyl of the present invention may be substituted with one or more identical or different groups.

[0038] According to the present invention, "cycloalkylalkyl" preferably represents a monocyclic, bicyclic or tricyclic cycloalkylalkyl having 4 to 10 or 4 to 7 carbon atoms, such as cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is also given to cycloalkylalkyl having 4, 5 or 7 carbon atoms, in particular cyclopropylmethyl or cyclobutylmethyl. Cycloalkylalkyl of the present invention may be substituted with one or more identical or different groups.

[0039] According to the present invention, "hydroxyalkyl" preferably denotes a straight-chain or branched alcohol having 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, s-butanol and t-butanol. Preference is also given to hydroxyalkyl groups having 1 to 4 carbon atoms. Hydroxyalkyl groups of the present invention may be substituted by one or more identical or different groups.

[0040] According to the present invention, "alkoxy" denotes a straight or branched O-alkyl, preferably having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy and t-butoxy. Preference is also given to alkoxy groups having 1 to 4 carbon atoms. The alkoxy groups of the present invention may be substituted by one or more identical or different groups.

[0041] According to the present invention, "alkylthio" or "alkylsulfanyl" represents a straight or branched S-alkyl group, preferably having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio and t-butylthio. Preference is also given to alkylthio groups having 1 to 4 carbon atoms. The alkylthio groups of the present invention may be substituted by one or more identical or different groups.

[0042] According to the present invention, "alkylsulfinyl" preferably represents a straight-chain or branched alkylsulfinyl having 1 to 6 carbon atoms, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, s-butylsulfinyl and t-butylsulfinyl. Also preferred are alkylsulfinyl groups having 1 to 4 carbon atoms. The alkylsulfinyl group of the present invention may be substituted by one or more identical or different groups and includes both enantiomers.

[0043] According to the present invention, "alkylsulfonyl" preferably represents a straight-chain or branched alkylsulfonyl having 1 to 6 carbon atoms, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, s-butylsulfonyl and t-butylsulfonyl. Also preferred are alkylsulfonyl groups having 1 to 4 carbon atoms. The alkylsulfonyl group of the present invention may be substituted with one or more identical or different groups.

[0044] According to the present invention, "cycloalkylthio" or "cycloalkylsulfanyl" preferably represents -S-cycloalkyl having 3 to 6 carbon atoms, such as cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio. Preference is also given to cycloalkylthio groups having 3 to 5 carbon atoms. The cycloalkylthio groups of the present invention may be substituted by one or more identical or different groups.

[0045] According to the present invention, "cycloalkylsulfinyl" preferably represents -S(O)-cycloalkyl having 3 to 6 carbon atoms, such as cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl. Preference is also given to cycloalkylsulfinyl groups having 3 to 5 carbon atoms. The cycloalkylsulfinyl groups of the present invention may be substituted by one or more identical or different groups and include both enantiomers.

[0046] According to the present invention, "cycloalkylsulfonyl" is preferably -SO having 3 to 6 carbon atoms. 2 -cycloalkyl, such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, and cyclohexylsulfonyl. Preferred are cycloalkylsulfonyl groups having 3 to 5 carbon atoms. The cycloalkylsulfonyl group of the present invention may be substituted with one or more of the same or different groups.

[0047] According to the present invention, "phenylthio" or "phenylsulfanyl" represents -S-phenyl, e.g., phenylthio. The phenylthio group of the present invention may be substituted with one or more identical or different groups.

[0048] According to the present invention, "phenylsulfinyl" denotes -S(O)-phenyl, for example phenylsulfinyl. The phenylsulfinyl group of the present invention may be substituted by one or more identical or different groups and includes both enantiomers.

[0049] According to the present invention, "phenylsulfonyl" refers to -SO 2 -phenyl, for example phenylsulfonyl. The phenylsulfonyl group of the present invention may be substituted with one or more identical or different groups.

[0050] According to the present invention, "alkylcarbonyl" preferably represents a straight or branched alkyl-C(=O) having 2 to 7 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl and t-butylcarbonyl. Also preferred is an alkylcarbonyl having 1 to 4 carbon atoms. The alkylcarbonyl of the present invention may be substituted with one or more identical or different groups.

[0051] According to the present invention, "alkoxycarbonyl", alone or as a component of a chemical group, preferably denotes a straight-chain or branched alkoxycarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkoxy moiety, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, s-butoxycarbonyl and t-butoxycarbonyl. The alkoxycarbonyl group of the present invention may be substituted by one or more identical or different groups.

[0052] According to the present invention, "alkylaminocarbonyl" preferably represents a straight-chain or branched alkylaminocarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl portion, such as methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl. The alkylaminocarbonyl group of the present invention may be substituted by one or more identical or different groups.

[0053] According to the present invention, "N,N-dialkylaminocarbonyl" preferably represents a linear or branched N,N-dialkylaminocarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as N,N-dimethylaminocarbonyl, N,N-diethylaminocarbonyl, N,N-di(n-propylamino)carbonyl, N,N-di(isopropylamino)carbonyl and N,N-di-(s-butylamino)carbonyl. The N,N-dialkylaminocarbonyl group of the present invention may be substituted by one or more identical or different groups.

[0054] According to the present invention, "aryl" refers to a monocyclic, bicyclic or polycyclic aromatic system having preferably 6 to 14, especially 6 to 10, ring carbon atoms, such as phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. Furthermore, aryl also refers to polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, etc., where the attachment site is on the aromatic system. The aryl group of the present invention may be substituted by one or more identical or different groups.

[0055] An example of a substituted aryl is arylalkyl, which is 1 -C 4 Alkyl and / or C 6 -C 14 The aryl portion may similarly be substituted with one or more of the same or different groups. Examples of such arylalkyl include benzyl and phenyl-1-ethyl.

[0056] According to the present invention, "heterocycle", "heterocyclic ring" or "heterocyclic ring system" refers to a carbocyclic ring system having at least one ring, in which at least one carbon atom is replaced by a heteroatom, preferably from the group consisting of N, O, S, P, B, Si, Se, which may be saturated, unsaturated or heteroaromatic, unsubstituted or substituted, and in which the binding site is on a ring atom. Unless otherwise defined, a heterocycle preferably contains 3 to 9 ring atoms, in particular 3 to 6 ring atoms, and one or more, preferably 1 to 4, in particular 1, 2 or 3 heteroatoms from the group consisting of N, O and S in the heterocycle, but no two oxygen atoms may be directly adjacent. A heterocycle usually contains up to 4 nitrogen atoms and / or up to 2 oxygen atoms and / or up to 2 sulfur atoms. When a heterocyclic group or heterocycle is optionally substituted, it may be fused to another carbocyclic or heterocyclic ring. In the case of optionally substituted heterocycles, the invention also includes polycyclic ring systems, such as 8-azabicyclo[3.2.1]octanyl or 1-azabicyclo[2.2.1]heptyl. In the case of optionally substituted heterocycles, the invention also includes spiro ring systems, such as 1-oxa-5-azaspiro[2.3]hexyl.

[0057] Heterocyclic groups of the present invention are, for example, piperidinyl, piperazinyl, morpholinyl, thiomorpholinyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, pyrrolinyl, pyrrolidinyl, imidazolinyl, imidazolidinyl, thiazolidinyl, oxazolidinyl, dioxolanyl, dioxolyl, pyrazolidinyl, tetrahydrofuranyl, dihydrofuranyl, oxetanyl, oxiranyl, azetidinyl, aziridinyl, oxazetidinyl, oxaziridinyl, oxazepanyl, oxazinanyl, azepanyl, oxopyrrolidinyl, dioxopyrrolidinyl, oxomorpholinyl, oxopiperazinyl and oxepanyl.

[0058] Of particular importance are heteroaryls, i.e. heteroaromatic systems. According to the present invention, the term heteroaryl denotes heteroaromatic compounds, i.e. fully unsaturated aromatic heterocyclic compounds, which meet the above definition of heterocycle. Preferred are 5-7 membered rings with 1-3, preferably 1 or 2, identical or different heteroatoms from the above group. Heteroaryl of the present invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and 1,2,4-diazepinyl. Heteroaryl groups of the present invention may be substituted by one or more identical or different groups.

[0059] The term "optionally substituted in each case" means that the group / substituent, such as alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclic and heteroaryl groups, is substituted, which means, for example, that the substituent, for example one substituent or multiple substituents, preferably 1, 2, 3, 4, 5, 6 or 7 substituents, are amino, hydroxyl, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, C 1 -C 4 Carboxyl, Carbonamide, SF 5 , aminosulfonyl, C 1 -C 4 Alkyl, C 1 -C 4 Haloalkyl, C 3 -C 4 Cycloalkyl, C 2 -C 4 Alkenyl, C 5 -C 6 Cycloalkenyl, C 2 -C4 Alkynyl, N-mono-C 1 -C 4 Alkylamino, N,N-di-C 1 -C 4 Alkylamino, NC 1 -C 4 Alkanoylamino, C 1 -C 4 Alkoxy, C 1 -C 4 Haloalkoxy, C 2 -C 4 Alkenyloxy, C 2 -C 4 Alkynyloxy, C 3 -C 4 Cycloalkoxy, C 5 -C 6 Cycloalkenyloxy, C 1 -C 4 Alkoxycarbonyl, C 2 -C 4 Alkenyloxycarbonyl, C 2 -C 4 Alkynyloxycarbonyl, C 6 -,C 10 -,C 14 -aryloxycarbonyl, C 1 -C 4 Alkanoyl, C 2 -C 4 Alkenyl carbonyl, C 2 -C 4 Alkynylcarbonyl, C 6 -,C 10 -,C 14 -arylcarbonyl, C 1 -C 4 Alkylthio, C 1 -C 4 Haloalkylthio, C 3 -C 4 Cycloalkylthio, C 2 -C 4 Alkenylthio, C 5 -C 6 Cycloalkenylthio, C 2 -C 4 Alkynylthio, C 1 -C 4 Alkyl sulfinyl (C1 -C 4 (including both enantiomers of the alkylsulfinyl group), C 1 -C 4 Haloalkylsulfinyl(C 1 -C 4 (including both enantiomers of the haloalkylsulfinyl group), C 1 -C 4 Alkylsulfonyl, C 1 -C 4 Haloalkylsulfonyl, N-mono-C 1 -C 4 Alkylaminosulfonyl, N,N-di-C 1 -C 4 Alkylaminosulfonyl, C 1 -C 4 Alkylphosphinyl, C 1 -C 4 Alkylphosphonyl(C 1 -C 4 Alkylphosphinyl and C 1 -C 4 (including both enantiomers of alkylphosphonyl), NC 1 -C 4 Alkylaminocarbonyl, N,N-di-C 1 -C 4 Alkylaminocarbonyl, NC 1 -C 4 Alkanoylaminocarbonyl, NC 1 -C 4 Alkanoyl-NC 1 -C 4 Alkylaminocarbonyl, C 6 -,C 10 -,C 14 -aryl, C 6 -,C 10 -,C 14 -aryloxy, benzyl, benzyloxy, benzylthio, C 6 -,C 10 -,C 14 -arylthio, C 6 -,C 10 -,C 14 -arylamino, benzylamino, heterocycle and trialkylsilyl, substituents attached via a double bond, e.g. C1 -C 4 It means a substituted group derived from an unsubstituted base structure selected from the group consisting of alkylidene (e.g., methylidene or ethylidene), oxo, imino and substituted imino. When two or more groups form one or more rings, these can be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, such as aromatic, and further substituted. The substituents mentioned in the examples ("first substituent level"), when they contain a hydrocarbonaceous moiety, may have further substitution therein ("second substituent level"), for example with one or more of the substituents each independently selected from halogen, hydroxyl, amino, nitro, cyano, isocyano, azido, acylamino, oxo and imino. The term "substituted (optionally substituted)" group preferably includes only one or two substituent levels.

[0060] The halogen-substituted or halogenated chemical groups of the present invention (e.g., alkyl or alkoxy) are mono- or poly-substituted with halogen up to the maximum possible number of substituents. Such groups are also referred to as halo groups (e.g., haloalkyl). In the case of polysubstitution with halogen, the halogen atoms may be the same or different and may all be bonded to one carbon atom or to several carbon atoms. The halogen is in particular fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine. In particular, the halogen-substituted groups are monohalocycloalkyl, such as 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl; monohaloalkyl, such as 2-chloroethyl, 2-fluoroethyl, 1-chloroethyl, 1-fluoroethyl, chloromethyl or fluoromethyl; perhaloalkyl, such as trichloromethyl or trifluoromethyl or CF 2 CF 3, polyhaloalkyl, such as difluoromethyl, 2-fluoro-2-chloroethyl, dichloromethyl, 1,1,2,2-tetrafluoroethyl or 2,2,2-trifluoroethyl. Further examples of haloalkyl are trichloromethyl, chlorodifluoromethyl, dichlorofluoromethyl, chloromethyl, bromomethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-chloro-2,2-difluoroethyl, pentafluoroethyl, 3,3,3-trifluoropropyl and pentafluoro-t-butyl. Preferred are haloalkyls having 1 to 4 carbon atoms and 1 to 9, preferably 1 to 5, identical or different halogen atoms selected from fluorine, chlorine and bromine. Particularly preferred are haloalkyls having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms selected from fluorine and chlorine, in particular difluoromethyl, trifluoromethyl or 2,2-difluoroethyl. Further examples of halogen substituted compounds are haloalkoxy, e.g. OCF 3 , O.C.H.F. 2 , O.C.H. 2 F, O.C.F. 2 CF 3 , O.C.H. 2 CF 3 , O.C.H. 2 CHF 2 and OCH 2 CH 2Cl, haloalkylsulfanyl, such as difluoromethylthio, trifluoromethylthio, oligochloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2,2,2-trifluoroethylthio or 2-chloro-1,1,2-trifluoroethylthio, haloalkylsulfinyl, such as difluoromethylsulfinyl, trifluoromethylsulfinyl, oligochloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl ... haloalkylsulfonyl groups, such as difluoromethylsulfinyl, trifluoromethylsulfinyl, oligochloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl; haloalkylsulfonyl groups, such as difluoromethylsulfonyl, trifluoromethylsulfonyl, oligochloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoroethylsulfonyl.

[0061] In the case of radicals having carbon atoms, radicals having 1 to 4 carbon atoms, especially 1 or 2 carbon atoms, are preferred. Preferred are usually halogens, such as fluorine and chlorine, (C 1 -C 4 ) alkyl, preferably methyl or ethyl; 1 -C 4) haloalkyl, preferably trifluoromethyl, (C 1 -C 4 ) alkoxy, preferably methoxy or ethoxy, (C 1 -C 4 ) substituents from the group haloalkoxy, nitro and cyano, where particular preference is given to the substituents methyl, methoxy, fluorine and chlorine.

[0062] Substituted amino, such as mono- or disubstituted amino, is, for example, alkyl, hydroxy, amino, alkoxy, acyl and aryl; preferably N-mono- and N,N-dialkylamino, (e.g. methylamino, ethylamino, N,N-dimethylamino, N,N-diethylamino, N,N-di-n-propylamino, N,N-diisopropylamino or N,N-dibutylamino), N-mono- or N,N-dialkoxyalkylamino groups (e.g. N-methoxymethylamino, N-methoxyethylamino, N,N-di(methoxymethyl)amino or N,N-di(methoxyethyl)amino). )amino), N-mono- and N,N-diarylamino, e.g. optionally substituted anilines, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino, further saturated N-heterocycles, which are N-substituted by one or two identical or different groups, preferably alkyl groups having 1 to 4 carbon atoms; where aryl is preferably phenyl or substituted phenyl; for acyl the definition provided further below applies, preferably (C 1 -C 4 The same applies to substituted hydroxylamino or hydrazino.

[0063] Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.

[0064] The optionally substituted phenyl is preferably unsubstituted or substituted with halogen, (C 1 -C 4) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 )Alkoxy-(C 1 -C 4 ) alkoxy, (C 1 -C 4 )Alkoxy-(C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl, (C 1 -C 4 ) haloalkoxy, (C 1 -C 4 ) alkylthio, (C 1 -C 4 ) haloalkylthio, (C 1 -C 4 ) Alkyl sulfinyl (C 1 -C 4 ) haloalkylsulfinyl, (C 1 -C 4 ) Alkyl sulfonyl (C 1 -C 4 ) haloalkylsulfonyl, cyano, isocyano and nitro, for example o-, m- and p-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and 4-oligochloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl, 4-heptafluorophenyl, mono- or polysubstituted, preferably trisubstituted, phenyl.

[0065] The optionally substituted cycloalkyl is preferably unsubstituted or substituted with halogen, cyano, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, (C 1 -C 4 )Alkoxy-(C 1 -C 4 ) alkoxy, (C 1 -C 4)Alkoxy-(C 1 -C 4 ) alkyl, (C 1 -C 4 ) haloalkyl and (C 1 -C 4 ) haloalkoxy, particularly one or two (C 1 -C 4 ) cycloalkyl which is mono- or polysubstituted, preferably trisubstituted, by identical or different radicals from the group of alkyl radicals.

[0066] The compounds of the present invention can be produced in preferred embodiments.The individual embodiments described herein can be combined with each other.Combinations that violate the law of nature and therefore would be excluded by a person skilled in the art based on their expertise are not included.For example, ring structures with three or more adjacent oxygen atoms are excluded.

[0067] Isomers Depending on the nature of the substituents, the compounds of formula (I) may be in the form of geometric and / or optically active isomers or corresponding isomeric mixtures of different compositions. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. The present invention therefore encompasses both the pure stereoisomers and any mixtures of these isomers.

[0068] Methods and Uses The present invention also relates to a method for controlling pests, which comprises applying a compound of formula (I) to pests and / or their habitats. Such control of pests is preferably carried out in agriculture and forestry, as well as in material protection. Preferably, surgical or therapeutic treatment methods of the human or animal body, as well as diagnostic methods carried out on the human or animal body, are excluded therefrom.

[0069] The present invention further relates to the use of the compounds of formula (I) as pesticides, in particular as crop protection agents.

[0070] In the context of this application, the term "pesticides" always also includes in each case the term "crop protection agents".

[0071] Compounds of formula (I) which have good plant tolerance, a desirable degree of toxicity to warm-blooded animals and good environmental compatibility are suitable for protecting plants and plant organs against biotic and abiotic stress factors, for increasing the yield, for improving the quality of the harvested product and for controlling pests, in particular insects, arachnids, worms, in particular nematodes and mollusks, encountered in agriculture, in horticulture, in animal husbandry, in aquaculture, in forests, in gardens and leisure facilities, in the protection of stored products and materials and in the field of hygiene.

[0072] Within the context of this patent application, the term "hygiene" is understood to mean any and all means, procedures and practices aimed at preventing diseases, in particular infectious diseases, and serving to protect human and animal health and / or to protect the environment and / or to maintain cleanliness. According to the invention, this includes in particular means for cleaning, disinfecting and sterilizing, for example, textiles or hard surfaces, in particular glass, wood, concrete, porcelain, ceramic, plastic surfaces or metal surfaces, in order to keep them free of sanitary pests and / or their excrement. Preferably, in this context, surgical or therapeutic treatment procedures that may be performed on the human or animal body, as well as diagnostic procedures performed on the human or animal body, are excluded from the scope of the invention.

[0073] The term "sanitation sector" therefore encompasses all areas, technical and industrial applications where these sanitary measures, procedures and practices are important, for example relating to hygiene in kitchens, bakeries, airports, bathrooms, swimming pools, department stores, hotels, hospitals, barns, animal husbandry, etc.

[0074] The term "sanitary pest" is therefore understood to mean one or more pests whose presence in the sanitary sector is problematic, in particular for health reasons. The main objective is therefore to avoid or minimize the presence of and / or exposure to sanitary pests in the sanitary sector. This can be achieved in particular by the application of pesticides that can be used both to prevent infestations and to combat infestations that are already present. Formulations that avoid or reduce exposure to pests can also be used. Sanitary pests include, for example, the following organisms:

[0075] The term "hygiene protection" therefore encompasses all activities aimed at maintaining and / or improving these hygiene measures, procedures and practices.

[0076] The compounds of formula (I) can preferably be used as pesticides. They are active against normally sensitive and resistant species and against all or some stages of development. The pests mentioned above are:

[0077] Pests from the phylum Arthropoda, in particular from the class Arachnida, for example Acarus spp., for example Acarus siro, Aceria kuko, Aceria sheldoni, Aculops spp., Aculus spp., for example Aculus fockeui, Aculus schlechtendali, Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp. spp., for example Brevipalpus phoenicis, Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., for example Eotetranychus hycoriae hicoriae, Epitrimerus pyri, Eutetranychus spp. e.g. Eutetranychus banksi, Eriophyes spp.), e.g. Eriophyes pyri, Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., e.g. Hemitarsonemus latus (= Polyphagotarsonemus latus), Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Neutrombicula autumnalis, Nuphersa spp. spp., Oligonychus spp., e.g. Oligonychus coffeae, Oligonychus coniferarum, Oligonychus ilicis, Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus yothersi, Ornithodorus spp., Ornithonyssus spp., Panonychus spp.), e.g. Panonychus citri (=Metatetranychus citri), Panonychus ulmi (=Metatetranychus ulmi), Phyllocoptruta oleivora, Platytetranychus multidigituli, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp. spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., e.g. Tarsonemus confusus, Tarsonemus pallidus, Tetranychus spp., e.g. Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae urticae, Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici;. From the class Chilopoda, for example, Geophilus spp., Scutigera spp.; From the order of the Collembola or class of the Collembola, for example, Onychiurus armatus; Sminthurus viridis; From the class Diplopoda, for example, Blaniulus guttulatus; From the class of Insecta, for example, from the order Blattodea, for example, Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophaea maderae, Loboptera decipiens, Neostylopyga rhombifolia, Panchlora spp., Parcoblatta spp., Periplaneta spp., for example Periplaneta americana, Periplaneta australasiae australasiae, Pycnoscelus surinamensis, Supella longipalpa; from the order Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethina tumida, Agelastica alni, Agrilus spp., for example Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus, Agrilus anxius, Agriotes spp., for example Agriotes linnaeus; linneatus, Agriotes mancus, Agriotes obscurus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anomala dubia, Anoplophora spp., e.g. Anoplophora glabripennis, Anthonomus spp., e.g. Anthonomus grandis, Anthrenus spp., Apion spp., Apogonia spp. spp., Athos haemorrhoidales, Atomaria spp. e.g. Atomaria linearis, Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp.), for example, Bruchus pisorum, Bruchus rufimanus, Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., for example, Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae, Chaetocnema spp., for example, Chaetocnema confinis, Chaetocnema denticulata, denticulata, Chaetocnema ectypa, Cleonus mendicus, Conoderus spp., Cosmopolites spp., e.g. Cosmopolites sordidus, Costelytra zealandica, Ctenicera spp., Curculio spp., e.g. Curculio caryae, Curculio caryatrypes, Curculio obtusus, Curculio sayi, Cryptolestes ferrugineus, ferrugineus, Cryptolestes pusillus, Cryptorhynchus lapathi, Cryptorhynchus mangiferae, Cylindrocopturus spp.), Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dendroctonus spp., for example Dendroctonus ponderosae, Dermestes spp., Diabrotica spp., for example Diabrotica balteata, Diabrotica barberi, Diabrotica undecimpunctata howardi, Diabrotica undecimpunctata undecimpunctata, Diabrotica virgifera virgifera, Diabrotica virgifera zeae, Dichocrocis spp., Dicladistella armigera, Diloboderus spp., Epicaerus spp., Epilachna spp., e.g. Epilachna borealis, Epilachna varivestis, Epitrix spp., e.g. Epitrix cucumeris, Epitrix fuscula fuscula, Epitrix hirtipennis, Epitrix subcrinita, Epitrix tuberis, Faustinus spp.), Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Heteronyx spp., Hoplia argentea, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., e.g. Hypothenemus hampeii, hampei, Hypothenemus obscurus, Hypothenemus pubescens, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa ​​decemlineata, Leucoptera spp., e.g. Leucoptera coffeella, Limonius ectipus ectypus, Lissorhoptrus oryzophilus, Listronotus (=Hyperodes) spp., Lixus spp., Luperodes spp., Luperomorpha xanthodera, Lyctus spp., Megacyllene spp.), for example Megacyllene robiniae, Megascelis spp., Melanotus spp., for example Melanotus longulus oregonensis, Meligethes aeneus, Melolontha spp., for example Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Neogalerucella spp. spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorhynchus spp., e.g. Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus, Otiorhynchus rugosostriarus, Otiorhynchus sulcatus, Oulema spp. spp., such as Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp.), for example, Phyllotreta armoraciae, Phyllotreta pusilla, Phyllotreta ramosa, Phyllotreta striolata, Popillia japonica, Premnotrypes spp., Prostephanus truncatus, Psylliodes spp., for example, Psylliodes affinis, Psylliodes chrysoseph. Psylliodes chrysocephala, Psylliodes punctulata, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum, Scolytus spp. such as Scolytus multistriatus, Sinoxylon perforans, Sitophilus spp. spp., for example, Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais, Sphenophorus spp., Stegobium paniceum, Sternechus spp., for example, Sternechus paludatus, Symphyletes spp., Tanymecus spp., for example, Tanymecus dilaticollis, Tanymecus indicus indicus, Tanymecus palliatus, Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp.), for example, Tribolium audax, Tribolium castaneum, Tribolium confusum, Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp., for example, Zabrus tenebrioides;. From the order Dermaptera, for example Anisolabis maritime, Forficula auricularia, Labidura riparia; From the order Diptera, for example, Aedes spp., for example Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans, Agromyza spp., for example Agromyza frontella, Agromyza parvicornis, Anastrepha spp., Anopheles spp., for example Anopheles quadrimaculatus, Anopheles gumbiae, gambiae, Asphondylia spp., Bactrocera spp., e.g. Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomya spp., Chrysops spp. spp.), Chrysozona pluvialis, Cochliomya spp., Contarinia spp.), for example, Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia sorghicola, Contarinia tritici, Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., for example, Culex pipiens, Culex quinquefasciatus, Culicoides spp., Culiseta spp. spp., Cuterebra spp., Dacus oleae, Dasineura spp., for example Dasineura brassicae, Delia spp., for example Delia antiqua, Delia coarctata, Delia florilega, Delia platura, Delia radicum, Dermatobia hominis, Drosophila spp., for example Drosophila melanogaster, Drosophila suzukii suzukii, Echinocnemus spp., Euleia heraclei, Fannia spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp.), Hydrellia griseola, Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp., e.g. Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae, Lucilia spp., e.g. Lucilia cuprina, Lutzomyia spp., Mansonia spp., Musca spp. spp., for example Musca domestica, Musca domestica vicina, Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomyia or Pegomyia spp., for example Pegomyia betae, Pegomyia hyoscyami, Pegomyia rubivora, Phlebotomus spp., Phorbia spp. spp., Phormia spp., Piophila casei, Platyparea poeciloptera, Prodiplosis spp., Psila rosae, Rhagoletis spp.), e.g. Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax, Rhagoletis pomonella, Sarcophaga spp., Simulium spp., e.g. Simulium meridionale, Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp. spp., e.g. Tipula paludosa, Tipula simplex, Toxotrypana curvicauda;. From the order of the Hemiptera, for example, Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosiphon spp., for example Acyrthosiphon pisum, Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp., e.g. Amrasca bigutulla, Amrasca devastans, Anuraphis cardui, Aonidiella spp., e.g. Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata, Aphanostigma piri, Aphis spp.), such as Aphis citricola, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii, Aphis pomi, Aphis spiraecola, Aphis biburniphila, Aphis viburniphila, Arboridia apicalis, Arytainilla spp., Aspidiella spp., Aspidiotus spp., e.g. Aspidiotus nerii, Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp. spp., Brevicoryne brassicae, Cacopsylla spp., e.g. Cacopsylla pyricola, Calligypona marginata, Capulinia spp.), Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus aonidum, Chrysomphalus ficus, Cicadulina mbira mbila, Coccomytilus halli, Coccus spp. such as Coccus hesperidum, Coccus longulus, Coccus pseudomagnoliarum, Coccus viridis, Cryptomyzus ribis, Cryptoneossa spp., Ctenarytaina spp., Dalbulus spp., Dialeurodes chittendeni, Dialeurodes citri, Diaphorina citri citri, Diaspis spp., Diuraphis spp., Doralis spp., Drosicha spp., Dysaphis spp.), for example, Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae, Dysmicoccus spp., Empoasca spp., for example, Empoasca abrupta, Empoasca fabae, Empoasca maligna, Empoasca solana, Empoasca stevensi, Eriosoma spp., for example, Eriosoma americanum, americanum, Eriosoma lanigerum, Eriosoma pyricola, Erythroneura spp., Eucalyptolyma spp., Euphyllura spp., Euscelis bilobatus, Ferrisia spp., Fiorinia spp., Furcaspis oceanica, Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Hyalopterus pruni, Icerya spp. e.g. Icerya purchasi, Idiocerus spp., Idioscopus spp.), Laodelphax striatellus, Lecanium spp., e.g. Lecanium corni (=Parthenolecanium corni), Lepidosaphes spp., e.g. Lepidosaphes ulmi, Lipaphis erysimi, Lopholeucaspis japonica, Lycorma delicatula, Macrosiphum spp., e.g. Macrosiphum euphorbiae, Macrosiphum lily lilii, Macrosiphum rosae, Macrosteles facifrons, Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metcalfa pruinosa, Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., e.g. Myzus ascalonicus, Myzus cerasi, Myzus ligustrii, Myzus spp., e.g. Myzus spp., ... ligustri, Myzus ornatus, Myzus persicae, Myzus nicotianae, Nasonovia ribisnigri, Neomaskellia spp., Nephotettix spp.), e.g. Nephotettix cincticeps, Nephotettix nigropictus, Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp., Parabemisia myricae, Paratrioza spp., e.g. Paratrioza cockerelli, Parlatoria spp. spp., Pemphigus spp., for example, Pemphigus bursarius, Pemphigus populivenae, Peregrinus maidis, Perkinsiella spp., Phenacoccus spp., for example, Phenacoccus madeirensis, us madeirensis, Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., e.g. Phylloxera devastatrix, Phylloxera notabilis, Pinnaspis aspidistrae, Planococcus spp., e.g. Planococcus citri, Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., e.g. Pseudococcus calceolariae, Pseudococcus comstocki, Pseudococcus longispinus, Pseudococcus maritimus, Pseudococcus viburni, Psyllopsis spp., Psylla spp., e.g. Psylla buxi, Psylla mali, Psylla pyri, Pteromalus spp. spp.), Pulvinaria spp., Pyrilla spp., Quadraspidiotus spp.), such as Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus, Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., such as Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum padi, Rhopalosiphum rufiabdominale, rufiabdominale, Saissetia spp., e.g. Saissetia coffeae, Saissetia miranda, Saissetia neglecta, Saissetia oleae, Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sipha flava, Sitobion avenae, Sogata spp., Sogatella furcifera, Sogatodes spp. spp., Stictocephala festina, Siphoninus phillyreae, Tenalapha malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomasis spp.), Toxoptera spp., e.g. Toxoptera aurantii, Toxoptera citricidus, Trialeurodes vaporariorum, Trioza spp., e.g. Trioza diospyri, Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.;. from the order Heteroptera, for example, Aelia spp., Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., for example Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex piloselus; pilosellus, Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., e.g. Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius, Eurydema spp. spp., Eurygaster spp., Halyomorpha halys, Heliopeltis spp., Horcias nobilellus, Leptocorisa spp.), Leptocorisa varicornis, Leptoglossus occidentalis, Leptoglossus phyllopus, Lygocoris spp., e.g. Lygocoris pabulinus, Lygus spp., e.g. Lygus elisus, Lygus hesperus, Lygus lineolaris, Macropes excavatus, Megacopta cribraria, Miridae, Monalonion atratum atratum, Nezara spp., e.g. Nezara viridula, Nysius spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., e.g. Piezodorus guildinii, Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea castanea), Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.;. From the order Hymenoptera, for example, Acromyrmex spp., Athalia spp., for example Athalia rosae, Atta spp., Camponotus spp., Dolichovespula spp., Diprion spp., for example Diprion similis, Hoplocampa spp., for example Hoplocampa cookei, Hoplocampa testudinea, Lasius spp., Linepithema fuscata, humile, Monomorium pharaonis, Paratrechina spp., Paravespula spp., Plagiolepis spp., Sirex spp., e.g. Sirex noctilio, Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa spp., e.g. Vespa crabro, Wasmannia auropunctata, Xeris spp. spp.); From the order Isopoda, e.g., Armadillidium vulgare, Oniscus asellus, Porcellio scaber; From the order Isoptera, for example, Coptotermes spp., such as Coptotermes formosanus, Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Kalotermes spp., Microtermes obesi, Nasutitermes spp., Odontotermes spp., Porotermes spp., Reticulitermes spp., such as Reticulitermes flavipes, flavipes, Reticulitermes hesperus; from the order of Lepidoptera, for example, Achroia grisella, Acronicta major, Adoxophyes spp., for example Adoxophyes orana, Aedia leucomelas, Agrotis spp., for example Agrotis segetum, Agrotis ipsilon, Alabama spp., for example Alabama argillacea, Amyelois transitella, Anarsia spp., Anticarsia spp. spp., such as Anticarsia gemmatalis, Argyroploce spp., Autographa spp., Barathra brassicae, Blastodacna atra, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp.), e.g. Chilo plejadellus, Chilo suppressalis, Choreutis pariana, Choristoneura spp., Chrysodeixis chalcites, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp. spp., e.g. Cydia nigricana, Cydia pomonella, Dalaca noctuides, Diaphania spp., Diparopsis spp., Diatraea saccharalis, Dioryctria spp., e.g. Dioryctria zimmermani, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp. spp., for example, Ephestia elutella, Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Erannis spp.), Erschoviella musculana, Etiella spp., Eudocima spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., for example Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Gracilaria spp., Grapholitha spp., for example Grapholitha molesta molesta, Grapholita prunivora, Hedylepta spp., Helicoverpa spp., for example Helicoverpa armigera, Helicoverpa zea, Heliothis spp., for example Heliothis virescens, Hepialus spp., for example Hepialus humuli, Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padera padella, Kakivoria flavofasciata, Lampides spp., Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp.), for example, Leucoptera coffeella, Lithocolletis spp., for example, Lithocolletis blancardella, Lithophane antennata, Lobesia spp., for example, Lobesia botrana, Loxagrotis albicosta, Lymantria spp., for example, Lymantria dispar, Lyonetia spp., for example, Lyonetia clerkella, Malacosoma neustria, neustria, Maruca testulalis, Mamestra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Omphisa spp., Operophtera spp., Oria spp., Orthaga spp., Ostrinia spp. spp., e.g. Ostrinia nubilalis, Panolis flammea, Parnara spp., Pectinophora spp., e.g. Pectinophora gossypiella, Perileucoptera spp., Phthorimaea spp.), for example, Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycter spp., for example, Phyllonorycter blancardella, Phyllonorycter crataegella, Pieris spp., for example, Pieris rapae, Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella (=Plutella maculipennis), Podesia spp., for example Podesia syringae, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., for example Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., for example Schoenobius bipunctifer, Scirpophaga spp. spp., e.g., Scirpophaga innotata, Scotia segetum, Sesamia spp., e.g., Sesamia inferens, Sparaganothis spp., Spodoptera spp.), such as Spodoptera eradiana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera praefica, Stathmopoda spp., Stenoma spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thaumetopoea spp., Thermesia gemmatalis, Tinea croacella, cloacella), Tinea pellionella, Chi. Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., e.g. Trichoplusia ni, Tryporyza incertulas, Tuta absoluta, Viracola spp.; From the order Orthoptera or Saltatoria, for example Acheta domesticus, Dichroplus spp., Gryllotalpa spp., for example Gryllotalpa gryllotalpa, Hieroglyphus spp., Locusta spp., for example Locusta migratoria, Melanoplus spp., for example Melanoplus devastator, Paratlanticus ussuriensis, Schistocerca gregaria; From the order Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Phthirus pubis, Trichodectes spp.; From the order Psocoptera, for example, Lepinotus spp., Liposcelis spp.; From the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp., for example Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis; from the order Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, tritici, Frankliniella vaccinii, Frankliniella williamsi, Haplothrips spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp., e.g. Thrips palmi, Thrips tabaci; From the order Zygentoma (=Thysanura), e.g., Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; from the class of the Symphyla, for example, Scutigerella spp., for example, Scutigerella immaculata; Pests from the phylum Mollusca, for example Bivalvia, for example Dreissena spp.; and also from the class of the Gastropoda, for example, Arion spp., for example Arion ater rufus, Biomphalaria spp., Bulinus spp., Deroceras spp., for example Deroceras laeve, Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.; Plant pests from the phylum Nematoda, i.e. plant parasitic nematodes, in particular Aglenchus spp., for example Aglenchus agricola, Anguina spp., for example Anguina tritici, Aphelenchoides spp., for example Aphelenchoides arachidis, Aphelenchoides fragariae, Belonolaimus spp., for example Belonolaimus gracilis, Belonolaimus longicausatus, longicaudatus, Belonolaimus nortoni, Bursaphelenchus spp., for example Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus, Cacopaurus spp., for example Cacopaurus pestis, Criconemella spp., for example Criconemella curvata, Criconemella onoensis, Criconemella ornata ornata, Criconemella rusium, Criconemella xenoplax (=Mesocriconema xenoplax), Criconemoides spp.), for example, Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum, Ditylenchus spp., for example, Ditylenchus dipsaci, Dolichodorus spp., Globodera spp., for example, Globodera pallida, Globodera rostochiensis, Helicotylenchus spp., for example, Helicotylenchus dihystera, dihystera, Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp., for example Heterodera avenae, Heterodera glycines, Heterodera schachtii, Hirschmaniella spp., Hoplolaimus spp., Longidorus spp., for example Longidorus africanus, Meloidogyne spp., for example Meloidogyne kitwooji chitwoodi, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita, Meloinema spp., Nacobbus spp., Neotylenchus spp., Paralongidorus spp.), Paraphelenchus spp., Paratrichodorus spp., for example Paratrichodorus minor, Paratylenchus spp., Pratylenchus spp., for example Pratylenchus penetrans, Pseudohalenchus spp., Psilenchus spp., Punctodera spp., Quinisulcius spp., Radopholus spp., for example Radopholus citrophilus citrophilus, Radopholus similis, Rotylenchulus spp., Rotylenchus spp., Scutellonema spp., Subanguina spp., Trichodorus spp., e.g. Trichodorus obtusus, Trichodorus primitivus, Tylenchorhynchus spp., e.g. Tylenchorhynchus annulatus, Tylenchulus spp. spp., e.g., Tylenchulus semipenetrans, Xiphinema spp., e.g., Xiphinema index.

[0078] The compounds of formula (I) can optionally be used as herbicides, safeners, growth regulators or plant property improving agents at certain concentrations or at certain application rates, or as microbicides or gametocides, for example as fungicides, antimycotics, bactericides or viricides, which also include agents acting against viroids, or as agents acting against MLOs (mycoplasma-like organisms) and RLOs (rickettsia-like organisms). Where appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.

[0079] Formulation / Use The invention further relates to formulations, in particular formulations for controlling unwanted pests, which can be applied to the pests and / or their habitat.

[0080] The formulations of the invention can be provided to the end user as "ready-to-use" use forms, i.e. the formulations can be applied directly to plants or seeds by suitable equipment, such as spraying or dispersing equipment. Alternatively, the formulations can be provided to the end user in the form of concentrates, which must be diluted, preferably with water, before use. Thus, unless otherwise specified, the expression "formulation" refers to such concentrates, whereas the expression "use form" refers to the "ready-to-use" solution for the end user, i.e. the end use form, usually as such a diluted formulation.

[0081] The formulations of the present invention can be prepared in a conventional manner, for example by mixing a compound of the present invention with one or more suitable adjuvants as disclosed herein.

[0082] The formulations comprise at least one compound of the invention and at least one agriculturally suitable adjuvant, such as a carrier and / or surfactant.

[0083] Carriers are solid or liquid natural or synthetic organic or inorganic substances that are usually inert. Carriers are usually those that improve the application of the compound to, for example, plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, especially ammonium sulfates, ammonium phosphates and ammonium nitrates, natural rock powders such as kaolins, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel and synthetic rock powders such as finely divided silica, alumina and silicates. Examples of solid carriers that are typically useful for making granules include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic powders and granules of organic materials such as paper, sawdust, coconut shells, corn cobs and tobacco stalks. Examples of suitable liquid carriers include, but are not limited to, organic solvents and combinations thereof.Examples of suitable solvents include, for example, aromatic and non-aromatic hydrocarbons (e.g., cyclohexane, paraffins, alkylbenzenes, xylene, toluene, tetrahydronaphthalene, alkylnaphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyhydric alcohols (which may be substituted, etherified and / or esterified; e.g., ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycols), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone or cyclohexanone), esters (including fats and oils) and (poly)ethers, substituted and / or etherified. These include polar and non-polar organic chemical liquids from the classes of unsubstituted and substituted amines, amides (e.g. dimethylformamide or / and fatty acid amides) and their esters, lactams (e.g. N-alkylpyrrolidones, especially N-methylpyrrolidone) and lactones, sulfones and sulfoxides (e.g. dimethyl sulfoxide), oils of vegetable or animal origin, nitriles (alkyl nitriles such as acetonitrile, propionitrile, butyronitrile, or aromatic nitriles such as benzonitrile), carbonates (cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, or dialkyl carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate, etc.). The carrier can also be a liquefied gas extender, i.e. a liquid that is gaseous at normal temperature and pressure, for example an aerosol propellant such as halohydrocarbons, butane, propane, nitrogen and carbon dioxide.

[0084] Preferred solid supports are selected from clays, talcs and silicas.

[0085] Preferred liquid carriers are selected from water, fatty acid amides and esters thereof, aromatic and non-aromatic hydrocarbons, lactams, lactones, carbonates, ketones, (poly)ethers.

[0086] The amount of the carrier will typically range from 1 to 99.99% by weight of the formulation, preferably from 5 to 99.9%, more preferably from 10 to 99.5% by weight, and most preferably from 20 to 99% by weight.

[0087] The liquid carrier will typically be present in the range of 20 to 90% by weight of the formulation, for example 30 to 80% by weight.

[0088] The solid carrier is typically present in the range of 0 to 50% by weight, preferably 5 to 45% by weight, for example 10 to 30% by weight of the formulation.

[0089] When the formulation includes two or more carriers, the ranges outlined refer to the total amount of carriers.

[0090] The surfactant may be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as an ionic or non-ionic emulsifier, foaming agent, dispersant, wetting agent, penetration enhancer and any mixture thereof. Examples of suitable surfactants include salts of polyacrylic acid, ethoxylated poly(α-substituted)acrylate derivatives, salts of lignosulfonic acid (e.g. sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and / or propylene oxide with or without alcohol, fatty acids or fatty amines (e.g. polyoxyethylene fatty acid esters, e.g. castor oil ethoxylate, polyoxyethylene fatty alcohol ethers, e.g. alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenol ... These include, but are not limited to, salts of sulfosuccinates, taurine derivatives (preferably alkyl taurates), phosphate esters of polyethoxylated alcohols or phenols, fatty esters of polyhydric alcohols (such as fatty acid esters of glycerol, sorbitol or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (e.g., alkyl sulfonates, aryl sulfonates and alkyl benzene sulfonates), sulfonated polymers of naphthalene / formaldehyde, phosphate esters, protein hydrolysates, lignosulfite waste liquor and methylcellulose. References to salts in this paragraph preferably refer to the respective alkali, alkaline earth and ammonium salts.

[0091] Preferred surfactants are selected from ethoxylated poly(α-substituted) acrylate derivatives, polycondensates of alcohols with ethylene oxide and / or propylene oxide, polyoxyethylene fatty acid esters, alkylbenzene sulfonates, sulfonated polymers of naphthalene / formaldehyde, polyoxyethylene fatty acid esters such as castor oil ethoxylates, sodium lignosulfonates and arylphenol ethoxylates.

[0092] The amount of surfactant will typically be in the range 5 to 40% by weight of the formulation, for example 10 to 20%.

[0093] Further examples of suitable auxiliaries include water repellents, drying agents, binders (adhesives, tackifiers, fixatives, e.g. carboxymethylcellulose, natural and synthetic polymers in the form of powders, granules or latexes, e.g. gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids, e.g. cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone and tyloses), thickeners and secondary thickeners (cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, e.g. the products available under the name Bentone, and finely divided silica), stabilizers (e.g. low-temperature stabilizers, preservatives (e.g. dichlorophen, benzyl alcohol hemiformal, 1,2-benzisothiazo phosphoric-3-one, 2-methyl-4-isothiazolin-3-one), antioxidants, light stabilizers, especially UV stabilizers, or other agents which improve chemical and / or physical stability), dyes or pigments (e.g. inorganic pigments, such as iron oxide, titanium oxide and Prussian blue; organic dyes, such as alizarin, azo and metal phthalocyanine dyes), defoamers (e.g. silicone-based defoamers and magnesium stearate), antifreeze agents, spreading agents, gibberellins and processing aids, mineral and vegetable oils, fragrances, waxes, nutrients (e.g. micronutrients, e.g. salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrating agents, sequestering agents and complexing agents.

[0094] The choice of auxiliary depends on the intended application form of the compound of the present invention and / or the physical properties of the compound.Furthermore, auxiliary can be selected to provide specific properties (technical, physical and / or physiological properties) to the formulation or the use form produced therefrom.The choice of auxiliary can customize the formulation to specific needs.

[0095] The formulations contain an insecticidally / acaricidal / nematicidally effective amount of the compounds of the invention. The term "effective amount" means an amount sufficient to control harmful insects / mites / nematodes on cultivated plants or in the protection of materials, causing little damage to the plants being treated. Such amounts can vary widely and depend on various factors such as the insect / mite / nematode species to be controlled, the cultivated plants or materials to be treated, the climatic conditions and the particular compound of the invention used. Usually, the formulations according to the invention contain 0.01-99% by weight, preferably 0.05-98% by weight, more preferably 0.1-95% by weight, even more preferably 0.5-90% by weight, most preferably 1-80% by weight of the compounds of the invention. I formulations can contain two or more compounds of the invention. In such cases, the outlined ranges refer to the total amount of the compounds of the invention.

[0096] The formulations of the present invention can be of any conventional formulation type, such as solutions (e.g., aqueous solutions), emulsions, water- and oil-based suspensions, dusts (e.g., wettable powders, soluble powders), dusts, pastes, granules (e.g., soluble granules, granules for spreading), suspoemulsion formulations, natural or synthetic products impregnated with the compounds of the present invention, fertilizers, and microencapsulation in polymeric materials.The compounds of the present invention can be present in suspended, emulsified or dissolved form. Examples of particularly suitable formulation types are liquids, water-soluble concentrates (e.g. SL, LS), dispersible concentrates (DC), suspensions and suspension concentrates (e.g. SC, OD, OF, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME, SE), capsules (CS, ZC, etc.), pastes, lozenges, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), compacts (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticides (e.g. LN) and gel formulations for the treatment of plant propagation material such as seeds (e.g. GW, GF). These and other formulation types are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview can be found in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, Croplife International.

[0097] Preferably, the formulation of the present invention is in the form of one of the following types: EC, SC, FS, SE, OD, WG, WP, CS, more preferably EC, SC, OD, WG, CS.

[0098] Details of the types of formulations and examples of their preparation are provided below.When two or more compounds of the present invention are present, the outlined amount of the compounds of the present invention refers to the total amount of the compounds of the present invention.This also applies mutatis mutandis to any further components of the formulation when two or more representatives of such components are present, such as wetting agents, binders.

[0099] i) Water-soluble concentrates (SL, LS) 10-60% by weight of at least one compound of the invention and 5-15% by weight of a surfactant (e.g., a polycondensate of ethylene oxide and / or propylene oxide with an alcohol) are dissolved in water and / or a water-soluble solvent (e.g., an alcohol such as propylene glycol or a carbonate such as propylene carbonate) in such an amount that the total amount is 100% by weight. Before application, the concentrate is diluted with water.

[0100] ii) Dispersible Concentrate (DC) 5-25% by weight of at least one compound of the present invention and 1-10% by weight of a surfactant and / or binder (e.g., polyvinylpyrrolidone) are dissolved in an organic solvent (e.g., cyclohexanone) in an amount such that the total amount is 100% by weight, and diluted with water to obtain a dispersion.

[0101] iii) Emulsifiable concentrate (EC) 15-70% by weight of at least one compound of the present invention and 5-10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in a water-insoluble organic solvent (e.g., an aromatic hydrocarbon or a fatty acid amide) and, if necessary, an additional water-soluble solvent in an amount such that the total amount is 100% by weight. Dilute with water to obtain an emulsion.

[0102] iv) Emulsions (EW, EO, ES) 5-40% by weight of at least one compound of the present invention and 1-10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate, or a polycondensate of ethylene oxide and / or propylene oxide with or without alcohol) are dissolved in 20-40% by weight of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon). This mixture is added to water in an amount to make the total amount 100% by weight by an emulsifier. The resulting formulation is a homogeneous emulsion. Before application, the emulsion can be further diluted with water.

[0103] v) Suspensions and suspension concentrates v-1) Water system (SC, FS) In a suitable grinding device, for example an agitator ball mill, 20-60% by weight of at least one compound according to the invention is ground with 2-10% by weight of surfactants (for example sodium lignosulfonate and polyoxyethylene fatty alcohol ethers), 0.1-2% by weight of a thickener (for example xanthan gum) and water to obtain a fine active substance suspension. The water is added in such an amount that the total amount is 100% by weight. Dilution with water results in a stable suspension of the active substance. In the case of FS type formulations, up to 40% by weight of a binder (for example polyvinyl alcohol) is added.

[0104] v-2) Oil-based (OD, OF) In a suitable grinding device, for example an agitator ball mill, 20-60% by weight of at least one compound according to the invention is ground with 2-10% by weight of surfactants (for example sodium lignosulfonate and polyoxyethylene fatty alcohol ethers), 0.1-2% by weight of thickeners (for example modified clays, in particular Bentone, or silica) and an organic carrier to obtain a finely divided active substance oil suspension. The organic carrier is added in such an amount that the total amount is 100% by weight. Dilution with water is performed to obtain a stable dispersion of the active substance.

[0105] vi) Water dispersible granules and water-soluble granules (WG, SG) 1-90% by weight, preferably 20-80% by weight, most preferably 50-80% by weight, of at least one compound of the invention is pulverized with surfactants (e.g. sodium lignosulfonate and sodium alkylnaphthylsulfonate) and potentially carrier materials and converted into water dispersible granules or water-soluble granules by typical technical equipment such as extrusion, spray drying, fluidized bed granulation, etc. The surfactants and carrier materials are used in such amounts that the total amount is 100% by weight. Dilution with water gives a stable dispersion or solution of the active substance.

[0106] vii) Hydrated powder and water-soluble powder (WP, SP, WS) 50-80% by weight of at least one compound of the present invention is ground in a rotor-stator mill with 1-20% by weight of a surfactant (e.g., sodium lignosulfonate, sodium alkylnaphthylsulfonate) and a solid carrier, such as silica gel, in an amount such that the total amount is 100% by weight, and diluted with water to obtain a stable dispersion or solution of the active substance.

[0107] viii) Gel (GW, GF) In a stirred ball mill, 5-25% by weight of at least one compound of the invention is milled with 3-10% by weight of a surfactant (e.g., sodium lignosulfonate), 1-5% by weight of a binder (e.g., carboxymethylcellulose) and an amount of water such that the total amount is 100% by weight. This gives a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

[0108] ix) Microemulsion (ME) 5-20% by weight of at least one compound of the present invention is added to 5-30% by weight of an organic solvent mixture (e.g., fatty acid dimethylamide and cyclohexanone), 10-25% by weight of a surfactant mixture (e.g., polyoxyethylene fatty alcohol ether and arylphenol ethoxylate), and an amount of water to bring the total to 100% by weight. The mixture is stirred for 1 hour, and a thermodynamically stable microemulsion is spontaneously formed.

[0109] x) Microcapsules (CS) An oil phase containing 5-50% by weight of at least one compound of the present invention, 0-40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and 2-15% by weight of an acrylic monomer (e.g., methyl methacrylate, methacrylic acid, and di- or triacrylate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol). Poly(meth)acrylate microcapsules are formed by radical polymerization initiated by a radical initiator. Alternatively, an oil phase containing 5-50% by weight of at least one compound of the present invention, 0-40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol), thereby forming a polyurea microcapsule. Optionally, the addition of a polyamine (e.g., hexamethylenediamine) is also used to form the polyurea microcapsule. The monomer represents 1-10% by weight of the total CS formulation.

[0110] xi) Dustable powder (DP, DS) 1-10% by weight of at least one compound of the present invention is finely ground and thoroughly mixed with a solid carrier, such as finely ground kaolin, in an amount sufficient to bring the total to 100% by weight.

[0111] xii) Granules (GR, FG) 0.5 to 30% by weight of at least one compound of the invention is finely ground and combined with a solid carrier (eg, a silicate) in an amount sufficient to bring the total to 100% by weight.

[0112] xiii) Ultra low volume liquid (UL) 1-50% by weight of at least one compound of the present invention is dissolved in an organic solvent, such as an aromatic hydrocarbon, in an amount such that the total amount is 100% by weight.

[0113] Formulations of types i) to xiii) may optionally contain further auxiliaries, such as 0.1 to 1% by weight of a preservative, 0.1 to 1% by weight of an antifoaming agent, 0.1 to 1% by weight of a dye and / or pigment, and 5 to 10% by weight of an antifreeze agent.

[0114] mixture The compounds of formula (I) can also be used in mixtures with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbicides, beneficial species, herbicides, fertilizers, bird repellents, phytotonic agents, sterilants, safeners, semiochemicals and / or plant growth regulators, for example to broaden the spectrum of action, extend the duration of action, increase the rate of action, prevent repulsion or prevent the development of resistance. Furthermore, such active compound combinations can improve plant growth and / or improve resistance to abiotic factors (e.g. high or low temperatures), to drought or to elevated salt content in water or soil. Furthermore, it may be possible to improve flowering and fruiting performance, optimize germination ability and root development, facilitate harvesting, increase yield, affect maturation, improve the quality and / or nutritional value of the harvested produce, increase the storage life of the harvested produce, and / or improve the processability of the harvested produce.

[0115] Furthermore, the compounds of formula (I) can be present in a mixture with other active compounds or semiochemicals (e.g. attractants, and / or bird repellents, and / or plant activators, and / or growth regulators, and / or fertilizers). Similarly, the compounds of formula (I) can be used to improve plant properties (e.g. growth, yield and quality of the harvested product).

[0116] In a particular embodiment according to the invention, the compound of formula (I) is present in the formulation or in the use form prepared from such a formulation in admixture with further compounds, preferably the compounds described below.

[0117] If one of the compounds described below can exist in various tautomeric forms, these are also included, even if not explicitly mentioned in each case. Moreover, all named mixture partners may, if possible due to their functional groups, form salts with suitable bases or acids.

[0118] Insecticides / Acaricides / Nematocides The active compounds identified herein by common name are known and can be found, for example, in The Pesticide Manual, 16th Ed., British Crop Protection Council 2012, or on the internet (e.g., http: / / www.alanwood.net / pesticides). Classification is based on the IRAC Mode of Action Classification Scheme as of the filing date of this patent application.

[0119] (1) Acetylcholinesterase (AChE) inhibitors, preferably carbamates selected from alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate , dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famfur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyaphos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl)salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydimeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimphos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion.

[0120] (2) GABA-gated chloride channel blockers, preferably cyclodiene organochlorines selected from chlordane and endosulfan; or phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

[0121] (3) Sodium channel regulators, preferably acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin s-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-( pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) isomer], tralomethrin, and transfluthrin, or pyrethroids selected from DDT or methoxychlor.

[0122] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam; or nicotine; or sulfoximines selected from sulfoxaflor; or butenolides selected from flupyradifurone; or mesoionic compounds selected from triflumezopyrim.

[0123] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators (site I), preferably spinosyns selected from spinetoram and spinosad.

[0124] (6) GluCl-gated chloride channel (GluCl) allosteric modulators, preferably avermectins / milbemycins selected from abamectin, emamectin benzoate, lepimectin, and milbemectin.

[0125] (7) Juvenile hormone mimetics, preferably juvenile hormone analogs selected from hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.

[0126] (8) Various non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides or chloropicrin or sulfuryl fluoride or borax or tartar emetic, or methyl isocyanate generators selected from dazomet and metham.

[0127] (9) Chordotonal TRPV channel modulators, preferably pyridineazomethanes selected from pymetrozine and pyrifluquinazone, or pyropenes selected from afidopyropene.

[0128] (10) A mite growth inhibitor that affects CHS1 selected from clofentezine, hexythiazox, diflovidazine and etoxazole.

[0129] (11) Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis tenebrionis), and a Bt plant protein selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, and Cry34 / 35Ab1.

[0130] (12) Inhibitors of mitochondrial ATP synthase, preferably ATP disruptors selected from diafenthiuron or organotin compounds selected from azocyclotin, cyhexatin and fenbutatin oxide or propargite or tetradifon. (13) An uncoupler of oxidative phosphorylation by proton gradient destruction selected from chlorfenapyr, DNOC, and sulfluramide.

[0131] (14) A nicotinic acetylcholine receptor channel blocker selected from bensultap, cartap hydrochloride, thiosultap-sodium.

[0132] (15) Inhibitors of chitin biosynthesis that affect CHS1, preferably benzoylureas selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.

[0133] (16) An inhibitor of chitin biosynthesis selected from buprofezin, type 1.

[0134] (17) Molting disruptors selected from Cyromagines (especially in the order Diptera, i.e., Diptera).

[0135] (18) Ecdysone receptor agonists, preferably diacylhydrazines selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0136] (19) An octopamine receptor agonist selected from amitraz.

[0137] (20) A mitochondrial complex III electron transport inhibitor selected from hydramethylnon, acequinocyl, fluacrypyrim, and bifenazate.

[0138] (21) Mitochondrial complex I electron transport inhibitors, preferably METI acaricides and insecticides selected from fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).

[0139] (22) Voltage-dependent sodium channel blockers, preferably oxadiazines selected from indoxacarb, or semicarbazones selected from metaflumizone.

[0140] (23) Inhibitors of acetyl-CoA carboxylase, preferably tetronic acid derivatives and tetramic acid derivatives selected from spirodiclofen, spiromesifen, spiropydione and spirotetramate.

[0141] (24) Mitochondrial complex IV electron transport inhibitors, preferably phosphides selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanides selected from calcium cyanide, potassium cyanide and sodium cyanide.

[0142] (25) Mitochondrial complex II electron transport inhibitors, preferably β-ketonitrile derivatives selected from cyenopyrafen and cyflumetofen, or carboxanilides selected from piflubumid.

[0143] (28) Ryanodine receptor modulators, preferably diamides selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

[0144] (29) A chordotonal organ modulator selected from flonicamide (target site undefined).

[0145] (30) A GABA-gated chloride channel allosteric modulator, preferably a metadiamide selected from broflanilide, or an isoxazole selected from fluxamethamide.

[0146] (31) A granulovirus (GV) selected from Baculovisuses, preferably Cydia pomonella GV and Thaumatotibia leucotreta (GV), or a nuclear polyhedrosis virus (NPV) selected from Anticarsia gemmatalis MNPV and Helicoverpa armigera NPV.

[0147] (32) Nicotinic acetylcholine receptor allosteric modulators (site II) selected from GS-omega / kappa HXTX-Hv1a peptides.

[0148] (33) Acinonapyr, Afoxolayner, Azadirachtin, Benclothiaz, Benzoximate, Benzpyrimoxane, Bromopropylate, Quinomethionate, Chloroprallethrin, Cryolite, Cyclobutrifluram, Cycloxapride, Sietopyrafen, Cyhalodiamide, Cyprofuranilide (CAS 2375110-88-4), Dichloromezothiaz, Dicofol, Dimpropyridaz, ε-Metofluthrin, ε-Momfluthrin, Flumetquin, Fluazaindolizine, Fluensulfone, Flufenerim, Flufenoxystrobin, Flufiprole, Fluhexafon, Fluopyram, Flupirimine, Fluralaner, Fufenozide, Flupentiofenox, Guadipyr, Heptaf Further active compounds selected from Lutrin, Imidaclotiz, Iprodione, Isocycloceram, κ-Bifenthrin, κ-Tefluthrin, Lotilaner, Meperfluthrin, Nicofluprol (CAS 1771741-86-6), Oxazosulfil, Paichongding, Pyridalyl, Pyrifluquinazon, Pyriminostrobin, Sarolaner, Spidoxamato, Spirobudiclofen, Tetramethylfluthrin, Tetrachlorantraniliprole, Tigolaner, Thioxazaphene, Thiofluoximate, Cyclopyrazoflurane, Iodomethane; and further active compounds selected from Bacillus firmus (Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), as well as the following compound: 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-Triazol-5-amine (known from WO2006 / 043635) (CAS 885026-50-6), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP2647626) (CAS-1440516-42-6), PF1364 (known from JP2010 / 018586) (CAS 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoropropan-2-one (known from WO2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from CN103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-Dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (known from WO2013 / 050317A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]-propanamide (known from WO2013 / 162715A2, WO2013 / 162716A2, US2014 / 0213448A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN101337937A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN103109816A) (CAS 1232543-85-9; N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO2012 / 034403A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from WO2011 / 085575A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-Dichloro-2-propen-1-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN101337940A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN101715774A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylic acid ester (known from CN103524422A) (CAS 1542271-46-4;(4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-carboxylic acid methyl ester (known from CN102391261A) (CAS 1370358-69-2);6-deoxy-3-O-ethyl-2,4-di-O-methyl-1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-Triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US2014 / 0275503A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 1253850-56-4), (8-anti)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (known from WO2007040280A1 and WO2007040282A1) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (CN 103265527A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014 / 187846A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl-carbonic acid ethyl ester (known from WO 2010 / 066780A1, WO 201 1151146A1) (CAS1229023-00-0), N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-1,2,3-triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS1594637-65-6), N-[1-(3,5-difluoro-2-pyridinyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO2014 / 053450A1) (CAS1594626-19-3), (3R)-3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (known from WO2018 / 177970A1) (CAS2246757-58-2); 3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)-propanamide (known from WO2019 / 236274A1) (CAS2396747-83-2), N-[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-3-[(4-fluorobenzoyl)amino]-benzamide (known from WO2019059412A1) (CAS1207977-87-4).

[0149] Fungicides The active ingredients specified herein by common name are well known and described, for example in the Pesticides Manual (16th Ed. British Crop Protection Council) or can be found on the internet (e.g. www.alanwood.net / pesticides ) can be searched for.

[0150] All listed fungicide mixing partners of classes (1) to (15) can optionally form salts with suitable bases or acids, if their functional groups allow. All listed mixing partners of classes (1) to (15) can include tautomers, if applicable.

[0151] 1) Inhibitors of ergosterol biosynthesis, for example: (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) ) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1 H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol (1.029) (2R)-2-(1-chlorocyclopropyl) -4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030)(2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.031)(2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl) (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl )-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl )-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2 ,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1. 050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2, 4-Triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2- Methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(arylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(arylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(arylsulfanyl)- 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N′-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N′-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methyl Imidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N -ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5 -Bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide,. (1.081) Ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridyl]- 1-(1,2,4-Triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluoro-phenyl)-2-hydroxy-propyl]imidazole-4-carbonitrile and (1.086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridyl]oxy]benzonitrile.

[0152] 2) Inhibitors of the respiratory chain at complex I or complex II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (anti-epimer enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimer enantiomer 1S,4 R,9R), (2.012) Isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) Isopyrazam (mixture of syn-epimeric racemate (1RS,4SR,9RS) and anti-epimeric racemate (1RS,4SR,9SR)), (2.014) Isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) Isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) Isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), (2.017) Penflufen, (2.018) Penthiopyrad, (2.019) Pydiflumetofen, (2.020) Pyraziflumid, (2.021) Sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) Inpirfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) Fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3 -dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorophenyl)phenyl (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide (2.037) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5- Fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoro Methyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048 ) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoine.

[0153] 3) Inhibitors of the respiratory chain at complex III, such as (3.001) amethoctrazine, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fumarolide, Ruoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N- Methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) Fenpicoxamide, (3.026) Mandestrobin , (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) methyltetraprole, (3.031) florylpicoxamide.

[0154] 4) Mitosis and cell division inhibitors, for example: (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)- (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1 ,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

[0155] 5) Compounds capable of multisite action, for example: (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper chloride basic, (5.009) copper(2+) sulfate, (5.010) dithianone, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) mancozeb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine copper, (5.018) propineb, (5.019) sulphur and sulphur agents such as calcium polysulphide, (5.020) thiuram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0156] 6) Compounds capable of inducing host defenses, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) thiadinil.

[0157] 7) Inhibitors of amino acid and / or protein biosynthesis, for example (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

[0158] 8) ATP production inhibitors, for example, (8.001) Silthiofam.

[0159] 9) Inhibitors of cell wall synthesis, for example: (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0160] 10) Inhibitors of lipid and membrane synthesis, for example, (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

[0161] 11) Inhibitors of melanin biosynthesis, for example, (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl{3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.

[0162] 12) Inhibitors of nucleic acid synthesis, for example, (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

[0163] 13) Signal transduction inhibitors, for example: (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazide, (13.005) quinoxyfen, (13.006) vinclozolin.

[0164] 14) Compounds which can act as uncouplers, for example, (14.001) fluazinam, (14.002) meptyldinocap.

[0165] 15) (15.001) Abscisic acid, (15.002) Benthazole, (15.003) Bethoxazin, (15.004) Capsimycin, (15.005) Carvone, (15.006) Quinomethionate, (15.007) Kufuraneb, (15.008) Cyflufenamid, (15.009) Cymoxanil, (15.010) Cyprosulfamide, (15.011) Flutianil, (15.012) Fosetyl aluminum, (15.013) Fosetyl calcium, (15.014) Fosetyl-sodium, (15.015) Methyl isothiocyanate, (15.016) Metrafenone, (15.017) Mildiomycin, (15.018) Natamycin, (15.019) Nickel dimethyldithiocarbamate, (15.020) Nitrothal-isopropyl, (15.021) Oxamocarb, (15.022) Oxathiapiproline, (15.023) Oxyfenthiin, (15.024) Pentachlorophenol and salts, (15.025 ) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriophenone (chlazafenone), (15.028) tebufloquine, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidine-1- (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipimethitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoro methyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl Methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) ipflufenoquine, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiproline, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-Phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumerine, (15.048) 4-amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N′-phenyl-N′-(prop-2-yn-1-yl)thiophene 2-Sulfonohydrazide, (15.052) 5-Fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-Fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-Fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) Buta- 3-yn-1-yl{6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) (2Z)-3-amino-2-cyano-3-phenylacrylic acid ethyl ester, (15.057) phenazine-1-carboxylic acid, (15.058) 3,4,5-trihydroxybenzoic acid propyl ester, (1 5.059) Quinolin-8-ol, (15.060) Quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonate nyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066)(2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067)(5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068)(3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069)(1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2, 4-oxadiazol-3-yl]benzamide), (15.074) (methyl{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}carbamate), (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyiminomethyl]-4-[5-( trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carbonimidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-benzamide, (15.084) N-[(Z)-N-meth (15.085) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]-methyl]propanamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, ,2,4-Oxadiazol-3-yl]-benzenecarbothioamide, (15.088) 5-Methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1-Methoxy-1-methyl-3-[[4-[5-(trifluoromethyl}-1,2,4- oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-Ethyl-2-methyl-N-[[. 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidine-2-one, (15.103) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.105) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.106) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.109) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.110) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.111) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1-[[3-fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one, (15.106) 4,4-dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one (15.107) 5,5-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) ethyl(1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazol-4-yl)acetate, (15.109) N,N-dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine and (15.110) A further fungicide selected from the group consisting of N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamides.

[0166] Biocontrol agents as mixture components The compounds of formula (I) may be combined with a biopesticide.

[0167] Biological pesticides include, inter alia, bacteria, fungi, yeasts, plant extracts and products formed by microorganisms (eg proteins or secondary metabolites).

[0168] Biological pesticides include bacteria, such as spore-forming bacteria, root-colonizing bacteria and bacteria which act as biological insecticides, fungicides or nematicides.

[0169] Examples of such bacteria that are used or can be used as biopesticides are: Bacillus amyloliquefaciens strain FZB42 (DSM 231179), or Bacillus cereus, in particular B. cereus strain CNCM I-1562, or Bacillus firmus strain I-1582 (accession number CNCM I-1582), or Bacillus pumilus, in particular strain GB34 (accession number ATCC 700814) and strain QST2808 (accession number NRRL B-30087), or Bacillus subtilis, in particular strain GB03 (accession number ATCC SD-1397), or Bacillus subtilis strain QST713 (accession number NRRL B-21661), or Bacillus subtilis strain OST 30002 (accession number NRRL B-50421), Bacillus thuringiensis, in particular B. thuringiensis subspecies israelensis (antigen type H-14) strain AM65-52 (accession number ATCC 1276), or B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), or B. thuringiensis subsp. kurstaki strain HD-1, or B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp.) (Rotylenchulus reniformis nematode)-PR3 (accession number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), and Streptomyces galbus strain AQ 6047 (accession number NRRL 30232).

[0170] Examples of fungi and yeasts that are or can be used as biopesticides are:

[0171] Beauveria bassiana, in particular the strain ATCC 74040, Coniothyrium minitans, in particular the strain CON / M / 91-8 (accession number DSM-9660), Lecanicillium spp., in particular the strain HRO LEC 12, Lecanicillium lecanii (formerly known as Verticillium lecanii), in particular the strain KV01, Metarhizium anisopliae, in particular the strain F52 (DSM3884 / ATCC 90448), Metschnikowia fructicola, in particular the strain NRRL Y-30752, Paecilomyces fumosoroseus (now: Isaria fumosorosea), in particular the strain IFPC 200613 or the strain Apopka 97 (accession number ATCC 20874), Paecilomyces lilacinus, in particular the P. lilacinus strain 251 (AGAL 89 / 030550), Talaromyces flavus, in particular the strain V117b, Trichoderma atroviride, in particular the strain SC1 (accession number CBS 122089), Trichoderma harzianum, in particular the strain IFPC 200613 or the strain Apopka 97 (accession number ATCC 20874), harzianum), in particular Trichoderma harzianum rifai (T. harzianum rifai) T39 (accession number CNCM I-952).

[0172] Examples of viruses that are or can be used as biological controls are: Adoxophyes orana granulosis virus (GV), codling moth (Cydia pomonella) granulosis virus (GV), Helicoverpa armigera nuclear polyhedrosis virus (NPV), Spodoptera exigua mNPV, Spodoptera frugiperda mNPV, and African cotton leafworm (Spodoptera littoralis) NPV.

[0173] Also included are bacteria and fungi that are added as "inoculants" to plants or plant parts or plant organs and that, due to their specific properties, promote plant growth and plant health. Examples that may be mentioned include:

[0174] Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly known as Pseudomonas cepacia), Gigaspora spp. or Gigaspora monosporum, Glomus spp., Laccaria spp. spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp.

[0175] Examples of plant extracts and products formed by microorganisms, including proteins and secondary metabolites, that are used or can be used as biopesticides are: Garlic (Allium sativum), Wormwood (Artemisia absinthium), Azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, Chitin, Armour-Zen, Dryopteris filix-mas, Horsetail (Equisetum arvense), Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), Pyrethrum / pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, ("Requiem® Insecticide"), rotenone, ryania / ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extracts, in particular rapeseed or mustard powder, as well as bioinsecticidal / acaricidal active substances obtained from olive oil, in particular those with carbon chain length C as active ingredients in products, for example under the trade name FLiPPER®. 16 -C 20 Unsaturated fatty / carboxylic acids having

[0176] Safeners as blend components The compounds of formula (I) may be used as safeners, for example benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0177] Plants and plant parts All plants and plant parts can be treated according to the invention. Here, plants are to be understood to mean all plants and plant parts, such as desirable and undesirable wild plants or crop plants (including naturally occurring crop plants), such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybean, potato, sugar beet, sugar cane, tomato, pepper, cucumber, melon, carrot, watermelon, onion, lettuce, spinach, leek, bean, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, rapeseed, and also fruit plants (fruits are apple, pear, citrus and grape). Crop plants can be plants obtainable by conventional breeding and optimization methods, or by biotechnological and genetic engineering methods, or by a combination of these methods. Such crop plants include transgenic plants and also plant varieties that may or may not be protected by plant variety property rights. Plants should be understood to mean all developmental stages, such as seeds, seedlings, young plants (immature plants) to mature plants. Plant parts should be understood to mean all parts and organs of the above-ground and below-ground parts of the plant, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as tubers, roots and rhizomes. Plant parts also include harvested plants or harvested plant parts, as well as vegetative and generative propagation material, such as seedlings, tubers, rhizomes, cuttings and seeds.

[0178] The treatment of plants and plant parts with the compounds of formula (I) according to the invention is carried out by customary treatment methods, for example by immersion, spraying, vaporization, fogging, broadcasting, painting, injection, etc., either directly or by applying the compounds to the surroundings, habitat or storage spaces of the plants and plant parts, and also, in the case of propagation material, in particular seeds, by applying one or more coatings.

[0179] As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, wild plant species and plant cultivars or plant species and cultivars obtained by conventional biological breeding methods such as crossing or protoplast fusion, as well as their parts, are treated. In yet another preferred embodiment, transgenic plants and plant cultivars obtained by genetic engineering methods, where appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The terms "parts" or "parts of plants" or "plant parts" have already been explained above. The invention is particularly preferably used to treat plants of individual commercial conventional cultivars or conventional cultivars in use. Plant cultivars should be understood to mean plants with new properties ("traits") obtained by conventional breeding or mutagenesis or recombinant DNA techniques. They can be cultivars, varieties, biotypes or genotypes.

[0180] Transgenic plants, seed treatments and integration events According to the present invention, the compounds of formula (I) can be advantageously used to treat transgenic plants, plant cultivars or plant parts that have received genetic material that confers advantageous and / or useful properties (traits) to these plants, plant cultivars or plant parts. It is therefore envisaged that the present invention can be combined with one or more recombinant traits or transgenic events, or combinations thereof. In the context of this application, a transgenic event is created by inserting a specific recombinant DNA molecule at a specific location (locus) within a chromosome of the plant genome. The insertion creates a new DNA sequence, called an "event", characterized by the inserted recombinant DNA molecule and some amount of genomic DNA flanking / adjacent both ends of the inserted DNA. Such traits or transgenic events include, but are not limited to, disease organism resistance, water use efficiency, yield performance, drought tolerance, seed quality, improved nutritional quality, hybrid seed production and herbicide tolerance, the traits being measured with respect to a plant lacking such trait or transgenic event. Examples of such advantageous and / or useful properties (traits) are better plant growth, vigor, stress resistance, self-sufficiency, lodging resistance, nutrient uptake, plant nutrients, and / or yield, in particular improved growth, increased resistance to high or low temperatures, improved resistance to drought or water or soil salinity levels, improved flowering performance, ease of harvesting, accelerated ripening, increased yield, improved quality and / or nutritional value of the harvested product, improved shelf life and / or processability of the harvested product, and increased resistance or tolerance to animal and microbial pests such as insects, arachnids, nematodes, mites, slugs and snails.

[0181] Among the DNA sequences encoding proteins that confer properties of resistance or tolerance to such animal and microbial pests, particularly insects, particular mention may be made of the genetic material from Bacillus thuringiensis encoding the Bt proteins, which have been widely described in the literature and are known to those skilled in the art, as well as proteins extracted from bacteria such as Photorhabdus (WO97 / 17432 and WO98 / 08932). In particular, the CryA, CryIAb, CryIAc, CryIIA, CryIIIA, CryIIIB2, Cry9cCry2Ab, Cry3Bb and CryIF proteins or toxic fragments thereof as well as hybrids or combinations thereof, in particular the CryIF protein or hybrids derived from the CryIF protein (e.g. hybrid CryIA-CryIF protein or toxic fragments thereof), CryIA type proteins or toxic fragments thereof, preferably the CryIAc protein or hybrids derived from the CryIAc protein (e.g. hybrid CryIAb-CryIAc protein) or the CryIAb or Bt2 protein or toxic fragments thereof, the Cry2Ae, Cry2Af or Cry2Ag protein or toxic fragments thereof, the CryIA.105 protein or toxic fragments thereof, the VIP3Aa19 protein, the VIP3Aa20 protein, the VIP3A protein produced in the COT202 or COT203 cotton event, Estruch et al., (1996), Proc Natl Acad Sci USA. 28;93(11):5389-94 or a toxic fragment thereof, a Cry protein as described in WO2001 / 47952, an insecticidal protein from Xenorhabdus, Serratia (in particular from S. entomophila) or from Photorhabdus species (as described in WO98 / 50427), e.g. a Bt Cry or VIP protein such as the Tc-protein from Photorhabdus as described in WO98 / 08932.Also included herein are variants or mutants of any of these proteins, or other proteins or peptides, which differ by several amino acids (1-10, preferably 1-5) from any of the above listed sequences, in particular the sequences of their toxic fragments, or which are fused to a transit peptide, e.g. a plastid transit peptide.

[0182] Another and particularly highlighted example of such a property is the conferred resistance to one or more herbicides, such as imidazolinones, sulfonylureas, glyphosate or phosphinothricin. Among the DNA sequences encoding proteins that confer resistance to specific herbicides to transformed plant cells and plants, there can be mentioned, in particular, the bar or PAT genes described in WO2009 / 152359, which confer resistance to glyphosate-based herbicides, or the Streptomyces coelicolor genes described in WO2009 / 152359, which confer resistance to glufosinate-based herbicides, genes encoding suitable EPSPS (5-enolpyruvylshikimate-3-phosphate-synthase), genes encoding glyphosate-n-acetyltransferase, or genes encoding glyphosate oxidoreductase, which confer resistance to herbicides having EPSPS as target, in particular herbicides such as glyphosate and its salts. Additional suitable herbicide tolerance traits include at least one ALS (acetolactate synthase) inhibitor (e.g., WO 2007 / 024782), mutated Arabidopsis ALS / AHAS genes (e.g., U.S. Pat. No. 6,855,533), genes encoding 2,4-D-monooxygenase that confers tolerance to 2,4-D (2,4-dichlorophenoxyacetic acid), and genes encoding dicamba monooxygenase that confers tolerance to dicamba (3,6-dichloro-2-methoxybenzoic acid).

[0183] Further particularly highlighted examples of such properties are increased resistance to phytopathogenic fungi, bacteria and / or viruses, e.g. by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors, and resistance genes and the corresponding expressed proteins and toxins.

[0184] Particularly useful transgenic events in transgenic plants or plant cultivars which can be preferably treated according to the invention include event 531 / PV-GHBK04 (cotton, insect control, described in WO 2002 / 040677), event 1143-14A (cotton, insect control, not yet deposited, described in WO 2006 / 128569); event 1143-51B (cotton, insect control, not yet deposited, described in WO 2006 / 128570); event 1445 (cotton, herbicide resistance, not yet deposited, described in US-A 2002-120964 or WO Event 17053 (rice, herbicide resistance, deposited as PTA-9843, described in WO2010 / 117737); Event 17314 (rice, herbicide resistance, deposited as PTA-9844, described in WO2010 / 117735); Event 281-24-236 (cotton, insect control-herbicide resistance, deposited as PTA-6233, described in WO2005 / 103266 or US-A2005-216969); Event 3006-210-23 (cotton, insect control-herbicide resistance, PTA-6233 and event 3272 (maize, quality traits, deposited as PTA-9972, described in WO2006 / 098952 or US-A2006-230473); event 33391 (wheat, herbicide resistance, deposited as PTA-2347, described in WO2002 / 027004), event 40416 (maize, insect control - herbicide resistance, deposited as ATCCPTA-11508, described in WO11 / 075593); event 43A47 ( corn, insect control-herbicide resistance, deposited as ATCCPTA-11509, described in WO2011 / 075595); event 5307 (corn, insect control, deposited as ATCCPTA-9561, described in WO2010 / 077816); event ASR-368 (bentgrass, herbicide resistance, deposited as ATCCPTA-4816, described in US-A2006-162007 or WO2004 / 053062); event B16 (corn, herbicide resistance, not yet deposited, described in US-A2003-126634);Event BPS-CV127-9 (soybean, herbicide resistance, deposited as NCIMB No. 41603, described in WO2010 / 080829); Event BLR1 (rapeseed, male sterility restoration, deposited as NCIMB41193, described in WO2005 / 074671); Event CE43-67B (cotton, insect control, described in DSMACC2724US-A2009-217423 or WO2006 / 128573); Event CE44-69D (cotton, insect control, not yet deposited, described in US-A2010-0024077); Event CE44-69D (cotton, insect control, not yet deposited, described in W event COT102 (cotton, insect control, not yet deposited, described in US-A2006-130175 or WO2004 / 039986); event COT202 (cotton, insect control, not yet deposited, described in US-A2007-067868 or WO2005 / 054479); event COT203 (cotton, insect control, not yet deposited, described in WO2005 / 054480); event DAS21606-3 / 1606 (soybean, herbicide resistant, deposited as PTA-11028, described in WO2012 / 033794), event DAS40278 (maize, herbicide resistant, deposited as ATCCPTA-10244, described in WO2011 / 022469); event DAS-44406-6 / pDAB8264.44.06.1 (soybean, herbicide resistant, deposited as PTA-11336, described in WO2012 / 075426), event DAS-14536-7 / pDAB8291.45.36.2 (soybean, herbicide resistant, PT A-11335, described in WO2012 / 075429), event DAS-59122-7 (maize, insect control-herbicide resistance, deposited as ATCCPTA11384, described in US-A2006-070139); event DAS-59132 (maize, insect control-herbicide resistance, not yet deposited, described in WO2009 / 100188); event DAS68416 (soybean, herbicide resistance, deposited as ATCCPTA-10442, described in WO2011 / 066384 or WO2011 / 066360);Event DP-098140-6 (maize, herbicide resistance, deposited as ATCCPTA-8296, described in US-A2009-137395 or WO08 / 112019); Event DP-305423-1 (soybean, quality traits, not yet deposited, described in US-A2008-312082 or WO2008 / 054747); Event DP-32138-1 (maize, hybridization system , deposited as ATCCPTA-9158, described in US-A2009-0210970 or WO2009 / 103049); Event DP-356043-5 (soybean, herbicide resistance, deposited as ATCCPTA-8287, described in US-A2010-0184079 or WO2008 / 002872); Event EE-I (eggplant, insect control, not yet deposited, described in WO07 / 091277); Event Fil 17 (corn, herbicide resistance, deposited as ATCC209031, described in US-A2006-059581 or WO98 / 044140); event FG72 (soybean, herbicide resistance, deposited as PTA-11041, described in WO2011 / 063413), event GA21 (corn, herbicide resistance, deposited as ATCC209033, described in US-A2005-086719 or WO98 / 044140); event GG25 (corn, herbicide resistance, deposited as ATCC209032, described in US-A2005-188434 or WO98 / 044140); event GHB119 (cotton, insect control-herbicide resistance, deposited as ATCCPTA-8398, described in WO20 08 / 151780); event GHB614 (cotton, herbicide resistance, deposited as ATCCPTA-6878, described in US-A2010-050282 or WO2007 / 017186); event GJ11 (maize, herbicide resistance, deposited as ATCC209030, described in US-A2005-188434 or WO98 / 044140); event GMRZ13 (sugar beet, virus resistance, deposited as NCIMB-41601, described in WO2010 / 076212); event H7-l (sugar beet, herbicide resistance, deposited as NCIMB41158 or NCIMB41159, described in US-A2004-172669 or WO2004 / 074492);Event JOPLINl (wheat, disease resistance, not yet deposited, described in US-A2008-064032); event LL27 (soybean, herbicide resistance, deposited as NCIMB41658, described in WO2006 / 108674 or US-A2008-320616); event LL55 (soybean, herbicide resistance, deposited as NCIMB41660, described in WO2006 / 108675 or US-A2008-196127); event LL cotton 25 (cotton, herbicide resistance, deposited as ATCCPTA-3343, described in WO2003 / 013224 or described in US-A2003-097687); event L RICE06 (rice, herbicide resistant, deposited under ATCC203353, described in US6,468,747 or WO2000 / 026345); event LL rice 62 (rice, herbicide resistant, deposited under ATCC203352, described in WO2000 / 026345), event LL rice 601 (rice, herbicide resistant, deposited under ATCCPTA-2600, described in US-A2008-2289060 or WO2000 / 026356); event L Y038 (corn, quality traits, deposited as ATCCPTA-5623, described in US-A2007-028322 or WO2005 / 061720); event MIR162 (corn, insect control, deposited as PTA-8166, described in US-A2009-300784 or WO2007 / 142840); event MIR604 (corn, insect control, not yet deposited, described in US-A2008-167456 or WO2005 / 103301); event MON15985 (cotton, insect control, deposited as ATCCPTA-5623, described in US-A2007-028322 or WO2005 / 061720); A-2516, described in US-A2004-250317 or WO2002 / 100163); event MON810 (maize, insect control, not yet deposited, described in US-A2002-102582); event MON863 (maize, insect control, deposited as ATCCPTA-2605, described in WO2004 / 011601 or US-A2006-095986); event MON87427 (maize, pollination control, deposited as ATCCPTA-7899, described in WO2011 / 062904);Event MON87460 (maize, stress tolerance, deposited as ATCCPTA-8910, described in WO2009 / 111263 or US-A2011-0138504); Event MON87701 (soybean, insect control, deposited as ATCCPTA-8194, described in US-A2009-130071 or WO2009 / 064652); Event MON87705 (soybean, quality traits - herbicide tolerance, deposited as ATCCPTA-9241, described in US-A2010-0080887 or WO2010 / 037016); Event MO Event MON87708 (soybean, herbicide tolerance, deposited as ATCCPTA-9670, described in WO2011 / 034704); Event MON87712 (soybean, yield, deposited as PTA-10296, described in WO2012 / 051199), Event MON87754 (soybean, quality traits, deposited as ATCCPTA-9385, described in WO2010 / 024976); Event MON87769 (soybean, quality traits, deposited as ATCCPTA-8911, described in US-A2011-0067141 or WO2009 / 102873); Event Event MON88017 (maize, insect control-herbicide resistance, deposited as ATCCPTA-5582, described in US-A2008-028482 or WO2005 / 059103); Event MON88913 (cotton, herbicide resistance, deposited as ATCCPTA-4854, described in WO2004 / 072235 or US-A2006-059590); Event MON88302 (oilseed rape, herbicide resistance, deposited as PTA-10955, described in WO2011 / 153186), Event MON88701 (cotton, herbicide resistance, deposited as PTA-11754 and event MON89034 (maize, insect control, deposited as ATCCPTA-7455, described in WO07 / 140256 or US-A2008-260932); event MON89788 (soybean, herbicide resistance, deposited as ATCCPTA-6708, described in US-A2006-282915 or WO2006 / 130436); event MS11 (rapeseed, pollination control - herbicide resistance, deposited as ATCCPTA-850 or PTA-2485, described in WO2001 / 031042);Event MS8 (oilseed rape, pollination control - herbicide resistance, deposited under ATCCPTA-730, described in WO2001 / 041558 or US-A2003-188347); Event NK603 (maize, herbicide resistance, deposited under ATCCPTA-2478, described in US-A2007-292854); Event PE-7 (rice, insect control, not yet deposited, described in WO2008 / 114282); Event RF3 (oilseed rape, pollination control - herbicide resistance, deposited as ATCCPTA-730, described in WO2001 / 041558 or US-A2003-188347); event RT73 (oilseed rape, herbicide resistance, not yet deposited, described in WO2002 / 036831 or US-A2008-070260); event SYHT0H2 / SYN-000H2-5 (soybean, herbicide resistance, PTA-112; 26, described in WO2012 / 082548); event T227-1 (sugar beet, herbicide resistance, not yet deposited, described in WO2002 / 44407 or US-A2009-265817); event T25 (corn, herbicide resistance, not yet deposited, described in US-A2001-029014 or WO2001 / 051654); event T304-40 (cotton, insect control - herbicide resistance, deposited as ATCCPTA-8171, described in US-A2010-077501 or WO2008 / 122406); event T342-142 (cotton, insect control, not yet deposited, described in WO2006 / 128568); event TC1507 (maize, insect control-herbicide resistance, not yet deposited, described in US-A2005-039226 or WO2004 / 099447); event VIP1034 (maize, insect control-herbicide resistance, deposited as ATCCPTA-3925, described in WO2003 / 052073), event 32316 (maize, insect control-herbicide resistance, deposited as PTA-11507, described in WO2011 / 084632), event 4114 (maize, insect control-herbicide resistance , PTA-11506, described in WO2011 / 084621), event EE-GM3 / FG72 (soybean, herbicide resistance, ATCC accession number PTA-11041), which may be cumulative with event EE-GM1 / LL27 or event EE-GM2 / LL55 (WO2011 / 063413A2), event DAS-68416-4 (soybean, herbicide resistance, ATCC accession number PTA-10442, WO2011 / 066360A1 ... 1 / 066384A1), event DP-040416-8 (maize, insect control, ATCC accession number PTA-11508, WO2011 / 075593A1), event DP-043A47-3 (maize, insect control, ATCC accession number PTA-11509, WO2011 / 075595A1), event DP-004114-3 (maize, insect control, ATCC accession number PTA-11506, WO2011 / 084621A1), event DP-032316-8 (maize, insect control, ATCC accession number PTA-11507,WO2011 / 084632A1), event MON-88302-9 (rapeseed, herbicide resistance, ATCC accession number PTA-10955, WO2011 / 153186A1), event DAS-21606-3 (soybean, herbicide resistance, ATCC accession number PTA-11028, WO2012 / 033794A2), event MON-87712-4 (soybean, quality traits, ATCC accession number PTA-10296, WO2012 / 051199A2), event DAS-44406-6 (soybean, cumulative removal herbicide resistance, ATCC accession no. PTA-11336, WO2012 / 075426A1), event DAS-14536-7 (soybean, cumulative herbicide resistance, ATCC accession no. PTA-11335, WO2012 / 075429A1), event SYN-000H2-5 (soybean, herbicide resistance, ATCC accession no. PTA-11226, WO2012 / 082548A2), event DP-061061-7 (oilseed rape, herbicide resistance, accession no. not available, WO2012071039A1), event DP -073496-4 (rapeseed, herbicide resistance, accession number not available, US2012131692), event 8264.44.06.1 (soybean, cumulative herbicide resistance, accession number PTA-11336, WO2012075426A2), event 8291.45.36.2 (soybean, cumulative herbicide resistance, accession number PTA-11335, WO2012075429A2), event SYHT0H2 (soybean, ATCC accession number PTA-11226, WO2012 / 082548A2), event MON88 701 (cotton, ATCC accession number PTA-11754, WO2012 / 134808A1), event KK179-2 (alfalfa, ATCC accession number PTA-11833, WO2013 / 003558A1), event pDAB8264.42.32.1 (soybean, cumulative herbicide resistance, ATCC accession number PTA-11993, WO2013 / 010094A1), event MZDT09Y (corn, ATCC accession number PTA-13025, WO2013 / 012775A1), etc.

[0185] In addition, a list of such transgenic events is provided by the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA), which lists aphis.usda.gov Website on the World Wide Web can be found at With respect to this application, what is relevant is the status of such lists as of the filing date of this application.

[0186] Genes / events that confer the desired trait of interest may also be present in combination with each other in transgenic plants. Examples of transgenic plants that may be mentioned are important crop plants such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybean, potato, sugarcane, sugarcane, tomato, pea and other types of vegetables, cotton, tobacco, oilseed rape, as well as fruit plants (including the fruits apple, pear, citrus fruits, grapes), with particular emphasis on corn, soybean, wheat, rice, potato, cotton, sugarcane, tobacco and oilseed rape. Particular emphasis on traits is the enhancement of the resistance of the plant to insects, arachnids, nematodes and slugs and snails, and the enhancement of the resistance of the plant to one or more herbicides.

[0187] Commercially available examples of such plants, plant parts or plant seeds which can be preferably treated according to the invention include GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY®, VT DOUBLE PRO®, VT TRIPLEPRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEN®, DTM , INTACTA RR2PRO®, VISTIVE GOLD®, and / or XTENDFLEX® trade names.

[0188] Crop protection - types of treatment The treatment of plants and plant parts with the compounds of formula (I) is carried out using customary treatment methods, for example by immersion, spraying, atomization, irrigation, vaporization, dusting, fume, broadcasting, foaming, painting, spreading-on, injection, watering (drenching), drip irrigation, etc., and in the case of propagation material, in particular seeds, also as dry seed treatment powders, liquid seed treatment solutions, as slurry treatment water-solubles, covering, coating with one or more films, etc., directly or by acting on the surroundings, habitat or storage space of the plants and plant parts. Furthermore, the compounds of formula (I) can also be applied by ultra-low volume methods or the application forms or the compounds of formula (I) themselves can be injected into the soil.

[0189] A preferred direct treatment of plants is foliar application, ie the compounds of formula (I) are applied to the foliage, in which case the frequency of treatment and the application rates should be adapted according to the level of infestation of the pest in question.

[0190] In the case of systemically active compounds, the compounds of formula (I) also reach the plant through the root system. Thus, the plant is treated by applying the compounds of formula (I) to the plant's habitat. This can be done, for example, by drenching, or by mixing into the soil or nutrient solution [i.e. impregnating the plant's growing locus (e.g. soil or hydroponic system) with a liquid form of the compounds of formula (I)], or by soil application [i.e. introducing the compounds of formula (I) according to the invention in solid form (e.g. in granular form) into the plant's growing locus], or by drip application (often also called "chemical solution irrigation"), i.e. liquid application of the compounds of formula (I) according to the invention from a surface or subsurface drip line for a specific period of time with various amounts of water at a defined location near the plant. In the case of rice crops, this can also be done by metering the compounds of formula (I) in solid application form (e.g. as granules) into the flooded rice field.

[0191] Digital Technology The compounds of the present invention can be used in combination with models embedded in computer programs for, for example, site-specific crop management, satellite cultivation, precision cultivation agriculture or precision agriculture. Such models support the site-specific management of agricultural sites using data from various sources such as soil, climate, crops (e.g., type, growth stage, plant health), weeds (e.g., type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield, etc., with the aim of optimizing profitability, sustainability and environmental protection. In particular, such models can help optimize agricultural decisions, control the accuracy of pesticide application, and record the work carried out.

[0192] As an example, a compound of the present invention can be applied to a crop plant according to an appropriate application method when the model models the development of a pest and calculates that a threshold has been reached at which it is recommended to apply the compound to the crop plant.

[0193] Commercially available systems that include agronomic models include, for example, FieldScripts™ from The Climate Corporation, Xarvio™ from BASF, and AGLogic™ from John Deere.

[0194] The compounds of the present invention can also be used in combination with smart spraying devices, such as spot spraying devices or precision spraying devices attached to or housed in agricultural vehicles, such as tractors, robots, helicopters, airplanes, unmanned aerial vehicles (UAVs), such as drones. Such equipment typically includes input sensors (e.g., cameras, etc.) and a processing unit configured to analyze the input data and provide a decision based on the analysis of the input data to apply the compounds of the present invention to crop plants (respectively weeds) in an individualized and precise manner. The use of such smart spraying devices typically also requires a location system (e.g., a GPS receiver) to localize the recorded data and guide or control the agricultural vehicle; a geographic information system (GIS) to represent the information on a clear map, and a suitable agricultural vehicle to perform the required agricultural operations, such as spraying.

[0195] In one example, pests can be detected from images captured by a camera. In one example, pests can be identified and / or classified based on the images. Such identification and / or classification can utilize image processing algorithms. Such image processing algorithms can utilize machine learning algorithms such as trained neutral networks, decision trees, and can utilize artificial intelligence algorithms. In this way, the compounds described herein can be applied only when necessary.

[0196] Seed treatment Control of pests by treating plant seeds has been known for a long time and is being continuously improved.However, seed treatment is accompanied by a series of problems that cannot always be solved satisfactorily.Thus, it is desirable to develop a method for protecting seeds and germinating plants, which makes it unnecessary or at least significantly reduces the additional application of pesticides during storage, after sowing or after emergence of the plants.Furthermore, it is desirable to optimize the amount of active compound used, so that the seeds and germinating plants are optimally protected from attack by pests, without causing damage to the plants themselves by the active compound used.In particular, the seed treatment method should also take into account the intrinsic insecticidal or nematicidal properties of pest-resistant transgenic plants or pest-resistant transgenic plants, in order to achieve the optimal protection of seeds and germinating plants using the minimum amount of pesticides.

[0197] Therefore, the present invention also relates to a method for protecting seeds and germinating plants from attack by pests, in particular by treating the seeds with one of the compounds of formula (I). The method of the present invention for protecting seeds and germinating plants from attack by pests also includes such a method that the seeds are treated with the compound of formula (I) and the mixed components simultaneously or sequentially in one operation. It also includes such a method that the seeds are treated with the compound of formula (I) and the mixed components at different times.

[0198] The present invention also relates to the use of the compounds of formula (I) for treating seeds to protect the seeds and the plants resulting from said seeds against pests.

[0199] The present invention also relates to a seed treated with the compound of formula (I) according to the present invention to provide protection against pests. The present invention also relates to a seed treated simultaneously with the compound of formula (I) and the mixture. The present invention also relates to a seed treated at different times with the compound of formula (I) and the mixture. In the case of a seed treated at different times with the compound of formula (I) and the mixture, the individual substances can be present in different layers on the surface of the seed. Here, the layers containing the compound of formula (I) and the mixture can be separated by an intermediate layer. The present invention also relates to a seed in which the compound of formula (I) and the mixture are applied as a component of a coating or as an additional layer or layers added to the coating.

[0200] The present invention further relates to seeds which, after being treated with a compound of formula (I), are subjected to a film-coating process in order to prevent abrasion of the seeds by dust.

[0201] One advantage offered by the systemically acting compounds of formula (I) is that by treating the seed, not only the seed itself but also the plant resulting from the seed is protected from pests after germination, thus avoiding the need for direct treatment of the crop at or shortly after sowing.

[0202] A further advantage to be considered is that by treating seeds with a compound of formula (I), the germination and emergence of the treated seeds may be enhanced.

[0203] It is likewise believed to be advantageous that the compounds of formula (I) can be used, in particular, in transgenic seeds.

[0204] Additionally, compounds of formula (I) can be used in combination with signaling technology compositions or compounds to result in better colonization by symbionts (e.g., rhizobia, mycorrhizal fungi and / or endophytic bacteria or fungi) and / or optimized nitrogen fixation.

[0205] The compounds of formula (I) are suitable for protecting the seeds of all plant varieties used in agriculture, in greenhouses, in forests or in horticulture.In particular, they are in the form of the seeds of cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, rapeseed, beet (such as sugar beet and fodder beet), peanut, vegetables (such as tomato, cucumber, bean, cruciferous vegetables, onion and lettuce), fruit plants, turf and ornamental plants.It is particularly important to treat the seeds of cereals (such as wheat, barley, rye and oats), corn, soybeans, cotton, canola, rapeseed, vegetables and rice.

[0206] As already mentioned above, the treatment of transgenic seeds with compounds of formula (I) is also of particular importance. This takes the form of a plant seed essentially containing at least one heterologous gene controlling the expression of a polypeptide having, in particular, insecticidal and / or nematicidal properties. These heterologous genes in the transgenic seed may be derived from microorganisms such as Bacillus sp., Rhizobium sp., Pseudomonas sp., Serratia sp., Trichoderma sp., Clavibacter sp., Glomus sp. or Gliocladium sp. The invention is particularly suitable for treating transgenic seeds containing at least one heterologous gene derived from Bacillus sp. It is particularly preferred that the heterologous gene is derived from Bacillus thuringiensis.

[0207] In the context of the present invention, the compound of formula (I) is applied to seeds. Preferably, the seeds are treated when they are sufficiently stable to avoid damage during treatment. In general, the seeds can be treated at any time between harvesting and sowing. The seeds usually used are separated from the plant and have had the cob, husk, petiole, husk, hair or flesh removed. For example, seeds can be used that have been harvested, cleaned and dried to a moisture content that allows storage. Alternatively, seeds can be used that have been treated after drying, for example with water and then dried again (for example, primed). In the case of rice seeds, it is also possible to use seeds that have been immersed in water, for example, until a certain stage of the rice embryo ("pigeon breast stage"), thereby stimulating germination and resulting in a more uniform emergence.

[0208] When treating seeds, care must generally be taken to select the amount of compound of formula (I) and / or the amount of further additives applied to the seeds so that the germination of the seeds is not adversely affected or the plants resulting from the seeds are not damaged. This must be ensured, in particular in the case of active compounds that may show phytotoxic effects at certain application rates.

[0209] Generally, the compounds of formula (I) are applied to the seeds in a suitable formulation. Suitable formulations and processes for treating seeds are known to those skilled in the art.

[0210] The compounds of formula (I) can be converted into conventional seed dressing formulations, such as solutions, emulsions, suspensions, dusts, foams, slurries or other coating compositions for seeds, and can also be converted into ULV formulations.

[0211] These formulations are prepared in known manner by mixing the compounds of formula (I) with conventional additives, such as conventional extenders and solvents or diluents, colorants, wetting agents, dispersants, emulsifiers, antifoaming agents, preservatives, secondary thickeners, adhesives, gibberellins, and the like, and further mixing with water.

[0212] Colorants that may be present in the seed dressing formulations that can be used according to the invention are all colorants that are customary for such purposes. Pigments that are poorly soluble in water or dyes that are soluble in water can be used. Examples include the colorants known under the names "Rhodamin B", "CI Pigment Red 112" and "CI Solvent Red 1".

[0213] Useful wetting agents that can be present in the seed dressing formulations that can be used according to the invention are all substances that promote wetting and are customarily used for the formulation of agrochemically active compounds. Preferably, alkylnaphthalenesulfonates, such as diisopropyl or diisobutylnaphthalenesulfonate, are used.

[0214] Useful dispersants and / or emulsifiers that can be present in the seed dressing formulations that can be used according to the invention are all nonionic, anionic and cationic dispersants that are conventionally used in the formulation of agrochemical active ingredients. Preferably, nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants are used. Suitable nonionic dispersants include, in particular, ethylene oxide / propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, as well as their phosphorylated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates and arylsulfonate / formaldehyde condensates.

[0215] Antifoaming agents which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances conventionally used in the formulation of active agrochemical ingredients. Preferably, silicone antifoaming agents and magnesium stearate are used.

[0216] Preservatives which may be present in the seed dressing formulations which may be used according to the invention are all substances which may be used for this purpose in agrochemical compositions, such as dichlorophene and benzyl alcohol hemiformal.

[0217] Secondary thickeners which may be present in the seed dressing formulations which may be used according to the invention are all substances which may be used for this purpose in agrochemical compositions, with preference given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and micronized silica.

[0218] Adhesives that may be present in the seed dressing formulations that can be used according to the invention are all conventional binders that can be used in seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose.

[0219] Gibberellins which may be present in the seed dressing formulations which can be used according to the invention are preferably gibberellin A1, gibberellin A3 (=gibberellic acid), gibberellin A4 and gibberellin A7, with gibberellic acid being particularly preferably used. Gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- and Schadlingsbekampfungsmittel", vol. 2, Springer Verlag, 1970, pp. 401-412).

[0220] The seed dressing formulations that can be used according to the invention can be used directly or after being diluted with water beforehand to treat a wide variety of seeds. For example, concentrates or preparations that can be obtained from concentrates by dilution with water can be used to dress cereal seeds, such as wheat, barley, rye, oats and triticale, and can also be used to dress corn, rice, rapeseed, pea, bean, cotton, sunflower, soybean and beet seeds, or to dress a wide variety of vegetable seeds. The seed dressing formulations that can be used according to the invention or their diluted application forms can also be used to dress the seeds of transgenic plants.

[0221] When treating seeds with the seed dressing formulation that can be used according to the present invention or the use form prepared from the seed dressing formulation by adding water, all mixing devices that can be used conventionally for seed dressing are useful.Specifically, the procedure for seed dressing is to place seeds in a mixer that operates batchwise or continuously, add a specific amount of the seed dressing formulation desired, either as is or after diluting it with water in advance, and mix everything until the formulation is distributed homogeneously on the surface of the seed.If appropriate, a drying step is then performed.

[0222] The application rate of the seed dressing formulation that can be used according to the present invention can vary within a relatively wide range.It depends on the specific content of the compound of formula (I) in the formulation and the seed.The application rate of the compound of formula (I) is generally 0.001 to 50 g per kg of seed, preferably 0.01 to 15 g per kg of seed.

[0223] animal health In the field of animal health, i.e. veterinary medicine, the compounds of formula (I) are active against animal parasites, in particular against ecto- or endoparasites. The term "endoparasites" includes in particular helminths and protozoa (e.g. coccidia). Ectoparasites are typically and preferably arthropods, in particular insects or mites.

[0224] In the field of veterinary medicine, the compounds of formula (I) have favorable toxicity in warm-blooded animals and are suitable in animal breeding and animal husbandry for controlling parasites occurring in livestock animals, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals.

[0225] Agricultural livestock include, for example, mammals, such as sheep, goats, horses, donkeys, camels, water buffaloes, rabbits, reindeer, fallow deer, and especially cattle and pigs; or poultry, such as turkeys, ducks, geese, and especially chickens; or fish or crustaceans, such as fish and crustaceans in aquaculture; or possibly insects, such as bees.

[0226] Domestic animals include, for example, mammals, such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, or, in particular, dogs, cats, caged birds, reptiles, amphibians, or aquarium fish.

[0227] According to certain embodiments, the compound of formula (I) is administered to a mammal.

[0228] According to another particular embodiment, the compounds of formula (I) are administered to birds, ie to caged birds or, in particular, to poultry.

[0229] The use of the compounds of formula (I) for controlling animal parasites is intended to reduce or prevent disease, mortality and loss of productivity (in the case of meat, milk, wool, leather, eggs, honey, etc.), so that more economical and simpler animal husbandry is possible and better animal health conditions can be achieved.

[0230] As used herein in the field of animal health, the term "control" or "controlling" means that the compounds of formula (I) are effective in reducing the occurrence of the individual parasite in an animal infected with the parasite to a harmless level. More specifically, as used herein, "control" means that the compounds of formula (I) are effective in killing, inhibiting the growth or inhibiting the proliferation of the individual parasite.

[0231] Examples of arthropods include, but are not limited to, the following:

[0232] from the order Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.; From the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Bovicola spp., Damalina spp., Felicola spp.; Lepikentron spp., Menopon spp., Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella spp.; From the order Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Atylotus spp., Braula spp., Calliphora spp., Chrysomyia spp., Chrysops spp., Culex spp., Culicoides spp., Eusimulium spp., Fannia spp., Gasterophilus spp. spp., Glossina spp., Haematobia spp., Haematopota spp., Hippobosca spp., Hybomitra spp., Hydrotaea spp., Hypoderma spp., Lipoptena spp., Lucilia spp., Lutzomyia spp., Melophagus spp., Morellia spp., Musca spp., Odagmia spp. spp.), Oestrus spp., Philipomyia spp., Phlebotomus spp., Rhinoestrus spp., Sarcophaga spp., Simulium spp., Stomoxys spp., Tabanus spp., Tipula spp., Wilhelmia spp., Wohlfahrtia spp.; From the order Siphonapterida, for example, Ceratophyllus spp., Ctenocephalides spp., Pulex spp., Tunga spp., Xenopsylla spp.; From the order Heteropterida, for example, Cimex spp., Panstrongylus spp., Rhodnius spp., Triatoma spp.; and harmful and hygiene pests from the order Blattaria.

[0233] Additionally, among arthropods, examples that may be mentioned include, but are not limited to, the following mites:

[0234] From the subclass Acari (Acarina) and the order Metastigmata, for example from the family Argasidae, for example Argas spp., Ornithodorus spp., Otobius spp., from the family Ixodidae, for example Amblyomma spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Ixodes spp., Rhipicephalus (Boophilus) spp. spp.), Rhipicephalus spp. (the original genus of multihost mites); from the order Mesostigmata, for example, Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Tropilaelaps spp., Varroa spp.; from the order Actinedida (Prostigmata), for example, Acarapis spp., Cheyletiella spp. spp., Demodex spp., Listrophorus spp., Myobia spp., Neotrombicula spp., Ornithocheyletia spp., Psorergates spp., Trombicula spp.; and from the order Acaridida (Astigmata), for example Acarus spp., Caloglyphus spp., Chorioptes spp.), Cytodites spp., Hypodectes spp., Knemidocoptes spp., Laminosioptes spp., Notoedres spp., Otodectes spp., Psoroptes spp., Pterolichus spp., Sarcoptes spp., Trixacarus spp., Tyrophagus spp..

[0235] Examples of parasitic protozoans include, but are not limited to:

[0236] Subphylum Mastigophora (Flagellata), for example: Metamonada: from the order Diplomonadida, e.g., Giardia spp., Spironucleus spp.; Parabasala: from the order Trichomonadida, for example, Histomonas spp., Pentatrichomonas spp., Tetratrichomonas spp., Trichomonas spp., Tritrichomonas spp.; Euglenozoa: from the order Trypanosomatida, e.g., Leishmania spp., Trypanosoma spp.; Sarcomastigophora (Rhizopoda), for example, Entamoebidae, for example, Entamoeba spp., Centramoebidae, for example, Acanthamoeba sp., Euamoebidae, for example, Hartmanella sp.; Alveolata, for example, Apicomplexa (Sporozoa), for example, Cryptosporidium spp.; from the order Eimeriida, for example, Besnoitia spp., Cystoisospora spp., Eimeria spp., Hammondia spp., Isospora spp., Neospora spp., Sarcocystis spp., Toxoplasma spp.; from the order Adeleida, for example, Hepatozoon spp. from the order Haemosporida, for example, Leucocytozoon spp., Plasmodium spp.; from the order Piroplasmida, for example, Babesia spp., Ciliophora spp., Echinozoon spp., Theileria spp.; from the order Vesibuliferida, for example, Balantidium spp., Buxtonella spp.; Microspora, for example Encephalitozoon spp., Enterocytozoon spp., Globidium spp., Nosema spp. and also, for example, Myxozoa spp.

[0237] Helminths that are pathogenic to humans or animals include, for example, acanthocephala, nematodes, pentastoma and platyhelminths (e.g. monogenea, cestodes and trematodes).

[0238] Examples of helminths include, but are not limited to:

[0239] Class Monogenea: for example: Dactylogyrus spp., Gyrodactylus spp., Microbothrium spp., Polystoma spp., Troglocephalus spp.; Cestodes: from the order Pseudophyllidea, for example, Bothridium spp., Diphyllobothrium spp., Diplogonoporus spp., Ichthyobothrium spp., Ligula spp., Schistocephalus spp., Spirometra spp.; From the order Cyclophyllida, for example: Andyra spp., Anoplocephala spp., Avitellina spp., Bertiella spp., Cittotaenia spp., Davainea spp., Diorchis spp., Diplopylidium spp., Dipylidium spp., Echinococcus spp., Echinocotyle spp., Echinolepis spp. spp.), Hydatigera spp., Hymenolepis spp., Joyeuxiella spp., Mesocestoides spp., Moniezia spp., Paranoplocephala spp., Raillietina spp., Stilesia spp., Taenia spp., Thysaniezia spp., Thysanosoma spp.; Trematodes: from the subclass Digenea, for example: Austrobilharzia spp., Brachylaima spp., Calicophoron spp., Catatropis spp., Clonorchis spp., Collyriclum spp., Cotylophoron spp., Cyclocoelum spp., Dicrocoelium spp., Diplostomum spp., Echinochasmus spp., Echinoparyphium spp. spp.), Echinostoma spp., Eurytrema spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Fischoederius spp., Gastrothylacus spp., Gigantobilharzia spp., Gigantocotyle spp., Heterophyes spp., Hypoderaeum spp., Leucochloridium spp. spp., Metagonimus spp., Metorchis spp., Nanophyetus spp., Notocotylus spp., Opisthorchis spp., Ornithobilharzia spp., Paragonimus spp., Paramphistomum spp., Plagiorchis spp.), Posthodiplostomum spp., Prosthogonimus spp., Schistosoma spp., Trichobilharzia spp., Troglotrema spp., Typhlocoelum spp.;. Nematodes: from the order Trichinellida, for example: Capillaria spp., Eucoleus spp., Paracapillaria spp., Trichinella spp., Trichomosoides spp., Trichuris spp.; From the order Tylenchida, for example: Micronema spp., Parastrongyloides spp., Strongyloides spp.; From the order of the Rhabditina, for example: Aelurostrongylus spp., Amidostomum spp., Ancylostoma spp., Angiostrongylus spp., Bronchonema spp., Bunostomum spp., Chabertia spp., Cooperia spp., Cooperioides spp., Crenosoma spp., Cyathostomum spp., Cyclococercus spp. spp.), Cyclodontostomum spp., Cylicocyclus spp., Cylicostephanus spp., Cylindropharynx spp., Cystocaulus spp., Dictyocaulus spp., Elaphostrongylus spp., Filaroides spp., Globocephalus spp., Graphidium spp., Gyalocephalus spp., Haemonchus spp. spp.), Heligmosomoides spp., Hyostrongylus spp., Marshallagia spp., Metastrongylus spp., Muellerius spp., Necator spp., Nematodirus spp., Neostrongylus spp.), Nippostrongylus spp., Obeliscoides spp., Oesophagodontus spp., Oesophagostomum spp., Ollulanus spp.; Ornithostrongylus spp., Oslerus spp., Ostertagia spp., Paracooperia spp., Paraclenosoma spp., Parafilaroides spp., Parelaphostrongylus spp. spp.), Pneumocaulus spp., Pneumostrongylus spp., Poteriostomum spp., Protostrongylus spp., Spicocaulus spp., Stephanurus spp., Strongylus spp., Syngamus spp., Teladorsagia spp., Trichonema spp., Trichostrongylus spp., Triodontophorus spp. spp.), Troglostrongylus spp., Uncinaria spp.;. From the order of the Spirurida, for example: Acanthocheilonema spp., Anisakis spp., Ascaridia spp.; Ascaris spp., Ascarops spp., Aspiculuris spp., Baylisascaris spp., Brugia spp., Cercopithifilaria spp., Crassicauda spp., Dipetalonema spp., Dirofilaria spp., Dracunculus spp. spp.); Draschia spp., Enterobius spp., Filaria spp., Gnathostoma spp., Gongylonema spp., Habronema spp., Heterakis spp.; Litomosoides spp., Loa spp., Onchocerca spp., Oxyuris spp., Parabronema spp., Parafilaria spp., Parascaris spp. spp., Passalurus spp., Physaloptera spp., Probstmayria spp., Pseudofilaria spp., Setaria spp., Skjrabinema spp., Spirocerca spp., Stephanofilaria spp., Strongyluris spp.), Syphacia spp., Thelazia spp., Toxascaris spp., Toxocara spp., Wuchereria spp.;. Phylum Acantocephala: from the order Oligacanthorhynchida, for example: Macracanthorhynchus spp., Prosthenorchis spp.; from the order Moniliformida, for example: Moniliformis spp.; from the order Polymorphida, for example: Filicollis spp.; from the order Echinorhynchida, for example: Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.; Phylum Pentastoma: Order Porocephalida, for example, Linguatula spp.

[0240] In the veterinary field and in animal husbandry, the administration of the compounds of formula (I) is carried out by methods generally known in the art, for example enterally, parenterally, transdermally or intranasally in the form of suitable preparations. The administration can be prophylactic, metaphylactic or therapeutic.

[0241] Thus, one embodiment of the present invention refers to a compound of formula (I) for use as a medicament.

[0242] Another embodiment refers to the compounds of formula (I) for use as anti-endoparasitic agents.

[0243] Another particular embodiment refers to the compounds of formula (I) for use as anthelmintics, in particular for use as nematicides, flatwormicides, acicularidicides or lingulicides.

[0244] Another particular embodiment refers to the compounds of formula (I) for use as antiprotozoal agents.

[0245] Another embodiment refers to the compounds of formula (I) for use as anti-ectoparasiticides, in particular arthropodicides, more particularly insecticides or acaricides.

[0246] A further aspect of the present invention is a veterinary formulation comprising an effective amount of at least one compound of formula (I) and at least one of the following: a pharmaceutically acceptable excipient (e.g. a solid or liquid diluent), a pharmaceutically acceptable auxiliary (e.g. a surfactant), in particular a pharmaceutically acceptable excipient, and / or a pharmaceutically acceptable auxiliary typically used in veterinary formulations.

[0247] A related aspect of the invention is a method for producing a veterinary formulation as described herein, comprising the step of mixing at least one compound of formula (I) with pharmaceutically acceptable excipients and / or adjuvants, in particular with pharmaceutically acceptable excipients and / or adjuvants commonly used in veterinary formulations.

[0248] Another particular aspect of the present invention is a veterinary formulation selected from the group of ectoparasiticide and endoparasiticide formulations, in particular selected from the group of anthelmintic, antiprotozoan and arthropodicide formulations, and even more particularly selected from the group of nematicidal, flatworm-cidal, stagnocide, rhetocephalic, insecticidal and acaricidal formulations according to the above aspects, and methods for their preparation.

[0249] Another aspect refers to a method of treating a parasitic infection, particularly an infection by a parasite selected from the group of ectoparasites and endoparasites described herein, by applying an effective amount of a compound of formula (I) in an animal, particularly a non-human animal, in need of such treatment.

[0250] Another aspect refers to a method of treating a parasitic infection, in particular an infection by a parasite selected from the group of ectoparasites and endoparasites as described above, by applying a veterinary preparation as defined herein in an animal, in particular a non-human animal, in need of such treatment.

[0251] Another aspect refers to the use of the compounds of formula (I) in the treatment of parasitic infections in animals (particularly non-human animals), in particular infections by parasites selected from the group of ectoparasites and endoparasites described above.

[0252] In the context of the animal health or veterinary field, the term "treatment" includes prophylactic, post-infection preventative or therapeutic treatment.

[0253] In a particular embodiment, there are provided mixtures of at least one compound of formula (I) with other active compounds, in particular endoparasiticides and ectoparasiticides, in the veterinary field.

[0254] In the field of animal health, "mixtures" does not only mean that two (or more) different active ingredients are formulated in a joint preparation and are thereby applied together, but also refers to products that contain separate preparations for each active compound. Thus, when more than two active compounds are used, all active compounds can be formulated in a joint preparation or all active compounds can be formulated in separate preparations; furthermore, mixed forms are also possible, where some of the active compounds are formulated together and some of the active compounds are formulated separately. In the separate preparations, the active compounds can be applied separately or sequentially.

[0255] The active compounds identified herein by "common name" are known and are described, for example, in the "Pesticide Manual" (see above) or can be found on the internet (e.g., http: / / www.alanwood.net / pesticides ").

[0256] Exemplary active ingredients selected from the group of ectoparasiticides as mixing partners include, but are not limited to, the insecticides and acaricides detailed above. Additional active ingredients that may be used are listed below according to the above classification based on the current "IRAC Mode of Action Classification Scheme": (1) acetylcholinesterase (AChE) inhibitors; (2) GABA-gated chloride channel blockers; (3) sodium channel modulators; (4) nicotinic acetylcholine receptor (nAChR) competitive modulators; (5) nicotinic acetylcholine receptor (nAChR) allosteric modulators; (6) glutamate-gated chloride channel (GluCl) allosteric modulators; (7) juvenile hormone mimetics; (8) various non-specific (multi-site) inhibitors; (9) chordotonal organ modulators; (10) mite growth inhibitors; (12) mitochondrial ATP synthase inhibitors, such as ATP disruptors; (13) inhibitors that disrupt the proton gradient. and uncouplers of oxidative phosphorylation by acetylcholine receptors;(14) nicotinic acetylcholine receptor channel blockers;(15) inhibitors of chitin biosynthesis (type 0);(16) inhibitors of chitin biosynthesis (type 1);(17) molting disruptors (especially in the order Diptera, i.e., Diptera);(18) ecdysone receptor agonists;(19) octopamine receptor agonists;(21) mitochondrial complex I electron transport inhibitors;(25) mitochondrial complex II electron transport inhibitors;(20) mitochondrial complex III electron transport inhibitors;(22) voltage-dependent sodium channel blockers;(23) inhibitors of acetyl-CoA carboxylase;(28) ryanodine receptor modulators;(30) GABA-gated chloride channel allosteric modulators.

[0257] Active compounds with unknown or non-specific mechanism of action, for example, fentrifanil, fenoxacrim, cycloprene, chlorobenzilate, chlordimeform, flubenzimine, dicyclanil, amidoflumet, quinomethionate, triaratene, clothiazoben, tetrasul, potassium oleate, petroleum, methoxadiazone, gossypurle, flutenzin, bromopropylate, cryolite; Another class of compounds, for example, butacarb, dimethylan, cloethocarb, phosphocarb, pirimiphos (-ethyl), parathion (-ethyl), methacrifos, isopropyl o-salicylate, trichlorfon, tigolaner, sulprofos, propafos, cebufos, pyridathion, protoate, diclofenthion, demeton-S-methylsulfone, isazofos, cyanofenphos, dialifos, carbophenothion, autathiophos, allofenvinphos (-methyl), azinphos (-ethyl), chlorpyrifos (-ethyl), phosmetilan, iodofenphos, dioxabenzophos, formothion, fonofos, flupyrazophos, fensulfothion, etrimphos; Organochlorines, such as camphechlor, lindane, heptachlor; or phenylpyrazoles, such as acetoprole, pyrafluprole, pyriprole, vaniliprole, cisapronil; or isoxazolines, such as sarolaner, afoxolaner, lotilaner, fluralaner; Pyrethroids, such as (cis-, trans-)metofluthrin, profluthrin, flufenprox, flubrocythrinate, fubufenprox, fenfluthrin, protrifenbut, pyresmethrin, RU15525, terallethrin, cis-resmethrin, heptafluthrin, bioethanomethrin, biopermethrin, fenpyrithrin, cis-cypermethrin, cis-permethrin, clocithrin, cyhalothrin (lambda-), clovaporthrin, or halogenated hydrocarbons (HCHs); Neonicotinoids, for example, nithiazine; Dichloromezotiaz, triflumezopyrim; Macrocyclic lactones, such as nemadectin, ivermectin, latidectin, moxidectin, selamectin, eprinomectin, doramectin, emamectin benzoate; milbemycin oxime; Triplen, epofenonane, diofenolan; Biological agents, hormones, or pheromones, such as natural products, e.g., thuringiensin, codlemone, or neem components; Dinitrophenols, such as dinocap, dinobuton, binapacryl; Benzoylureas, for example, Fluazuron, Penfluron; Amidine derivatives, such as chlormebuform, cymiazole, demiditraz; 10. Beehive varroa acaricides, for example, organic acids, e.g., formic acid, oxalic acid.

[0258] Exemplary active ingredients selected from the group of endoparasiticides as mixing partners include, but are not limited to, anthelmintic active compounds and antiprotozoan active compounds.

[0259] The anthelmintic active compounds include, but are not limited to, the following nematicidal, flukecidal and / or cestocidal active compounds;

[0260] From the class of macrocyclic lactones, for example: eprinomectin, abamectin, nemadectin, moxidectin, doramectin, selamectin, lepimectin, latidectin, milbemectin, ivermectin, emamectin, milbemycin; From the class of the benzimidazoles and probenzimidazoles, for example: oxibendazole, mebendazole, triclabendazole, thiophanate, parbendazole, oxfendazole, netobimin, fenbendazole, febantel, thiabendazole, cyclobendazole, cambendazole, albendazole sulfoxide, albendazole, flubendazole; From the class of the depsipeptides, preferably from the class of the cyclic depsipeptides, in particular from the class of the 24-membered cyclic depsipeptides, for example: emodepside, PF1022A; From the class of tetrahydropyrimidines, for example: morantel, pyrantel, oxantel; From the class of imidazothiazoles, for example: butamisole, levamisole, tetramisole; From the class of aminophenylamidines, for example: amidantel, deacylated amidantel (dAMD), tribendimidine; From the class of aminoacetonitriles, for example: monepantel; Of the paraherquamide type, for example: paraherquamide, delquantel; From the class of salicylanilides, for example: tribromosalan, bromoxanide, brothianide, clioxanide, closantel, niclosamide, oxyclozanide, lafoxanide; Of the types of substituted phenols, for example: nitroxynil, bithionol, disophenol, hexachlorophene, niclofolane, meniclopholan; Of the organophosphate type, for example: trichlorfon, naphthalofos, dichlorvos / DDVP, crufomate, coumaphos, haloxon; From the piperazinone / quinoline class, for example: praziquantel, epsiprantel; From the piperazine family, for example: piperazine, hydroxyzine; Of the tetracycline class, for example: tetracycline, chlortetracycline, doxycycline, oxytetracycline, rolitetracycline; Various other types, for example: bunamidine, niridazole, resorantel, omfalotin, oltipraz, nitrosucanate, nitroxynil, oxamniquine, mirasan, miracil, lucantone, hycantone, hetolin, emetine, diethylcarbamazine, dichlorophene, diamphenetide, clonazepam, bephenium, amoscanate, clorsulon.

[0261] Antiprotozoan active compounds include, but are not limited to, the following active compounds;

[0262] From the triazines class, for example: diclazuril, ponazuril, letrazuril, toltrazuril; From the class of polyether ionophores, for example: monensin, salinomycin, maduramycin, narasin; From the class of macrocyclic lactones, for example: milbemycin, erythromycin; From the quinolone class, for example: enrofloxacin, pradofloxacin; Of the quinines class, for example: chloroquine; From the class of pyrimidines, for example: pyrimethamine; From the class of sulfonamides, for example: sulfaquinoxaline, trimethoprim, sulfaclozine; Of the thiamine family, for example: amprolium; From the class of lincosamides, for example: clindamycin; Of the carbanilide class, for example: imidocarb; Of the nitrofuran class, for example: nifurtimox; From the class of quinazoline alkaloids, for example: halofuginone; Various other types, for example: oxamniquine, paromomycin; Types of vaccines or antigens from microorganisms, for example: Babesia canis rossi, Eimeria tenella, Eimeria praecox, Eimeria necatrix, Eimeria mitis, Eimeria maxima, Eimeria brunetti, Eimeria acervulina, Babesia canis vogeli, Leishmania infantum, Babesia canis canis, Dictyocaulus viviparus.

[0263] All mixing partners mentioned are capable, if this is possible due to their functional groups, of forming salts with suitable bases or acids.

[0264] Vector control The compounds of formula (I) can also be used in the control of vectors. In the context of the present invention, vectors are arthropods (e.g. insects or arachnids) capable of carrying pathogens (e.g. viruses, worms, single-cell organisms and bacteria) from a reservoir (e.g. plants, animals, humans, etc.) to the host. The pathogens can be carried to the host mechanically (e.g. trachoma by non-biting flies) or after injection into the host (e.g. malaria parasites by mosquitoes).

[0265] Examples of vectors and the diseases or pathogens they carry are: 1) Mosquitoes -Anopheles: malaria, filariasis; - Culex: Japanese encephalitis, other viral diseases, filariasis, carrying helminths; -Aedes: Yellow fever, dengue fever, other viral diseases, filariasis; - Black flies (Simulidae): carrying worms (especially Onchocerca volvulus); - Moth flies (Psychodidae): transmission of leishmaniasis; 2) Lice: skin infections, epidemic typhus; 3) Fleas: contagious disease, typhus, tapeworms; 4) Flies: sleeping sickness (trypanosomiasis); cholera, another bacterial disease; 5) Acaridae: acarosis, epidemic typhus, rickettsial pox, tularemia, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borreliosis; 6) Ixodes: borellioses, e.g. Borrelia burgdorferi sensu lato., Borrelia duttoni, tick-borne encephalitis, Coxiella burnetii, Babesia canis canis, ehrlichiosis.

[0266] In the sense of the present invention, examples of vectors are insects capable of transmitting plant viruses to plants, such as aphids, flies, leafhoppers or thrips. Further vectors capable of transmitting plant viruses are spider mites, lice, beetles and nematodes.

[0267] Further examples of vectors within the meaning of the present invention are insects and arachnids capable of transmitting pathogens to animals and / or humans, such as mosquitoes (in particular Aedes mosquitoes, Anopheles mosquitoes, such as A. gambiae, A. arabiensis, A. funestus, A. dirus (malaria) and Culex mosquitoes), Psychodidids, such as Phlebotomus, Lutzomyia, lice, fleas, flies, mites and ticks.

[0268] If the compounds of formula (I) are resistance-breaking, vector control is possible as well.

[0269] The compounds of formula (I) are suitable for use in the prevention of diseases and / or vector-borne pathogens. Thus, a further aspect of the invention is the use of the compounds of formula (I) for controlling vectors, for example in agriculture, in horticulture, in gardens and leisure facilities, and also in the protection of materials and stored products.

[0270] Protection of industrial materials The compounds of formula (I) are suitable for protecting industrial materials against attack or destruction by insects (e.g. insects of the orders Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma).

[0271] In the context of the present invention, industrial materials are understood to mean non-living materials, such as, preferably, plastics, adhesives, sizes, paper and cardboard, leather, wood, engineered wood products and paints, etc. The present invention is particularly preferably used for protecting wood.

[0272] In a further embodiment, the compounds of formula (I) are used together with at least one further insecticide and / or at least one fungicide.

[0273] In a further embodiment, the compounds of formula (I) are present as ready-to-use pesticides, i.e. they can be applied to the material without further modification. Suitable further insecticides or fungicides are in particular those listed above.

[0274] Surprisingly, it has also been found that the compounds of formula (I) can be used to protect against fouling objects in contact with seawater or brackish water, in particular ship hulls, screens, nets, buildings, moorings and signalling systems, etc. Likewise, the compounds of formula (I) can be used as antifouling agents, either alone or in combination with other active compounds.

[0275] Pest control in the sanitation sector The compounds of formula (I) are suitable for controlling pests in the hygiene field.In particular, the present invention can be applied in the domestic field, in the hygiene field and in the protection of stored products, especially to control insects, arachnids, ticks and mites encountered in enclosed spaces, such as dwellings, factory corridors, offices, vehicle cabins, animal breeding facilities.To control pests, the compounds of formula (I) are used alone or in combination with other active compounds and / or adjuvants.They are preferably used in household insecticide products.The compounds of formula (I) are effective against sensitive and resistant species, and are also effective against all developmental stages.

[0276] These pests include, for example, pests from the orders Scorpiones, Araneae and Opiliones of the Arachnida, pests from the orders Chilopoda and Diplopoda of the Centipedes, pests from the orders Blattodea, Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or from the class Insecta. Examples of such pests include pests of the orders Orthoptera, Siphonaptera and Zygentoma, as well as pests of the order Isopoda in the class Malacostraca.

[0277] They are used, for example, in aerosols, non-pressurized spray products such as pump sprays and atomizing sprays, automatic fogging systems, foggers, foams, gels, evaporator products with cellulose or plastic evaporator tablets, liquid evaporators, gel and film evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and moth gels, as granules or dusts, in broadcast bait or at bait stations.

[0278] Abbreviations and symbols AcOH: acetic acid aq.: water-based br.:Wide Boc: tert-butyloxycarbonyl d: double line DCC: N,N'-dicyclohexylcarbodiimide DIPEA: N,N-diisopropylethylamine DMF: N,N-dimethylformamide DMSO: Dimethyl sulfoxide ee: enantiomeric excess eq.: equivalent ES: electrospray ionization Et 3 N: Triethylamine EtOAc: ethyl acetate hr(s): time HATU: 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluorophosphate HOBt: 1-Hydroxybenzotriazole hydrate HPLC: High-performance liquid chromatography iPrOH: Isopropanol J: Coupling constant LCMS: Liquid chromatography-mass spectrometry m / z: mass / charge ratio M: Molar concentration m: multiplet MeCN: Acetonitrile MeOH: Methanol NaH 2 PO 4 : Monosodium phosphate NaOH: Sodium hydroxide Na 2 SO 4 : Sodium sulfate NH 4 Cl: Ammonium chloride NMR: nuclear magnetic resonance q:Quarter rt: room temperature R t :Holding time s: single wire sat.: saturation T: Temperature t: Mie line T3P®: Propylphosphonic anhydride THF: tetrahydrofuran TMSOK: Potassium trimethylsilanolate wt.: weight δ: chemical shift λ: Wavelength.

[0279] Process and Intermediate Description The compounds of formula I and shown in Table 3 can be prepared as shown in Scheme 1 below, where R 1 , R 2 , R 3 , R 4 and R 5 are as previously defined or represent the corresponding fragments of the compounds shown in Table 3. X represents OH or Cl.

[0280] Scheme 1 [ka]

[0281] X=OH: A triazole compound of formula (a) is reacted with a carboxylic acid of formula (b) (X=OH) to form a compound of formula I. For example, a mixture of a triazole of formula (a), a carboxylic acid of formula (b) (X=OH), a suitable coupling reagent such as T3P®, HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA in a suitable solvent such as ethyl acetate or DMF at a temperature ranging from about 0-100° C. provides a compound of formula I, which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0282] X=Cl: A triazole compound of formula (a) is reacted with a carboxylic acid chloride of formula (b) (X=Cl) to form a compound of formula I. For example, a mixture of a triazole of formula (a), a carboxylic acid chloride of formula (b) (X=Cl), and a suitable base such as triethylamine or DIPEA in a suitable solvent such as dichloromethane or THF at a temperature ranging from about 0 to 100° C. provides a compound of formula I, which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0283] Carboxylic acids of formula (b) (X=OH) and carboxylic acid chlorides of formula (b) (X=Cl) are commercially available or can be synthesized by methods known to those skilled in the art. The synthesis of certain carboxylic acids of formula (b) (X=OH) is described in WO2019197468.

[0284] The requisite triazole compounds of formula (a) can be prepared according to the method shown in Scheme 2 below, where R 3 and R 4 is as mentioned above, and R 1 is C 1 -C 6 is alkyl, R 5 is ethyl or n-propyl; or R 1 , R 3 , R 4 and R 5 represents the corresponding fragment of the compound shown in Table 3. LG is a suitable leaving group (see also WO2017192385).

[0285] Diagram 2 [ka]

[0286] An amine of formula (c) is reacted with a substituted triazole of formula (d) to form a compound of formula (a). For example, a triazole of formula (d), an amine of formula (c), K, in a suitable solvent such as acetonitrile or DMF is reacted with 2 CO 3、 A mixture of a suitable base, such as NaH or DIPEA, at a temperature in the range of about 20-120° C. provides a compound of formula (a), which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0287] Alternatively, the substituted triazole of formula (d) is reacted with ammonia to form the compound of formula (e). For example, solutions of ammonia and the substituted azole of formula (d) in a suitable solvent, such as methanol, are mixed in a sealed tube at a temperature ranging from about 0 to 25° C. to provide the compound of formula (e), which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as trituration. The substituted triazole of formula (e), the compound of formula (f), K, in a suitable solvent, such as acetonitrile or DMF, can be mixed to form the compound of formula (e). 2 CO 3 or DIPEA, at a temperature in the range of about 20-120° to provide a compound of formula (a), which can then be isolated and purified, if necessary, using techniques known in the art, such as chromatography.

[0288] The amines of formula (c) and compounds of formula (f) are either commercially available or can be synthesized by methods known to those skilled in the art. The requisite triazole compounds of formula (d) can be prepared according to the method shown in Scheme 3 below, where R 3 and R 4 is as mentioned above, and R 5 is ethyl or n-propyl; or R 3 , R 4 and R 5 represents the corresponding fragment of the compound shown in Table 3, and LG is a suitable leaving group (see also WO2017192385).

[0289] Diagram 3 [ka]

[0290] The amide of formula (h) is reacted with N,N-dimethylamide dimethyl acetal (g) to form a compound of formula (i), which is then reacted with hydrazine (j) under acidic conditions to form a compound of formula (d). For example, the compound of formula (h) and the N,N-dimethylamide dimethyl acetal of formula (g) can be reacted with CH under reflux to form a compound of formula (i). 2 Cl 2to provide a compound of formula (i). Upon removal of the solvent, the compound of formula (i) is reacted with a substituted hydrazine (j) in a suitable solvent such as 1,4-dioxane, acetic acid or a mixture of such solvents at a temperature ranging from about 20 to 100° C. to provide a compound of formula (d), which may then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0291] The N,N-dimethylamide acetals of formula (g), amides of formula (h) and hydrazines of formula (j) are either commercially available or can be synthesized by methods known to those skilled in the art.

[0292] for example: For 5-bromo-2-hydrazinopyridine, see WO2013 / 038362.

[0293] For 2-hydrazino-1,3-thiazoles, see US2008 / 0234327, WO2018 / 064119, WO2008 / 144767, WO2008 / 121861, WO2004 / 046120.

[0294] Compounds of formula I and those shown in Table 3 can be prepared according to the method shown in Scheme 4 below, where R 1 , R 2 , R 3 and R 4 is as previously defined, and R 5 is ethyl or n-propyl; or R 1 , R 2 , R 3 , R 4 and R 5 represents the corresponding fragment of the compound shown in Table 3.

[0295] Diagram 4 [ka]

[0296] An amide of formula (n) is reacted with an N,N-dimethylamide dimethyl acetal of formula (g) to form a compound of formula (o), which is subsequently reacted with a substituted hydrazine of formula (j) under acidic conditions to form a compound of formula I. For example, a compound of formula (n) and an N,N-dimethylamide dimethyl acetal of formula (g) can be reacted under reflux with CH 2 Cl 2 to obtain a compound of formula (o). The solvent is removed and the compound of formula (o) is reacted with a substituted hydrazine of formula (j) in a suitable solvent such as 1,4-dioxane, acetic acid or a mixture of such solvents at a temperature ranging from about 20 to 100° C. The resulting compound of formula I can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0297] The requisite amides of formula (n) can be prepared according to the method shown in Scheme 5 below, where R 2 and R 3 is as mentioned above, and R 1 is C 1 -C 6 alkyl or H (see also WO2017192385); or R 1 , R 2 and R 3 represents the corresponding fragment of the compound shown in Table 3.

[0298] Diagram 5 [ka]

[0299] An aminoamide of formula (p) is reacted with a carboxylic acid of formula (b) to form a compound of formula (n). For example, a mixture of an aminoamide of formula (p), a carboxylic acid (b), a suitable coupling reagent such as T3P®, HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA in a suitable solvent such as ethyl acetate or DMF at a temperature ranging from about 0 to 100° C. provides a compound of formula (n), which can then be isolated and purified as necessary and desired using techniques known in the art, such as chromatography.

[0300] Alternatively, an amino acid of formula (q) is reacted with thionyl chloride in a suitable solvent such as MeOH at room temperature to provide an amino ester of formula (r). The resulting amino ester (r) can be reacted with an aldehyde or ketone, a suitable reducing agent such as sodium triacetoxyborohydride, Na in a suitable solvent such as acetic acid at room temperature to provide an amino ester of formula (r). 2 SO 4 The resulting amino ester of formula (s) is then reacted with a carboxylic acid of formula (b), a suitable coupling agent such as T3P®, and a suitable base such as DIPEA in a suitable solvent such as ethyl acetate at about 90° C. to obtain an amide ester of formula (t), which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography. The resulting amide ester of formula (t) is reacted with magnesium nitride in a suitable solvent such as MeOH at about 80° C. in a sealed tube to obtain a compound of formula (n), which can then be isolated and purified, if necessary and desired, using techniques well known in the art, such as chromatography or extraction.

[0301] Compounds of formula (b) and (q) are either commercially available or can be synthesized by methods known to those skilled in the art. The synthesis of certain carboxylic acids (X=OH) of formula (b) is described in WO2019197468. The requisite aminoamide compounds of formula (p) are either commercially available or can be prepared according to the method shown in Scheme 6 below, where R 1 and R 3is as previously described or represents the corresponding fragment of a compound shown in Table 3, and LG is a suitable leaving group (see also WO2017192385).

[0302] Compounds of formula (c) and (h) are commercially available.

[0303] The requisite amine of formula (p) can be prepared according to the method shown in Scheme 6 below, 1 and R 3 are as previously described (see also WO2017192385) or represent the corresponding fragments of the compounds shown in Table 3.

[0304] Diagram 6 [ka]

[0305] The amine of formula (c) is reacted with an amide of formula (h) to form a compound of formula (p). For example, in a suitable solvent such as acetonitrile or DMF, an amine of formula (c), an amide of formula (h), K 2 CO 3 or DIPEA, at 25-80° C. to obtain the compound of formula (p), which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0306] In another approach, compounds of formula I can be prepared according to the method shown in Scheme 7 below, where R 1 , R 2 , R 3 , R 4 is as previously defined, and R 5 is ethyl, n-propyl, isopropyl, difluoromethyl or cyclopropyl; or R 1 , R 2 , R 3 , R 4 and R 5 represents the corresponding fragment of the compound shown in Table 3.

[0307] Diagram 7 [ka]

[0308] The amidine hydrochloride of formula (u) is reacted with an acid of formula (v). For example, the amidine hydrochloride of formula (u), the carboxylic acid (v), a suitable coupling reagent such as HATU, DCC or HOBt, and a suitable base such as triethylamine or DIPEA in a suitable solvent such as acetonitrile or DMF are combined at a temperature ranging from about 0 to 100° C. to form a compound of formula (w), which is then reacted with a substituted hydrazine of formula (j) under acidic conditions to form a compound of formula I, which can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0309] The amidine hydrochlorides of formula (u), the carboxylic acid derivatives of formula (v) and the hydrazines of formula (j) are either commercially available or can be synthesized by methods known to those skilled in the art.

[0310] Compounds of formula (j') can be prepared according to the method shown in Scheme 8 below, where E is trifluoromethoxy, difluoromethoxy or trifluoromethylsulfanyl, LG is chlorine, fluorine, methylthio, methylsulfinyl or methylsulfonyl, and A is N or CH.

[0311] Diagram 8 [ka]

[0312] A compound of formula (x) containing a leaving group (LG) (WO2016 / 00126 for LG=methylsulfonyl) is reacted with hydrazine hydrate to form a hydrazine of formula (j'). For example, a mixture of the leaving group-containing compound (x) and hydrazine hydrate in a suitable solvent such as methanol or ethanol is reacted at 0-80° C. to provide a compound of formula (j') or its hydrochloride, hydrobromide or methanesulfonate salt, which can then be isolated and purified as necessary and desired using techniques known in the art.

[0313] Compounds of formula (x) are either commercially available or can be synthesised by methods known to those skilled in the art.

[0314] Sulfoxides (sulfines) of general formula (z) and sulfones of formula (za) can be prepared as shown in Scheme 9 below, where Ar is phenyl or hetaryl and R x is C 1 -C 3 Alkyl, C 1-2 C haloalkyl or cyclopropyl.

[0315] Diagram 9 [ka]

[0316] The sulfanyl group-containing compound of formula (y) is reacted with an oxidizing reagent (abbreviated as [O] in Scheme 9) such as 3-chloroperbenzoic acid, ruthenium(III) chloride in combination with sodium periodate, or a combination of formic acid and hydrogen peroxide to form a compound of formula (z) or (za), depending on the molar equivalents of oxidizing agent used. Using one equivalent of oxidizing agent gives the sulfinyl compound of formula (z) and using two equivalents gives the sulfone compound of formula (za). The sulfinyl compound of formula (z) is a chiral compound that forms a mixture of optical isomers.

[0317] Compounds of formula (zd) may be prepared according to the method shown in Scheme 10 below, where E is H or C1 -C 6 A is an alkyl group, Hal is bromine or iodine, and G is cyclopropyl, which may be substituted with 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, and trifluoromethyl. * is fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclopropylsulfonyl, difluoromethylsulfonyl, trifluoroethylsulfonyl, trifluoromethylsulfonyl, -SF 5 and cyclopropyl, which is optionally substituted by 1 to 2 substituents selected from the group consisting of halogen, —CN, methyl, difluoromethyl and trifluoromethyl.

[0318] Diagram 10 [ka]

[0319] A halogen-containing compound of formula (zb) is reacted with a boronic acid of formula (zc) to form a compound of formula (zd). For example, a mixture of a halogen-containing compound of formula (zb), a boronic acid (zc), a suitable catalyst such as palladium (II) acetate in combination with tricyclohexylphosphine, and a suitable base such as tripotassium phosphate in a suitable solvent or mixture of solvents such as toluene and water is reacted at a temperature ranging from about 0 to 100° C. to provide a compound of formula (zd), which can then be isolated and purified as necessary and desired using techniques known in the art, such as chromatography. 1 -C 6 Compounds of formula (zd) where E is H can be converted to compounds of formula (zd) where E is H by treatment with an alkali hydroxide in a suitable solvent or mixture of solvents including, for example, tetrahydrofuran, ethanol or water at a temperature in the range of about 0-100° C.

[0320] Compounds of formula (zb) are commercially available or can be synthesized by methods known to those skilled in the art. * The synthesis of compounds of formula (zb) where is equal to methylsulfonyl, ethylsulfonyl, isopropylsulfonyl, cyclopropylsulfonyl is described by Scheme 11 and Schemes 12 and 9.

[0321] Compounds of formula (zf) may be prepared according to the method shown in Scheme 11 below, where E is H or C 1 -C 6 alkyl; Hal is iodine or bromine; R a is C 1 -C 3 alkyl or cyclopropyl; A * is fluorine, chlorine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl, and cyclopropyl is optionally substituted by 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl, and trifluoromethyl.

[0322] Diagram 11 [ka]

[0323] An aryl halide of formula (zb) is reacted with a sulfinate of formula (ze) under copper catalysis to form a sulfone of formula (zf).

[0324] For example, a mixture of a compound of formula (zb), a sodium sulfinic acid salt of formula (ze), copper(I) iodide, proline and sodium hydroxide is reacted in a suitable solvent such as dimethylsulfoxide at a temperature ranging from 40 to 140° C. (compare WO2019197468). In another approach, a mixture of a compound of formula (zb), a sodium sulfinic acid salt of formula (ze), copper(I) iodide, trans-N,N-dimethylcyclohexane-1-2-diamine and cesium carbonate is reacted in a suitable solvent such as DMF at a temperature ranging from 40 to 140° C. (see, for example, 3-methylsulfonyl-5-(trifluoromethoxy)benzoic acid reported in the present application).

[0325] The resulting compound of formula (zf) can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography. 1 -C 6 Compounds of formula (zf) where E is H can be converted to compounds of formula (zf) where E is H by treatment with an alkali hydroxide in a suitable solvent or mixture of solvents, such as containing tetrahydrofuran, ethanol or water, at a temperature in the range of about 0-100° C. When E is a tert-butyl group, the ester can be cleaved under acidic conditions in a suitable solvent, such as dichloromethane, in the presence of a suitable acid, such as trifluoroacetic acid, at a temperature in the range of 0-40° C. (see also the synthesis of 3-bromo-5-(1-fluorocyclopropyl)benzoic acid herein as an example of acidic cleavage of a tert-butyl ester).

[0326] Aryl halides (zb) and sulfinates of formula (zf) are either commercially available or can be synthesized by methods known to those skilled in the art. * The synthesis of compounds of formula (zb) where is cyclopropyl optionally substituted with 1-2 substituents selected from the group of halogen, -CN, methyl, difluoromethyl and trifluoromethyl is described in Scheme 10 and Scheme 21.

[0327] Compounds of formula (zj) can be prepared according to the method shown in Scheme 12 below, in which Hal is fluorine or chlorine and Rd is a C group optionally substituted by fluorine. 1 -C 3 alkyl or cyclopropyl; A * is chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, and cyclopropyl, and cyclopropyl is optionally substituted by 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl, and trifluoromethyl.

[0328] Diagram 12 [ka]

[0329] An aryl halide of formula (zg) is reacted with a thiolate salt of formula (zh) to form a thioether of formula (zi), which is then hydrolyzed to form a carboxylic acid of formula (zj).

[0330] For example, a mixture of a halide of formula (zg) and a sodium thiolate of formula (zh) is reacted in a suitable solvent such as N,N-dimethylformamide at a temperature in the range of -20 to 50°C. The resulting nitrile of formula (zi) is then hydrolyzed under basic conditions, for example with aqueous sodium hydroxide in a suitable solvent or solvent mixture such as ethanol or methanol / THF at a temperature in the range of 40 to 100°C, or under acidic conditions in a suitable strong acid such as sulfuric acid or hydrochloric acid, neat or diluted with a suitable diluent such as water, at a temperature in the range of 40 to 100°C. The resulting carboxylic acid (zj) is then purified as necessary and desired using techniques known in the art, such as chromatography. The sulfanyl group contained in the carboxylic acid (zj) can then be oxidized to a sulfinyl or sulfonyl group according to the method described in Scheme 9.

[0331] The requisite aryl halides (zg) and thiolate salts of formula (zh) are either commercially available or can be synthesized by methods known to those skilled in the art (e.g., WO2013049250 for the synthesis of cyclopropanethiols). The thiolate salts can be synthesized from the corresponding thiols by deprotonation with sodium hydride in a suitable solvent such as N,N-dimethylformamide. * The synthesis of compounds of formula (zg) where is cyclopropyl optionally substituted with 1-2 substituents selected from the group of halogen, -CN, methyl, difluoromethyl and trifluoromethyl can be accomplished by procedures similar to those described in Scheme 10 and Scheme 21.

[0332] Scheme 13 illustrates the preparation of the 3-haloalkyltriazole-containing amine (e') used, for example, in the synthesis of Example I-5. 5 is difluoromethyl, E' is hydrogen, chlorine or CN, A is N or CH.

[0333] Diagram 13 [ka]

[0334] In the first step, the hydrazone amide (zl) is formed according to the method described in EP1099695. In the second step, (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride, prepared according to Tetrahedron: Asymmetry, 21(8), 936-942, 2010 from (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) and oxalyl chloride, is reacted with the hydrazone amide in the presence of a base, such as pyridine, according to the method described in EP1099695 to form a triazole of formula (zm); partial or complete racemization is possible. In the third step, the phthalimide protecting group is removed by reaction with hydrazine hydrate in a suitable solvent, such as ethanol, according to the method described in WO2018086605. In the final step, the resulting amine is reacted with a carboxylic acid as described in Scheme 1 to form an example compound, such as I-5.

[0335] Compounds of formula (a) may also be prepared according to the method shown in Scheme 14 below, where R 1 , R 3 and R 4 is as previously defined, and R 5 is hydrogen, methyl, ethyl or n-propyl; or R 1 , R 3 and R 4 represents the corresponding fragment of the compound shown in Table 3.

[0336] Diagram 14 [ka]

[0337] An amide of formula (zn) is reacted with an N,N-dimethylamide dimethyl acetal of formula (g) to form a compound of formula (zo), which is then reacted with a substituted hydrazine of formula (j) under acidic conditions to form a compound of formula (zp). For example, a compound of formula (zn) and an N,N-dimethylamide dimethyl acetal of formula (g) can be reacted with CH under reflux to form a compound of formula (zo). 2 Cl 2 to provide a compound of formula (zo). After removal of the solvent, the compound of formula (zp) is reacted with a substituted hydrazine of formula (j) in a suitable solvent such as 1,4-dioxane, acetic acid or a mixture of such solvents at a temperature ranging from about 20 to about 80° C. The resulting compound of formula (zp) can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0338] The carbamate of formula (zp) is treated with an acid to form an amine of formula (a). For example, the carbamate of formula (zp) is reacted with a suitable acid, such as hydrogen chloride or trifluoroacetic acid, in a suitable solvent, such as dioxane, or in the case of trifluoroacetic acid, without additional solvent, at a temperature ranging from about 0 to 80° C. The resulting amine of formula (a) can then be isolated as an acid salt or as the free amine after treatment with a base, and purified as necessary and desired using techniques known in the art, such as chromatography.

[0339] The requisite amides of formula (zn) and hydrazines of formula (j) are either commercially available or can be synthesized by methods described herein or known to those skilled in the art.

[0340] Scheme 15 illustrates the preparation of alkyltriazole-containing amines (e″), such as those used in the synthesis of Example I-1. 5 is ethyl, n-propyl, isopropyl, cyclopropyl, and E' is hydrogen, -CN or chlorine. Z is NH 2 Or O.C. 1 -C 6 A is N or CH.

[0341] Diagram 15 [ka]

[0342] N-(tert-butoxycarbonyl)-L-alanine was reacted with alkyl amidine (Z=NH 2 When Z=OC 1 -C 6 In the case of an alkyl group, the intermediate of formula (zr) is reacted with a substituted hydrazine of formula (j″′) to form an alkyl triazole of formula (zs). For example, Z=NH 2 In the case of (compare J. Org. Chem. 2011, 76, 1177-1179), N-(tert-butoxycarbonyl)-L-alanine and an alkyl amidine of formula (zq) are reacted in the presence of a suitable coupling reagent, such as HATU, a suitable base, such as triethylamine or DIPEA, in a suitable solvent, such as DMF, at a temperature ranging from 0 to 50° C. to form an acylamidine intermediate of formula (zr). After removal of the solvent, the intermediate of formula (zr) is reacted with a substituted hydrazine of formula (j″′) in a suitable solvent, such as acetic acid, at a temperature ranging from about 20 to 80° C. The resulting alkyl triazole of formula (zs) can then be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0343] Z=OC 1 -C 6In the case of alkyl, N-(tert-butoxycarbonyl)-L-alanine and an alkyl imidate of formula (zq), or a suitable salt thereof, are reacted in the presence of a suitable coupling reagent, such as HATU, a suitable base, such as triethylamine or DIPEA, in a suitable solvent, such as THF, at a temperature ranging from about 0-25° C. to form an acylimidate intermediate of formula (zr). A substituted hydrazine of formula (j″′) is added and the intermediate of formula (zr) is reacted at a temperature ranging from about 20-80° C. to provide an alkyl triazole of formula (zs), which can be isolated and purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0344] A carbamate of formula (zs) is treated with an acid according to the method shown in Scheme 14 to form an amine of formula (e″).

[0345] The required alkyl amidines and alkyl imidates of formula (j"') or suitable salts and hydrazines thereof are either commercially available or can be synthesized by methods described herein or known to those skilled in the art (see, for example, WO2011133447 for the synthesis of methylcyclopropanecarboximidate hydrochloride).

[0346] Scheme 16 illustrates the preparation of alkoxytriazole-containing amines (e') used, for example, in the synthesis of Example I-7. Alkyl is methyl, ethyl, or isopropyl, E' is hydrogen, chlorine, or CN. A is N or CH.

[0347] Diagram 16 [ka]

[0348] The synthesis begins with the reaction of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl chloride with potassium thiocyanate (KSCN) in acetone to produce the corresponding isocyanate intermediate (zt), which in the next step is treated with the corresponding alcohol to give the O-alkyl[(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate (zu). Reaction between intermediate (zu) and hydrazine of formula (j″′) in ethanol gives the cyclization product of formula (zv) as described in Bioorganic & Medicinal Chemistry 26(2018)3321-3344. Deprotection of the amino group with hydrazine hydrate gives the primary amine of formula (e′). In the final step, the resulting amine is reacted with a carboxylic acid to form the exemplary compound, e.g., I-10 as described in Scheme 1.

[0349] Compounds of formula (zx) can be prepared according to the method shown in Scheme 17 below, where Alk is C 1 -C 6 is alkyl, R 4 is 5-cyanopyridin-2-yl, R 5 is ethyl, n-propyl, isopropyl or cyclopropyl.

[0350] Diagram 17 [ka]

[0351] (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride is reacted with an imidate (zq) or a suitable salt thereof to form an acyl imidate intermediate of formula (zw), which is then reacted with a hydrazine of formula (j) to produce a triazole of formula (zx). For example, a mixture of an acid chloride and an imidate of formula (zq) is reacted in a suitable solvent such as THF at a temperature ranging from −20 to 25° C. The resulting intermediate of formula (zw) is then reacted with a hydrazine of formula (j) in a suitable solvent such as THF at a temperature ranging from 0° C. to 80° C. The resulting triazole of formula (zx) is then purified as necessary and desired using techniques known in the art, such as chromatography. The phthalimide protecting group is removed using hydrazine as described in Scheme 13 to provide the respective free amine.

[0352] The requisite acid chlorides can be obtained as described in Scheme 13, and imidates of formula (zq) or salts thereof are either commercially available or can be synthesized by methods known to those skilled in the art.

[0353] Scheme 18 illustrates the preparation of the 5-halogen triazole-containing amine (e″) used, for example, in the synthesis of Example I-28. 5 is chlorine, bromine, or iodine, E' is hydrogen, chlorine, or -CN, A is N or CH.

[0354] Diagram 18 [ka]

[0355] In the first step, (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) is reacted with 1-N-Boc-2-methyl-isothiourea (purchased from ABCR) in the presence of a base and the coupling reagent HATU to form the N-acylated 1-N-Boc-2-methyl-isothiourea (zz); partial or complete racemization is possible. In the second step, cyclization occurs with hydrazine (A is nitrogen and E′ is hydrogen) in the presence of a base such as pyridine to form the 1,2,4-triazole of formula (ya) (R 5 is NH-Boc. After N-Boc-deprotection in the third step under acidic conditions (HCl in dioxane), 3-amino-1,2,4-triazole hydrochloride (yb) (R 5 =NH 2 ), which in the fourth step is reacted first with tert-butyl nitrite and then with CuCl as described in N. Desroy et al., J. Med. Chem. 2013, 56, 1418-1430. 2 (R5=Cl), CuBr as described in Japanese Patent 2010070503A 2 (R 5 =Br), CuI / I as described in K. Pchalek and MP Hay J. Org. Chem. 2006, 71, 6530-6535 2 Mixture (R 5 =I) or 1,2-diiodomethane (R 5 =I) to form 3-halogen-substituted 1,2,4-triazoles. Alternatively, fluorine (R 5=F) can be introduced. In the fifth step, the phthalimide protecting group is removed by reaction with hydrazine hydrate in a suitable solvent such as ethanol as described in WO2018086605. In the final step, the resulting amine (e″) is reacted with a carboxylic acid to form example compounds, such as I-28, as described in Scheme 1.

[0356] Compounds of formula (ye) may be prepared according to the method shown in Scheme 19 below, 2 is as previously defined; Hal is chlorine, bromine or iodine; or R 2 represents the corresponding fragment of the compound shown in Table 3.

[0357] Diagram 19 [ka]

[0358] Compounds of formula (yd) can be further derivatized by halogenation of thiazole. The necessary methods are known to those skilled in the art. For example, iodination is carried out using a halogenating agent such as N-iodosuccinimide in a suitable solvent such as DMF (synthesis of Example II-51 described in the present application).

[0359] Scheme 20 shows the preparation of 3-halogen-1,2,4-triazole-containing compound (Ia) starting from 3-amino-1,2,4-triazole-containing compound (yg). Hal is chlorine, bromine, or iodine, E' is hydrogen, chlorine, or -CN. A is N or CH.

[0360] Diagram 20 [ka]

[0361] In the first step, N-Boc-alanine is reacted with 1-N-Boc-2-methyl-isothiourea (zy) (purchased from ABCR) (see Schemes 18 and 20) in the presence of a base and the coupling reagent HATU to form tert-butyl N-[(1S)-2-[[(tert-butoxycarbonylamino)-methylsulfanyl-methylene]amino]-1-methyl-2-oxo-ethyl]carbamate (yd), which can be used without purification. In the second step, cyclization of (yd) occurs with hydrazine (j″′) in the presence of an acid such as acetic acid to form a 1,2,4-triazole of formula (ye). In the third step, both N-Boc protecting groups are removed from the 1,2,4-triazole of formula (ye) by reaction with 4N HCl / dioxane to form the 3-amino-1,2,4-triazole-containing amine containing hydrochloride salt (yf). In the fourth step, the resulting amine salt (yf) is reacted with a carboxylic acid to form the enantiomerically enriched compound (yg), which is then converted in the fifth step to an enantiomerically enriched form (yg) by tert-butyl nitrite first and then CuCl as described in N. Desroy et al., J. Med. Chem. 2013, 56, 1418-1430. 2 (R5=Cl), CuBr as described in Japanese Patent 2010070503A 2 (R 5 =Br), CuI / I as described in K. Pchalek and MP Hay J. Org. Chem. 2006, 71, 6530-6535 2 Mixture (R 5 =I) or 1,2-diiodomethane (R 5 =I) to form 3-halogen substituted 1,2,4-triazole containing compounds (Ia), such as I-95 and I-96.

[0362] Acids of formula (ym) containing a substituted cyclopropyl group may also be prepared according to the method shown in Scheme 21 below: *is fluorine, chlorine, bromine, iodine, -CN, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, -SF 5 and cyclopropyl, which is optionally substituted with 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl and trifluoromethyl. 1 is -CN or -CO 2 C 1 -C 6 Alkyl. Z 2 and Z 3 are independently selected from the group consisting of hydrogen, halogen, -CN, methyl, difluoromethyl and trifluoromethyl, while the substituent Z 2 and Z 3 The prerequisite is that up to two of the aryl groups be different from hydrogen. L is iodo or trifluoroacetate. M is a transition metal complex fragment containing iron, copper, palladium or rhodium with appropriate ligand substitution.

[0363] Diagram 21 [ka]

[0364] Alkene-containing compounds of formula (yh) are reacted with free carbenes (yi), zinc carbenoids (yk) and certain transition metal carbene complexes (yj) to produce cyclopropyl-containing compounds of formula (yl). These can then be subjected to ester cleavage (Z 1 Ga-CO 2 C 1 -C 6 alkyl) or hydrolysis of the cyano group (Z 1 (x, ym) can be converted to an acid of formula (ym) by either cyclopropanation or cyclopropanation of the corresponding aryl group (x, ym) or by -CN (x, ym) or by -CN (x, ym). Different cyclopropanation reactions are known to those skilled in the art and can be found in the literature (e.g. Chem. Rev. 2017, 117, 11651-11679).

[0365] For the reaction with zinc carbenoid (yk), first Et 2Zn is reacted with trifluoroacetic acid in a suitable solvent such as anhydrous dichloromethane at 0 °C, followed by CH 2 I 2 Upon addition of an alkene (yh), a zinc carbenoid is generated. Upon addition of an alkene (yh), the preformed zinc carbenoid reacts with the alkene to form a cyclopropane at temperatures in the range of 20-40 °C (see also WO2012139775).

[0366] Different transition metal carbene complexes (yj) have been found to be suitable for cyclopropanation reactions. Examples of suitable precursors for such complexes are CuBr, Pd(OAc) 2 , Rh(OAc) 4 , or iron(III)-5,10,15,20-tetraphenylporphyrin (Fe(TPP)Cl).

[0367] For reactions mediated by palladium carbene complexes, a solution of alkene (yh) in a suitable solvent such as tetrahydrofuran or diethyl ether is reacted with Pd(OAc) 2 (See also the synthesis of tert-butyl 3-bromo-5-(1-fluorocyclopropyl)benzoate described in WO2014023367 or herein). Trifluoromethyl-substituted cyclopropyl groups can be obtained by reaction of alkenes (yh) with in situ generated trifluoromethyldiazomethane and iron carbene complexes obtained from Fe(TPP)Cl according to the method described in Angew. Chem. Int. Ed. 2010, 49, 938-941.

[0368] For the reaction with the free carbene (yi), a solution of the alkene (yh) in a suitable solvent is mixed with a carbene precursor from which the free carbene is generated in situ. For example, a solution of the alkene (yh) in diglyme is heated in the presence of sodium bromo(difluoro)acetate at a temperature in the range of 60-80 °C (see the synthesis of 3-bromo-5-(2,2-difluorocyclopropyl)benzonitrile described herein). An alternative carbene precursor is, for example, trimethyl(trifluoromethyl)silane, which is used in combination with sodium iodide (as described in WO2017040742).

[0369] Final hydrolysis of the cyano group to the corresponding acid (ym) can be carried out under basic or acidic conditions as described in Scheme 12. Hydrolysis of the ester can be carried out as described in Scheme 11.

[0370] The necessary alkenes (yh) and reagents required for the formation of the free carbenes (yi), zinc carbenoids (yk) and specific transition metal carbene complexes (yj) are commercially available or can be synthesized by methods known to those skilled in the art. For the synthesis of substituted alkenes (yh) via palladium catalyzed coupling reactions, see, for example, WO2013178362 (1-bromo-3-(1,1-dimethylethyl)-5-(1-methylethenyl)benzene), WO2012035011 (1,5-dichloro)-2-fluoro-3-(3,3,3-trifluoroprop-1-en-2-yl)benzene) and the present application (1-bromo-3-(1,1-difluoroethyl)-5-vinylbenzene).

[0371] A * is cyclopropyl, optionally substituted with 1 to 2 substituents selected from the group consisting of halogen, -CN, methyl, difluoromethyl and trifluoromethyl, can be obtained by the compound (yl) (Z 1 HA-CO 2 C 1 -C 6 is alkyl, and A * is iodine or bromine.) or acid (ym) (A* is iodine or bromine.) can be treated with the reaction conditions described in Scheme 10. * is the alkene fragment -(Z 2 C=CZ 2 Z 2 Compounds of formula (yh) corresponding to A can be reacted with two equivalents of a free carbene (yi), a zinc carbenoid (yk) and certain transition metal carbene complexes (yj) to give symmetrically substituted acids (ym). * Compounds of formula (yl), where is bromine or iodine, can be converted to optionally substituted alkenes of formula (yh) via a palladium catalyzed coupling reaction (see above), which can then be reacted as described in Scheme 21 to provide acids of formula (ym).

[0372] Compounds of formula (ys) can be prepared according to the method shown in Scheme 22 below. f is difluoromethyl and trifluoromethyl, and A * is chlorine, bromine, iodine, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy. Hal is R f is trifluoromethyl, it is iodine, R f If A is difluoromethyl, it is chlorine. * When is iodine or bromine, it can be converted to an optionally substituted cyclopropyl group as described in Scheme 10.

[0373] Diagram 22 [ka]

[0374] The aryl fluoride of formula (yn) is reacted with sodium sulfide to form a thiol of formula (yo), for example as described in Tetrahedron Letters, 2012, 53(20), 2548-2551. The haloalkyl thioether (yq) is then formed under alkylation conditions using trifluoromethyl iodide or difluoromethyl chloride and a suitable base. In the case of trifluoromethyl iodide, an additional catalyst is used, for example as described in WO2015035223. The nitrile functionality is then hydrolyzed to form a carboxylic acid of formula (yr). In an additional step, the thioether of formula (yr) is oxidized to a sulfone of formula (ys).

[0375] For example, a mixture of an aryl fluoride of formula (yn) and sodium sulfide is reacted in a suitable solvent such as N,N-dimethylformamide at a temperature ranging from −20 to 50° C. The resulting thiol of formula (yo) is then alkylated in the presence of, for example, triethylamine and 1,1′-dimethyl-4,4′-bipyridinium dichloride in a suitable solvent such as N,N-dimethylformamide at a temperature ranging from −20 to 50° C.

[0376] The resulting thioether of formula (yq) is hydrolyzed under basic conditions, for example using aqueous sodium hydroxide in a suitable solvent such as methanol at a temperature in the range of 40-100° C., or under acidic conditions in a suitable strong acid such as sulfuric or hydrochloric acid, neat or diluted with a suitable diluent such as water, at a temperature in the range of 40-100° C. The resulting carboxylic acid (yr) is then purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0377] The thioether-containing compound of formula (yr) is reacted with an oxidizing reagent, such as 3-chloroperbenzoic acid, in a suitable solvent, such as dichloromethane or a combination of acetic acid and hydrogen peroxide, at a temperature ranging from 0 to 50° C. to form a sulfone of formula (ys). The resulting sulfone of formula (ys) is then purified, if necessary and desired, using techniques known in the art, such as chromatography.

[0378] The requisite aryl fluorides (yn) are either commercially available or can be synthesized by methods known to those skilled in the art. EXAMPLES

[0379] The following preparation and use examples are illustrative of the present invention but are not intended to be limiting thereof.

[0380] Manufacturing Example Synthesis of 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-4) Phase 1 2-[6-Cyano-3-pyridinyl]hydrazide-2,2-difluoro-ethanimidic acid [ka]

[0381] To 2.33 g (17.4 mmol) of 5-hydrazinyl-2-pyridinecarbonitrile in methanol (30 mL) was added 3.15 g (24.3 mmol) of ethyl 2,2-difluoroethanecarboximidate (purchased from Enamine Building Blocks) and the reaction mixture was stirred overnight at room temperature. The solvent was evaporated and the residue was stirred with n-hexane (30 mL) and ethyl acetate (3 mL). The brownish precipitate was separated and dried to give 3.38 g of 2-[6-cyano-3-pyridinyl]hydrazido-2,2-difluoro-ethanimidic acid (purity: 90.4%; yield: 83.0%).

[0382] ESI mass [m / z]:211.1[M+H] + .

[0383] Phase 2 6-[3-(difluoromethyl)-5-[1-(1,3-dioxoisoindolin-2-yl)ethyl]-1,2,4-triazol-1-yl]pyridine-3-carbonitrile [ka]

[0384] To 3.28 g (14.0 mmol) of 2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoro-ethanimidic acid in pyridine (20 mL) was added 3.32 g (14.0 mmol) of (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride (prepared from (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH purchased from ABCR) and oxalyl chloride, see DA Gruzdev et al., Tetrahedron:Asymmetry, 21(8), 936-942, 2010) and the reaction mixture was stirred overnight at room temperature. Then, water (200 mL) was added and the mixture was extracted with dichloromethane (200 mL). The organic layer was washed with saturated NaHCO 3 Extract twice with aqueous solution (100 mL) and add Na 2 SO 4 The mixture was dried at 40° C. and evaporated under reduced pressure to give a solid residue which was purified by chromatography on silica gel with a cyclohexane / acetone gradient to give 1.09 g (purity: 95.7%; yield: 18.8%) of the racemic title compound as a colorless solid.

[0385] ESI mass [m / z]:395.2[M+H] + .

[0386] Phase 3 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-4) [ka]

[0387] To 1.0 g (2.5 mmol) of 6-[3-(difluoromethyl)-5-[1-(1,3-dioxoisoindolin-2-yl)ethyl]-1,2,4-triazol-1-yl]pyridine-3-carbonitrile in ethanol (20 mL) was added 577 mg (6.34 mmol) of hydrazine hydrate and the reaction mixture was heated to reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated to reflux for an additional hour, acetone (15 mL) was added, and heating was continued for an additional 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give 663 mg of racemic 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, which was used without further purification.

[0388] ESI mass [m / z]:265.2[M+H] + .

[0389] Synthesis of 6-{5-[(1S)-1-aminoethyl]-3-cyclopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride (1:1) (INT-3) Phase 1 tert-Butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate [ka]

[0390] To a solution of 2.0 g (10.5 mmol) of N-(tert-butoxycarbonyl)-L-alanine in 37.5 mL of N,N-dimethylformamide, 1.91 g (15.9 mmol) of cyclopropylamidine was added followed by 4.42 g (11.63 mmol) of HATU and 5.52 mL (31.7 mmol) of N,N-diisopropylethylamine, and the reaction mixture was stirred at room temperature for 3 hours. Then, 6.05 mL (105.7 mmol) of acetic acid and 2.13 g (15.8 mmol) of 6-hydrazinonicotinonitrile were added, and the reaction mixture was stirred at 80° C. for 5 hours and then at room temperature overnight. The reaction mixture was cooled to room temperature and diluted with saturated Na 2 CO 3 Aqueous solution was added and the mixture was then extracted with EtOAc. The combined organic layers were washed with water, 5% NaH 2 PO 4 aqueous solution, then brine, and finally Na 2 SO 4 After filtration and evaporation under reduced pressure, the crude was purified by preparative HPLC (water / acetonitrile). The combined product fractions were evaporated to give the title compound (0.77 g, 21%).

[0391] ESI mass [m / z]:355.3[M+H] + . 1 H-NMR peak list (400.2MHz, CD 3 CN): δ=8.8116 (6.3); 8.8100 (6.6); 8.8062 (6.7); 8.8046 (5.9); 8.2628 (4.8); 8.2573 (4.6); 8.2412 (5.5); 8.2357 (5.4); 7.9980 (7.0); 7.9964 (6.6); 7.9764 (5.9); 7.9747 (5.6); 5.8766 (0.8); 5.7388 (0.5); 5.7213 (1.4); 5.7031 (1.9); 5.6849 (1.3); 5.6682 (0.4); 2.1614 (41.0); 2.0585 (1.0); 2.0462 (2.0); 2.0378 (2.2); 2.0344 (1.4); 2.0255 (3.5); 2.0194 (1.3); 2.0132 (2.1); 2.0049 (2.2); 1.9926 (1.1); 1.9648 (4.6); 1.9528 (18.4); 1.9467 (34.9); 1.9405 (49.0); 1.9343 (33.6); 1.9281 (17.1); 1.4498 (14.5); 1.4328 (14.5); 1.3608 (16.0); 1.2685 (1.1); 1.2388 (0.7); 1.1974 (0.7); 1.0334 (0.4); 1.0281 (0.4); 1.0173 (1.7); 1.0106 (5.0); 1.0083 (4.1); 1.0049 (6.3); 0.9990 (1.5); 0.9901 (6.0); 0.9848 (6.4); 0.9754 (1.5); 0.9669 (2.7); 0.9546 (1.2); 0.9464 (3.2); 0.9446 (3.1); 0.9403 (2.8); 0.9385 (2.8); 0.9342 (3.2); 0.9324 (3.0); 0.9274 (4.6); 0.9204 (2.9); 0.9154 (3.3); 0.9084 (2.6); 0.9047 (1.3); 0.9014 (1.4); 0.8974 (1.0); 0.8927 (0.8); 0.8872 (0.7); 0.8837 (0.6); 0.1459 (0.8); 0.0080 (6.7); -0.0002 (166.9); -0.0086 (6.2); -0.0171 (0.6); -0.1495 (0.8).

[0392] Phase 2 6-{5-[(1S)-1-aminoethyl]-3-cyclopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride (1:1) (INT-3) [ka]

[0393] A solution of 830 mg (2.34 mmol) of tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate in 22 mL of dioxane was treated with 4N HCl / dioxane (10.9 mL). The reaction mixture was stirred at room temperature overnight. The resulting precipitate was separated by filtration and air-dried to give the title compound (0.71, 100%).

[0394] ESI mass [m / z]: 255.1 [amine + H] + .

[0395] Synthesis of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfonyl]benzamide (Example I-21) Phase 1 6-{5-[(1S)-1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile [ka]

[0396] Dissolve 5.00 g (95% purity, 21.6 mmol) of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid in 0.08 mL (1 mmol) of DMF in anhydrous CH 2 Cl 2 The solution in (30 mL) was treated with 3.78 mL (43.3 mmol) of oxalyl chloride at 0° C. The reaction mixture was stirred at ambient temperature for 2 days. All volatiles were removed under reduced pressure and the residue was used in the next step without further purification.

[0397] To a solution of 3.13 g (95% purity, 21.6 mmol) of methyl 2-methylpropanimidate hydrochloride (1:1) in 40 mL of anhydrous THF was added 15.1 mL (86.4 mmol) of anhydrous DIPEA at 0° C. The acid chloride prepared in the first step was dissolved in 20 mL of anhydrous THF and added dropwise to the solution of the imidate within 25 min. After stirring at 0° C. for 30 min, 3.19 g (23.7 mmol) of 6-hydrazinonicotinonitrile and 10 mL of anhydrous THF were added. The reaction mixture was stirred at 0° C. for 30 min and at ambient temperature overnight. All volatiles were removed under reduced pressure. To the residue was added 200 mL of water and the mixture was extracted with 200 mL of EtOAc. The phases were separated and the aqueous layer was extracted several times with EtOAc. The combined organic layers were washed with brine and Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by chromatography on silica (cyclohexane / ethyl acetate) to give 5.57 g of 6-{5-[(1S)-1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile.

[0398] ESI mass [m / z]:387.5[M+H] + .

[0399] Phase 2 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile (INT-2) [ka]

[0400] A solution of 2.00 g (5.17 mmol) of 6-{5-[(1S)-1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile and 0.38 mL of hydrazine hydrate in 40 mL of ethanol was heated at 80° C. for 2 h. The resulting suspension was stirred at ambient temperature overnight and then cooled to 10° C. The mixture was filtered and the residue was washed with ice-cold ethanol. The filtrate was concentrated under reduced pressure to give 1.57 g (70% purity) of 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile.

[0401] ESI mass [m / z]:257.2[M+H] + .

[0402] Phase 3 3-Chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfanyl]benzamide [ka]

[0403] A mixture of 98 mg (0.36 mmol) of 3-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzoic acid, 249 mg (0.65 mmol) of HATU, 0.15 mL (1.1 mmol) of N-ethyldiisopropylamine, and 2 mL of DMF was stirred at room temperature for 60 minutes. 120 mg (70% purity, 0.32 mmol) of 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile was added, and the mixture was stirred overnight. Water was added, and the mixture was repeatedly extracted with EtOAc. The combined organic layers were washed with brine and Na2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 166 mg of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfanyl]benzamide.

[0404] ESI mass [m / z]:509.3[M+H] + .

[0405] Phase 4 3-Chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfonyl]benzamide (Example I-21) [ka]

[0406] 165 mg (0.32 mmol) of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfanyl]benzamide CH 2 Cl 2 The solution in (2 mL) was treated with 168 mg (70% purity, 0.68 mmol) of m-chloroperbenzoic acid at 0° C. The mixture was stirred at 0° C. for 3 h, then another 84 mg (70% purity, 0.34 mmol) of m-chloroperbenzoic acid was added. The reaction mixture was stirred at 0° C. for an additional 2 h and at ambient temperature overnight. Saturated NaHCO 3 3 mL of aqueous solution was added and the mixture was stirred at ambient temperature for 1 h. The layers were separated and the aqueous layer was diluted with CH 2 Cl 2 The combined organic layers were washed with brine and 2 SO 4The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 124 mg of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-isopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(2,2,2-trifluoroethyl)sulfonyl]benzamide.

[0407] 1 H-NMR (400 MHz, d 6 -DMSO): See NMR peak list in Table 1.

[0408] ESI mass [m / z]:541.4[M+H] + .

[0409] Synthesis of 3-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzoic acid Phase 1 3-Chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzonitrile [ka]

[0410] To a suspension of 310 mg (7.1 mmol) of sodium hydride (55% suspension in mineral oil) in 15 mL of anhydrous N,N-dimethylformamide was carefully added 0.74 mL (8.35 mmol) of 2,2,2-trifluoroethanethiol. After stirring at room temperature for 30 min, 1.00 g (6.42 mmol) of 3-chloro-5-fluorobenzonitrile was added. The mixture was stirred at room temperature for 5 h and then diluted with H 2 The reaction was quenched by the addition of 1 mL O and 1.1 mL glacial acetic acid. The volatiles were removed under reduced pressure. Water and ethyl acetate were added to the residue. The layers were separated and the aqueous layer was extracted repeatedly with ethyl acetate. The combined organic layers were washed with brine and then with Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2O / acetonitrile) to give 1.40 g of 3-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzonitrile.

[0411] 1 H-NMR (400 MHz, d 6 -DMSO): 8.03 - 8.02 (m, 1H), 7.98 - 7.97 (m, 1H), 7.93 - 7.92 (m, 1H), 4.30 - 4.22 (q, 2H). ESI mass [m / z]:252.1[M+H] + .

[0412] Phase 2 3-Chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzoic acid [ka]

[0413] A mixture of 800 mg (3.17 mmol) of 3-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzonitrile, 3.5 mL of water, and 3.6 mL of concentrated sulfuric acid was heated at 100° C. for 2 days. Water and ethyl acetate were added. The layers were separated, and the aqueous layer was extracted repeatedly with ethyl acetate. The combined organic layers were washed with brine and then with Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 728 mg of 3-chloro-5-[(2,2,2-trifluoroethyl)sulfanyl]benzoic acid.

[0414] 1 H-NMR (400 MHz, d 6 -DMSO): 13.55 (s, 1H, COOH), 7.91 - 7.89 (m, 2H), 7.77 - 7.76 (m, 1H), 4.23 - 4.16 (q, 2H). ESI mass [m / z]:269.0[MH]- .

[0415] Synthesis of 6-{5-[(1S)-1-aminoethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile Phase 1 O-Methyl [(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate [ka]

[0416] To a solution of 1.0 g (4.6 mmol) of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid in 15 mL of toluene was added 0.80 mL (9.12 mmol) of oxalyl chloride and one drop of N,N-dimethylformamide. The reaction mixture was stirred at room temperature for 3 hours, then hexane (15 mL) was added and stirring was continued overnight. Then additional oxalyl chloride (0.5 mL) was added again and the reaction mixture was stirred for 3 hours and finally the solvent was evaporated. The crude residue was dissolved in acetone (15 mL), then 0.44 g (4.56 mmol) of KSCN was added as a solution in 5 mL of acetone and the mixture was stirred at 60° C. for 2 hours. Then 0.46 mL (11.4 mmol) of methanol was added and the mixture was stirred at 60° C. overnight, cooled to room temperature and evaporated under reduced pressure. The resulting residue was dissolved in EtOAc and washed with water and brine respectively, and finally the organic layer was washed with anhydrous Na 2 SO 4 The mixture was dried at rt and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to give the title compound (0.82 g, 59%).

[0417] ESI mass [m / z]:293.1[M+H] + .

[0418] Phase 2 6-{5-[(1S)-1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile [ka]

[0419] To a solution of 1.5 g (5.1 mmol) of O-methyl[(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate in 30 mL of ethanol was added 0.69 g (5.1 mmol) of 6-hydrazinonicotinonitrile and the reaction mixture was stirred at 90° C. overnight. The mixture was cooled to room temperature and the solvent was evaporated under reduced pressure, and the resulting residue was dissolved in EtOAc and washed with water and brine, respectively. The organic layer was extracted with anhydrous Na 2 SO 4 The mixture was dried at rt and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to give the title compound (1.23 g, 58%).

[0420] ESI mass [m / z]:375.1[M+H] + .

[0421] Phase 3 6-{5-[(1S)-1-aminoethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile (INT-5) [ka]

[0422] To a solution of 1.20 g (3.20 mmol) of 6-{5-[(1S)-1-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)ethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile in 30 mL of ethanol was added 0.39 mL (8.01 mmol) of hydrazine hydrate and the reaction was heated at reflux overnight. After the mixture was cooled to room temperature, acetone (10 mL) was added and it was heated again at reflux for 3 h. The resulting precipitate was filtered and the filtrate was evaporated under reduced pressure to give a residue that was used in the next step without further purification (1.05 g, 44% purity, 59% yield).

[0423] ESI mass [m / z]:245.1[M+H] + .

[0424] Following the procedure described above, (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethanamine (INT-22) and (1S)-1-[1-(5-chloropyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethanamine (INT-18) were also obtained. In these cases, the crude amine obtained after removal of the phthalimide protecting group was purified by reversed phase chromatography (H 2 The purified amine was isolated as the formate salt by elution with saturated NaHCO 3 This mixture was repeatedly extracted with ethyl acetate, and the combined organic layers were diluted with Na 2 SO 4 Drying by hexanes and removal of the solvent under reduced pressure isolated the free amines (INT-22) and (INT-18), which were used in the synthesis of example compounds.

[0425] Synthesis of 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride Phase 1 tert-Butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate [ka]

[0426] N 2 -(tert-Butoxycarbonyl)-L-alaninamide 2.00 g (10.6 mmol) CH 2 Cl 2 To the solution in (40 mL) was added 2.1 mL (16 mmol) of N,N-dimethylformamide dimethyl acetal. The solution was heated to reflux for 2 h, after which the solvent was removed under reduced pressure. The residue was dissolved in a mixture of 20 mL of 1,4-dioxane and 20 mL of glacial acetic acid. 1.7 g (13 mmol) of 6-hydrazinonicotinonitrile was added and the mixture was stirred at 50° C. for 60 min. The solvent was removed under reduced pressure and saturated NaHCO 3 Aqueous solution was added and the mixture was extracted repeatedly with ethyl acetate. The combined organic layers were washed with brine and 2 SO 4 The residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 3.0 g of tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate.

[0427] TIFF0007689109000043.tif9144

[0428] 1 H NMR (DMSO-d 6 , 400 MHz): 9.10 (s, 1H), 8.57 (dd, 1H), 8.21 (s, 1H), 8.05 (d, 1H), 7.52 (d, 1H), 5.63 (m, 1H), 1.43 (d, 3H), 1.31 (s, 9H). ESI mass [m / z]:259.2[MC 4 H8 +H] + .

[0429] Phase 2 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride [ka]

[0430] To a solution of 2.9 g (9.2 mmol) of tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate in 40 mL of 1,4-dioxane was added 23 mL of 4M HCl / 1,4-dioxane solution. The mixture was stirred at 50° C. for 4 h and at room temperature overnight. The solvent was removed under reduced pressure to give 2.81 g of residue containing 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride, which was used without further purification.

[0431] 1 H NMR (DMSO-d 6 , 400 MHz): 9.11 (d, 1H), 8.80 (br d, 3H), 8.61 (dd, 1H), 8.45 (s, 1H), 8.13 (d, 1H), 5.39 (m, 1H), 1.63 (d, 3H). ESI mass [m / z]: 215.2 [amine + H] + .

[0432] Synthesis of 3-chloro-5-(ethylsulfonyl)benzoic acid [ka]

[0433] A mixture of 0.47 g (4.1 mmol) of proline and 0.16 g (4.0 mmol) of sodium hydroxide in dimethyl sulfoxide (24 mL) was degassed by purging with argon for 30 min. 1.5 g (5.1 mmol) of methyl 3-chloro-5-iodobenzoate, 4.7 g (40 mmol) of sodium ethanesulfonate and 0.77 g (4.0 mmol) of copper(I) iodide were added and the mixture was further purged with argon for 5 min. The mixture was stirred at 120° C. for 3 h, cooled to room temperature and then treated with 4 mL of 2 M aqueous sodium hydroxide. It was further stirred at room temperature overnight, cooled to 10° C. and acidified to pH 1 with concentrated hydrochloric acid. Water was added to the mixture and it was extracted with ethyl acetate. The layers were separated and the aqueous layer was repeatedly extracted with ethyl acetate. The combined organic layers were washed twice with water and once with brine and then with Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 1.00 g of 3-chloro-5-(ethylsulfonyl)benzoic acid.

[0434] 1 H NMR (DMSO-d 6 , 400 MHz): NMR peak list: δ=8.2775 (3.5); 8.2737 (6.8); 8.2698 (4.4); 8.2363 (3.4); 8.2325 (4.0); 8.2313 (5.4); 8.2277 (4.1); 8.2090 (4.8); 8.2046 (5.5); 8.1997 (3.0); 3.4891 (1.9); 3.4707 (6.7); 3.4523 (6.8); 3.4340 (2.1); 3.3298 (6.3); 2.5259 (0.6); 2.5212 (1.0); 2.5125 (17.2); 2.5080 (36.2); 2.5034 (48.0); 2.4988 (33.7); 2.4942 (15.6); 1.1402 (6.9); 1.1219 (16.0); 1.1034 (6.8); -0.0002 (5.1). ESI mass [m / z]:247.1[MH]- .

[0435] Synthesis of 3-cyano-5-(methylsulfanyl)benzoic acid [ka]

[0436] To a solution of 1.00 g (6.06 mmol) of 3-cyano-5-fluorobenzoic acid in anhydrous N,N-dimethylformamide (20 mL) was added 363 mg (9.0 mmol) of sodium hydride (55% suspension in mineral oil) and 849 mg (12.1 mmol) of sodium methanethiolate. The mixture was stirred at room temperature for 90 min and at 80° C. overnight. The mixture was quenched by adding water. EtOAc was added and the layers were separated. The pH of the aqueous layer was adjusted to pH 1 by adding hydrochloric acid and the mixture was extracted repeatedly with EtOAc. The combined organic layers were washed with brine and then with Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 688 mg of 3-cyano-5-(methylsulfanyl)benzoic acid.

[0437] 1 H-NMR (400 MHz, d 6 -DMSO): 13.6 (brs, 1H), 8.03 - 7.95 (m, 3H), 2.58 (s, 3H). ESI mass [m / z]:192.1[MH] - .

[0438] Synthesis of 3-chloro-5-(1-cyanocyclopropyl)benzoic acid Phase 1: Methyl 3-chloro-5-(1-cyanocyclopropyl)benzoate [ka]

[0439] To a solution of methyl 3-chloro-5-(cyanomethyl)benzoate (12 g, 57 mmol) in 1,2-dibromoethane (150 mL) was added NaOH (4.58 g, 114 mmol) and benzyl(trimethyl)ammonium chloride (10.32 g, 68.69 mmol) in one portion at 25° C. The mixture was stirred at 65° C. for 12 h and then washed with saturated NH 4 The mixture was diluted with aqueous Cl (50 mL) and extracted with EtOAc (50 mL). The aqueous layer was extracted twice with EtOAc (30 mL). The combined organic layers were washed with Na 2 SO 4 The mixture was dried at 40° C. and filtered. The solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, petroleum ether / EtOAc=100 / 1 to 20 / 1) to give methyl 3-chloro-5-(1-cyanocyclopropyl)benzoate (8.8 g, 65% yield) as a yellow oil.

[0440] Phase 2: 3-Chloro-5-(1-cyanocyclopropyl)benzoic acid [ka]

[0441] To a solution of methyl 3-chloro-5-(1-cyanocyclopropyl)benzoate (8.8 g, 37 mmol) in THF (100 mL) at 25° C., TMSOK (6.71 g, 52.3 mmol) was added in one portion. The mixture was stirred at 25° C. for 12 h. The reaction suspension was adjusted to pH=5-6 with 1 M hydrochloric acid. The color of the suspension became orange-red. The mixture was diluted with H 2 The water was diluted with O (15 mL). The water was extracted three times with EtOAc (50 mL). The combined organic layers were washed with Na 2 SO 4 The extract was dried at 40° C., filtered, and concentrated under reduced pressure to give 3-chloro-5-(1-cyanocyclopropyl)benzoic acid (5.05 g, 61% yield) as a pale yellow solid.

[0442] 1H-NMR (400 MHz, MeOD): δ, 7.85 - 7.93 (m, 2H), 7.55 (t, J=1.9 Hz, 1H), 1.78 - 1.82 (m, 2H), 1.55 - 1.59 (m, 2H). Measured on a Varian 400MR NMR instrument.

[0443] Synthesis of 5-(difluoromethoxy)-2-hydrazinopyrimidine [ka]

[0444] A solution of 500 mg (2.60 mmol) of 5-(difluoromethoxy)-2-(methylsulfanyl)pyrimidine in ethanol (2 mL) was treated with 0.52 mL (11 mmol) of hydrazine hydrate. The mixture was heated to reflux overnight. The reaction mixture was then cooled to 5° C., at which point a white precipitate formed. The suspension was filtered and the precipitate was washed with ethanol. The residue was dried under vacuum to give 125 mg of 5-(difluoromethoxy)-2-hydrazinopyrimidine.

[0445] 1 H NMR (DMSO-d 6 , 400 MHz): 8.35 (s, 1 H), 8.28 (s, 2 H), 7.06 (t, J = 74 Hz, 1 H), 4.17 (br s, 2 H). ESI mass [m / z]:177.2[M+H] + .

[0446] Synthesis of 3-chloro-5-(difluoromethyl)benzoic acid (INT-09) Phase 1: O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate [ka]

[0447] 38.9 mL (279 mmol) of triethylamine, 1.14 g (9.3 mmol) of N,N-dimethylpyridin-4-amine (DMAP) and 13.8 g (112 mmol) of dimethylcarbamothioyl chloride were added in that order to a vigorously stirred suspension of 14.3 g (93 mmol) of 3-chloro-5-hydroxybenzonitrile in 450 mL of anhydrous EtOAc. The reaction mixture was brought to 55-60° C. and stirred at this temperature for 24 h. After cooling to room temperature, the reaction mixture was washed with 450 mL of water and 450 mL of brine. The organic layer was separated and concentrated with NaCl. 2 SO 4 The concentrate was dried at 40° C. and filtered. The filtrate was concentrated under reduced pressure to a volume of approximately 50 mL. The concentrate was diluted with 150 mL of n-hexane and the precipitate that formed was filtered off, washed with 150 mL of a 1:1 mixture of diethyl ether and n-hexane, and dried in vacuum at 60° C. (1 Torr, 3 h) to give 9.3 g (86%) of O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate as colorless crystals.

[0448] 1 H NMR (400 MHz, CDCl 3 ) δ: 3.35 (s, 3H), 3.46 (s, 3H), 7.30 (s, 1H), 7.35 (s, 1H), 7.53 (s, 1H) (measured on a Varian Gemini 2000 instrument).

[0449] Phase 2: S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate [ka]

[0450] A solution of 2.41 g (10 mmol) of O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate in 20 mL of anhydrous dimethylacetamide was heated at 220° C. for 35 min in a Biotage Initiator microwave. The reaction mixture was brought to room temperature and diluted with 40 mL of water. The resulting precipitate was filtered off, washed with hot (ca. 70° C.) water and n-hexane, and dried in vacuum at 60° C. (1 Torr, 3 h) to give 2.05 g (85%) of S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate as a white powder.

[0451] 1 H NMR (400 MHz, CDCl 3 ) δ: 3.05 (s, 3H), 3.10 (s, 3H), 7.64 (s, 1H), 7.69 (s, 1H), 7.73 (s, 1H) (measured on a Varian Gemini 2000 instrument).

[0452] Phase 3: 3-Chloro-5-sulfanylbenzoic acid [ka]

[0453] A hot (ca. 70° C.) solution of 68.5 g (1.71 mol) NaOH in 300 mL water was added to a suspension of 27.5 g (114 mmol) S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate in 700 mL warm (ca. 40° C.) methanol. The reaction mixture was stirred under reflux (20 h). Methanol was removed under reduced pressure and the aqueous solution was washed twice with 200 mL diethyl ether. The aqueous layer was separated and added dropwise to a suspension of 300 g ice in concentrated aqueous HCl (cooled in an ice bath under argon). The solution formed was filtered off, washed twice with 50 mL water and 50 mL n-hexane and dried in vacuum at 60° C. (1 torr, 3 h) to give 21.2 g (98%) 3-chloro-5-sulfanylbenzoic acid as a white powder.

[0454] 1 H NMR (400 MHz, CDCl3 ) δ: 3.65 (s, 1H), 7.50 (s, 1H), 7.86 (s, 1H), 7.89 (s, 1H), 10.80 (brs, 1H) (measured on a Varian Gemini 2000 instrument).

[0455] Phase 4: 3-Chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (INT-09) [ka]

[0456] K 2 CO 3 12.44 g (90 mmol) of 3-chloro-5-sulfanylbenzoic acid and 18.3 g (120 mmol) of sodium chloro(difluoro)acetate were added in that order to a solution of 11.32 g (60 mmol) of 3-chloro-5-sulfanylbenzoic acid in anhydrous DMF under an argon atmosphere. The reaction mixture was stirred at 95-100 °C for 3 h. Note: At 90-95 °C, CO 2 Vigorous evolution of volatiles! Volatiles were removed under reduced pressure and the residue was diluted with water to a volume of 500 mL. The product was extracted with diethyl ether. The aqueous layer was separated and added dropwise to a suspension of about 100 g of ice in 5% hydrochloric acid (200 mL). The suspension was stirred at room temperature for 20 h and the precipitate was filtered off and washed with 2 x 50 mL of water and a 1 / 1 mixture of n-hexane and diethyl ether. Drying in vacuum at 60°C (1 Torr, 3 h) gave 11 g of crude product ( 1 H and 19 85% purity by F NMR. Sublimation at 90-95 °C / 0.01 Torr gave 7.7 g (54%) of 3-chloro-5-[(difluoromethyl)sulfanyl]benzoic acid as a white powder.

[0457] 1 H NMR (400 MHz, CDCl 3) δ: 6.90 (t, 1H, J = 74.4 Hz), 7.83 (t, 1H, J = 2 Hz), 8.14 (t, 1H, J = 2 Hz), 8.20 (s, 1H), 10.50 (br s, 1H). (measured with a Varian Gemini 2000 instrument).

[0458] Synthesis of 3-chloro-5-[(difluoromethyl)sulfonyl]benzoic acid (INT-16) [ka]

[0459] Oxone (41.2 g, 67 mmol) was added in one portion to a stirred solution of 3-chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (8.0 g, 33.5 mmol) in methanol (200 mL) and water (50 mL). The reaction mixture was stirred at 25° C. for 48 h. It was filtered and the filter cake was washed with methanol. The combined filtrate was concentrated under reduced pressure and diluted with water. A white precipitate formed which was filtered, washed with water and dried in an oven at 100° C. to give 8.95 g of a white powder which was purified by CombiFlash to give 6.9 g (76%) of the pure acid.

[0460] 1 H-NMR (400 MHz, CD 3 OD) δ = 8.46 (s, 1H), 8.39 (s, 1H), 8.07 (s, 1H), 6.85 (t, 1H, J = 52.7 Hz). (measured on a Varian Gemini 2000 instrument).

[0461] Synthesis of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-[(difluoro-methyl)sulfinyl]benzamide (Example II-18) [ka]

[0462] 100 mg (0.20 mmol) of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-[(difluoromethyl)sulfanyl]benzamide CH 2 Cl 2 The solution in (2 mL) was treated with 62 mg (70% purity, 0.20 mmol) of m-chloroperbenzoic acid at 0° C. The mixture was stirred at 0° C. for 4 h and at room temperature overnight. 3 5 mL of aqueous solution was added and the mixture was stirred at ambient temperature for 30 min. The layers were separated and the aqueous layer was extracted repeatedly with EtOAc. The combined organic layers were washed with brine and diluted with Na 2 SO 4 The solvent was removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 88 mg of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-[(difluoromethyl)sulfinyl]benzamide.

[0463] 1 H-NMR (400 MHz, d 6 -DMSO): See NMR peak list in Table 3.

[0464] ESI mass [m / z]:451.1[M+H] + .

[0465] Synthesis of (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride (1:1) (INT-8) Phase 1: tert-Butyl {(1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate [ka]

[0466] To a solution of 3.0 g (15.8 mmol) of N-(tert-butoxycarbonyl)-L-alanine in 65 mL of THF, 3.56 g (23.7 mmol) of ethyl cyclopropanecarboximidate hydrochloride (1:1), 6.61 g (17.4 mmol) of HATU, and 10.25 mL (79.2 mmol) of N,N-diisopropylethylamine were added. The reaction mixture was stirred at room temperature for 3 hours. Then, 4.31 g (23.7 mmol) of 5-chloro-2-hydrazinopyrimidine hydrochloride (1:1) was added, and the reaction mixture was stirred at room temperature overnight. Saturated NaHCO 3 An aqueous solution was added and the mixture was then extracted with EtOAc. The combined organic layers were washed with water and brine. All volatiles were removed under reduced pressure and the residue was purified by reverse phase chromatography (H 2 O / acetonitrile) to give 1.1 g of tert-butyl {(1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate.

[0467] ESI mass [m / z]:365.4[M+H] + .

[0468] Phase 2: (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride (1:1) (INT-8) [ka]

[0469] To a solution of 1.10 g (3.01 mmol) of tert-butyl {(1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate in 20 mL of 1,4-dioxane was added 7.54 mL (30.1 mmol) of a 4M HCl / 1,4-dioxane solution. The mixture was stirred at 50° C. overnight. The solvent was removed under reduced pressure to give 987 mg of a residue containing (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride (1:1), which was used without further purification.

[0470] 1 H NMR (DMSO-d 6 , 400 MHz): 9.10 (s, 2H), 8.65 (br s, 3H), 5.18 - 5.28 (br m, 1H), 2.08 - 2.15 (m, 1H), 1.59 (d, 3H, J = 6.8 Hz), 0.89 - 1.08 (m, 4H). ESI mass [m / z]: 265.3 [amine + H] + .

[0471] Following the above procedure, (1S)-1-[1-(5-chloropyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride (1:1) (INT-20) was also obtained.

[0472] Synthesis of 3-cyclopropyl-5-(trifluoromethoxy)benzoic acid Phase 1: Methyl 3-cyclopropyl-5-(trifluoromethoxy)benzoate [ka]

[0473] Methyl 3-bromo-5-(trifluoromethoxy)benzoate 1.89 g (6.30 mmol), cyclopropylboronic acid 700 mg (8.15 mmol), K 3 PO 4 4.7 g (22 mmol), 178 mg (0.64 mmol) of tricyclohexylphosphine in toluene (40 mL) and H 2 The mixture in O (2 mL) was degassed by purging with argon. 72 mg (0.32 mmol) of palladium(II) acetate was added. The mixture was stirred at 100° C. overnight. Water and ethyl acetate were added, the layers were separated, and the aqueous layer was extracted several times with ethyl acetate. The combined organic layers were washed with Na 2 SO 4 The mixture was dried at 40° C., filtered, and concentrated under reduced pressure to give 2.00 g of a residue containing methyl 3-cyclopropyl-5-(trifluoromethoxy)benzoate which was used without further purification.

[0474] ESI mass [m / z]:261.2[M+H] + .

[0475] Phase 2: 3-Cyclopropyl-5-(trifluoromethoxy)benzoic acid [ka]

[0476] A solution of 2.00 g of the crude product obtained in the first step in methanol (30 mL) was treated with 22 mL of 1 M aqueous sodium hydroxide. The mixture was stirred at room temperature overnight. The volatiles were removed under reduced pressure. Water was added, the pH was adjusted to pH 1 by addition of 1 M hydrochloric acid, and the mixture was repeatedly extracted with ethyl acetate. The combined organic layers were washed with Na 2 SO 4 After drying at 40° C., the solvent was removed under reduced pressure to give 1.55 g of 3-chloro-5-cyclopropylbenzoic acid.

[0477] 1 H NMR (DMSO-d 6, 400 MHz): 13.4 (br s, 1H), 7.65 (t, 1H, J = 1.6 Hz), 7.56 (t, 1H, J = 1.2 Hz), 7.34 (s, 1H), 2.05 - 2.15 (m, 1H), 1.00 - 1.08 (m, 2H), 0.72 - 0.80 (m, 2H). ESI mass [m / z]:247.2[M+H] + .

[0478] Synthesis of 3,5-dicyclopropylbenzoic acid [ka]

[0479] 3,5-Dicyclopropylbenzoic acid was synthesized in a similar manner to the previous benzoic acid using methyl 3,5-dibromobenzoate and 2.4 equivalents of cyclopropylboronic acid as starting materials. 1 H-NMR (400 MHz, DMSO-d6): δ = 7.38 (d, J = 1.6 Hz, 2H), 7.03 (t, J = 1.6 Hz, 1H), 2.00 - 1.91 (m, 2 H), 0.98 - 0.89 (m, 4H), 0.74 - 0.66 (m, 4H).

[0480] Synthesis of 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoic acid Phase 1: [3-Chloro-5-(methoxycarbonyl)phenyl]boronic acid [ka]

[0481] 12 g (40 mmol) of methyl 3-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate in 30 mL of acetone and H 2To a suspension in 20O (30 mL) was added 17.3 g (80.9 mmol) of sodium periodate and 6.24 g (80.9 mmol) of ammonium acetate. The mixture was stirred at 25° C. for 2 h and then filtered through Celite. The filtrate was evaporated. The residue was diluted with 200 mL of ethyl acetate and diluted with H 2 The organic layer was washed with 100 mL of O. The organic layer was washed with brine and anhydrous Na 2 SO 4 The mixture was dried at 40° C., filtered and concentrated under reduced pressure. The crude product was triturated with 10 mL of petroleum ether at 15° C. for 20 minutes. The mixture was filtered and the residue was dried in vacuum to give 7 g of [3-chloro-5-(methoxycarbonyl)phenyl]boronic acid as a white solid.

[0482] 1 H-NMR (400 MHz, CDCl 3 ): δ = 8.72 (s, 1H), 8.35 (s, 1H), 8.27 (s, 1H), 4.02 (s, 3H). Trace CHCl at 7.25 ppm. 3 The signal was used as the reference. Measurements were performed using a Varian 400MR NMR instrument.

[0483] Phase 2: Methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate [ka]

[0484] 13 g (61 mmol) of [3-chloro-5-(methoxycarbonyl)phenyl]boronic acid, 43.1 g (303 mmol) of trimethyl(trifluoromethyl)silane, Ag in 500 mL of DMF 2 CO 3 33.4g (121mmol), K 3 PO 4 38.6 g (182 mmol), CuSCN 762 mg (6.06 mmol), 1,10-phenanthroline 2.2 g (12 mmol), sulfur 46.7 g (1.46 mol), and 4 Å molecular sieves 13 g were mixed in a N 2The mixture was stirred at 25° C. for 16 hours under reduced pressure. The mixture was filtered through Celite. The filtrate was diluted with 1.5 L of methyl tert-butyl ether and diluted with H 2 The organic layer was washed with brine and anhydrous NaCl. 2 SO 4 The mixture was dried at 40° C., filtered and concentrated under reduced pressure. The crude product was purified by MPLC on silica gel (petroleum ether:ethyl acetate=1:0 to 20:1) to give 5.5 g of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate as a pale yellow oil.

[0485] 1 H-NMR (400 MHz, CDCl 3 ): δ =8.20 (s, 1H), 8.10 - 8.15 (m, 1H), 7.83 (s, 1H), 3.96 (s, 3H). Traces of CHCl at 7.25 ppm. 3 The signal was used as the reference. Measurements were performed using a Varian 400MR NMR instrument.

[0486] Phase 3: 3-Chloro-5-[(trifluoromethyl)sulfanyl]benzoic acid [ka]

[0487] Dissolve 5.5 g (20 mmol) of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate in 12 mL of tetrahydrofuran and H 2 The mixture was dissolved in 12 mL of 0. 1.63 g (40.6 mmol) of NaOH was added to the mixture, which was then stirred at 25° C. for 2 h. The mixture was adjusted to pH 5 by adding 40 mL of 1 M HCl and extracted with 150 mL of ethyl acetate. The organic layer was washed with brine and diluted with anhydrous Na 2 SO 4The crude product was triturated with 50 mL of petroleum ether at 25° C. for 15 min. The mixture was filtered and the residue was dried in vacuo to give 3.0 g of 3-chloro-5-(trifluoromethylsulfanyl)benzoic acid as a yellow solid.

[0488] 1 H-NMR (400 MHz, CDCl 3 ): δ =11.28 (br s, 1H), 8.29 (s, 1H), 8.20 - 8.25 (m, 1H), 7.91 (s, 1H). Traces of CHCl at 7.25 ppm. 3 The signal was used as the reference. Measurements were performed using a Varian 400MR NMR instrument.

[0489] ESI mass [m / z]:254.8[MH] - .

[0490] The LC-MS measurements were performed using a mobile phase of acetonitrile and 10 mM ammonium bicarbonate in water; a linear gradient from 15% acetonitrile to 90% acetonitrile, flow rate 0.80 mL / min; Agilent 1200 & Agilent 6120. The column used for chromatography was a 2.1 x 50 mm Xbridge Shield RPC18 column (5 μm particles). The detection methods were diode array (DAD) and evaporative light scattering (ELSD) detection, and negative electrospray ionization.

[0491] Synthesis of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(trifluoromethyl)sulfonyl]benzamide (Example II-15) Phase 1: N-[(2S)-1-amino-1-oxopropan-2-yl]-3-chloro-5-[(trifluoromethyl)sulfanyl]benzamide [ka]

[0492] 4.31 g (16.8 mmol) of 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoic acid was dissolved in dichloromethane, then 2 drops of DMF and 2.93 mL (34 mmol) of oxalyl chloride were added. The mixture was stirred at room temperature overnight. Dichloromethane and excess oxalyl chloride were removed under reduced pressure, and the remaining residue was diluted with acetonitrile. This solution was added dropwise to a solution of 8.37 g (67.2 mmol) of (2S)-2-aminopropanamide hydrochloride and 15.2 mL (109 mmol) of triethylamine in acetonitrile. The mixture was stirred at room temperature overnight. Water was added, and a precipitate formed. The mixture was filtered. The precipitate was dried to give 3.59 g of the title compound as a white solid with a purity of 98%. The filtrate was repeatedly extracted with dichloromethane. The combined organic layers were washed with water and diluted with anhydrous Na 2 SO 4 The mixture was dried at 4° C., filtered and concentrated under reduced pressure to give another batch of the title compound, 4.14 g, 70% pure.

[0493] ESI mass [m / z]:325.1[MH] + .

[0494] Phase 2: N-[(2S)-1-amino-1-oxopropan-2-yl]-3-chloro-5-[(trifluoromethyl)sulfonyl]benzamide [ka]

[0495] 3.6 g (11 mmol) of N-[(2S)-1-amino-1-oxopropan-2-yl]-3-chloro-5-[(trifluoromethyl)sulfanyl]benzamide was suspended in a mixture of 57 mL of dichloromethane, 56 mL of acetonitrile and 113 mL of water. 7.07 g (33.1 mmol) of sodium periodate and 2 mg (11 μmol) of ruthenium(III) chloride were added to the mixture, which was then stirred overnight at room temperature. The mixture was diluted by adding water and extracted repeatedly with dichloromethane. The combined organic layers were washed with brine and extracted with anhydrous Na 2 SO 4 The mixture was dried at 40° C., filtered, and concentrated under reduced pressure to give 3.07 g of the title compound as a colorless solid, which was used crude in the next step.

[0496] ESI mass [m / z]:359.0[M+H] + .

[0497] Phase 3: 3-Chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(trifluoromethyl)sulfonyl]benzamide (Example II-15) [ka]

[0498] 100 mg (279 μmol) of N-[(2S)-1-amino-1-oxopropan-2-yl]-3-chloro-5-[(trifluoromethyl)sulfonyl]-benzamide was dissolved in 20 mL of dichloromethane. 56 mg (0.42 mmol) of N,N-dimethylformamide dimethyl acetal was added and the reaction mixture was refluxed for 2 h. The solvent was removed under reduced pressure and the remaining residue was dissolved in a mixture of 5 mL of dioxane and 0.5 mL of acetic acid. 49 mg (0.36 mmol) of 6-hydrazinonicotinonitrile was added. The reaction mixture was stirred at 80° C. for 2 h, concentrated under reduced pressure and the residue was dissolved in CH 2 Cl 2 This solution was dissolved in saturated NaHCO 3The organic layer was then separated from the aqueous layer using a Chromabond™ PTS separation column and concentrated under reduced pressure. The remaining residue was purified by chromatography on silica (cyclohexane / ethyl acetate) to give 147 mg of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methyl-1H-1,2,4-triazol-5-yl]ethyl}-5-[(trifluoromethyl)sulfonyl]-benzamide as a colorless solid.

[0499] 1 H-NMR (400 MHz, d 6 -DMSO): See NMR peak list in Table 3.

[0500] ESI mass [m / z]:499.1[M+H] + .

[0501] Synthesis of 3-chloro-N-{1-[3-chloro-1-pyrimidinyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(methylsulfonyl)benzamide (Example I-29) Phase 1 tert-Butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanyl-carbonimidoyl]carbamate [ka]

[0502] To 1.09 g (5.0 mmol) of (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) and 0.95 g (5.0 mmol) of 1-N-Boc-2-methyl-isothiourea (purchased from ABCR) dissolved in tetrahydrofuran (30 mL), triethylamine (2.1 mL) and [O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluoro-phosphate] (HATU) were added and the reaction mixture was stirred at a temperature of 80° C. for 2 hours. Water was then added and the mixture was extracted with sodium bicarbonate solution and dichloromethane. The organic layer was separated and diluted with Na 2 SO 4 The mixture was dried at 40° C., filtered and the solvent was evaporated. The remaining solid residue was purified by chromatography on silica gel using a cyclohexane / acetone gradient to give 1.40 g of the racemic title compound (purity: 97.0%; yield: 69.6%).

[0503] ESI mass [m / z]:392.2[M+H] + . 1 H-NMR (400 MHz, DMSO-d 6, ppm): NMR peak list: δ =11.8958 (0.5); 11.4353 (0.9); 7.9299 (0.5); 7.9221 (1.0); 7.9152 (1.2); 7.9102 (1.0); 7.9063 (1.2); 7.9000 (2.1); 7.8930 (1.1); 7.8847 (2.6); 7.8785 (1.3); 7.8744 (1.2); 7.8627 (0.8); 4.9976 (0.8); 4.9794 (0.8); 3.3230 (9.5); 2.5251 (0.4); 2.5204 (0.6); 2.5117 (8.2); 2.5072 (16.6); 2.5027 (21.9); 2.4981 (15.8); 2.4936 (7.6); 2.2949 (2.4); 1.9720 (6.0); 1.6029 (2.9); 1.5848 (3.0); 1.5719 (1.3); 1.5540 (1.1); 1.4430 (16.0); 1.3971 (11.0); 1.2665 (6.6); -0.0002 (0.5).

[0504] Phase 2 2-[1-[3-(N-Boc-amino)-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione [ka]

[0505] To a solution of 1.0 g (2.6 mmol) of tert-butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanyl-carbonimidoyl]carbamate in 50 mL of pyridine was added 338 mg (3.06 mmol) of 2-hydrazinopyrimidine at room temperature. The reaction mixture was stirred at 80° C. for 2 h. The solvent was then evaporated under reduced pressure and the crude product was chromatographed on silica gel with a cyclohexane / acetone gradient to give 780 mg of the racemic title compound (purity: 95.9%; yield: 67.2%).

[0506] ESI mass [m / z]:436[M+H] + . 1 H-NMR (600 MHz, DMSO-d 6 , ppm): NMR peak list: δ =9.9739 (1.2); 8.7635 (2.7); 8.7554 (2.7); 7.8169 (0.6); 7.8126 (0.8); 7.8097 (2.9); 7.8052 (3.0); 7.8020 (0.9); 7.7979 (0.6); 7.4395 (0.7); 7.4315 (1.4); 7.4234 (0.7); 6.0850 (0.8); 6.0732 (0.8); 5.7533 (0.3); 3.3088 (9.2); 2.5080 (3.8); 2.5050 (8.0); 2.5020 (11.1); 2.4989 (8.1); 2.4960 (3.8); 1.9448 (0.4); 1.9123 (0.4); 1.8008 (2.4); 1.7890 (2.4); 1.4365 (16.0); 1.3974 (6.1); -0.0001 (1.9).

[0507] Phase 3 2-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]isoindoline-1,3-dione hydrochloride [ka]

[0508] 8.8 g (17.1 mmol) of 2-[1-[3-(N-Boc-amino)-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione was treated with 4N HCl / dioxane solution (150 mL) and the reaction mixture was stirred at room temperature for 18 h. The reaction mixture was then concentrated and the racemic solid residue was used for halogen introduction (step 4) without further purification.

[0509] ESI mass [m / z]:336.2[M-Cl] + .

[0510] Phase 4 2-[1-[3-chloro-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione [ka]

[0511] To 300 mg (0.89 mmol) of 2-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]isoindoline-1,3-dione-hydrochloride in acetonitrile (20 mL) was added 205 mg (1.52 mmol) of copper(II) chloride, and then 129 mg (1.25 mmol) of tert-butyl nitrite was added dropwise to the reaction mixture at room temperature. The reaction mixture was then stirred at a temperature of 70° C. for 1 hour. The reaction mixture was treated with ethyl acetate, followed by saturated NaHCO 3 The organic layer was separated, dried, and the solvent was evaporated to give 178 mg of the racemic title compound (purity: 77%; yield: 56.0%), which was used in the deprotection reaction (step 5) without further purification. ESI mass [m / z]:355.3[M+H] + .

[0512] Phase 5 1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-10) [ka]

[0513] To 499 mg (2.5 mmol) of 2-[1-[3-chloro-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (20 mL) was added 320 mg (3.51 mmol) of hydrazine-hydrate and the reaction mixture was heated to reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated to reflux for an additional 2 h, acetone (2 mL) was added, and heating was continued for an additional 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give 310 mg (purity: 70-80%, yield: 98%) of racemic 1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-10), which was used in step 6 without further purification.

[0514] ESI mass [m / z]:225.1[M+H] + .

[0515] Phase 6 3-Chloro-N-[1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-methylsulfonyl-benzamide (Example I-29) [ka]

[0516] To 150 mg (0.66 mmol) of 1-(5-chloro-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-10), 160 mg (0.66 mmol) of 3-chloro-5-(sulfonylmethyl)-benzoic acid, 120 mg (0.92 mmol) of N,N-diisopropylethylamine (Hunig's base) in N,N-dimethylformamide (DMF) (3 mL) was added 310 mg (0.81 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluoro-phosphate] (HATU) and the reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure and the solid residue was treated with dichloromethane and then saturated NaHCO 3 The organic layer was separated and extracted with Na 2 SO 4 The mixture was dried at 40° C. and the solvent was evaporated under reduced pressure. The remaining solid residue was purified by chromatography on silica gel with a cyclohexane / acetone gradient to give 99 mg of the racemic title compound (purity: 100%; yield: 34%).

[0517] ESI mass [m / z]:441.2[M+H] + .

[0518] 1 H-NMR: See the NMR peak list in Table 1.

[0519] Synthesis of 3-chloro-N-{1-[3-bromo-1-pyrimidinyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(methylsulfonyl)benzamide (Example I-35) Phase 4 2-[1-[3-bromo-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione [ka]

[0520] To 2.0 g (5.9 mmol) of 2-[1-(5-amino-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]isoindoline-1,3-dione-hydrochloride in acetonitrile (133 mL) was added 2.7 g (12 mmol) of copper(II) bromide, and then 1.0 g (9.7 mmol) of tert-butyl nitrite was added dropwise to the reaction mixture at room temperature. The reaction mixture was then stirred at a temperature of 70° C. for 1 hour. The reaction mixture was treated with ethyl acetate, followed by saturated NaHCO 3 The solution was extracted with water and the organic layer was separated, dried and the solvent was evaporated to give 1.10 g of the racemic title compound (purity: 97%; yield: 45%), which was used in the coupling reaction (step 5) without further purification.

[0521] ESI mass [m / z]:399.2[M+H] + .

[0522] Phase 5 1-(5-Bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-11) [ka]

[0523] To 1.16 g (2.91 mmol) of 2-[1-[3-bromo-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (30 mL) was added 678.8 mg (7.45 mmol) of hydrazine-hydrate and the reaction mixture was heated to reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated to reflux for an additional 2 h, acetone (20 mL) was added and heating was continued for an additional 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give 0.9 g (purity: 50-60%) of racemic 1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-11), which was used in step 6 without further purification.

[0524] ESI mass [m / z]:271.1[M+H] + .

[0525] Phase 6 N-[1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-3-chloro-5-methylsulfonyl-benzamide (Example I-35) [ka]

[0526] To 180 mg (0.66 mmol) of 1-(5-bromo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-011), 160 mg (0.66 mmol) of 3-chloro-5-(sulfonylmethyl)-benzoic acid, 124 mg (0.95 mmol) of N,N-diisopropylethylamine (Hunig's base) in acetonitrile (5 mL) and 320 mg (0.84 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluoro-phosphate] (HATU) were added. The reaction mixture was then stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure and the solid residue was treated with dichloromethane and then saturated NaHCO 3 The organic layer was separated and extracted with Na 2 SO 4 The mixture was dried at 40° C. and the solvent was removed under reduced pressure. The remaining solid residue was purified by HPLC with a water / acetonitrile gradient (neutral) to give 111 mg of the racemic title compound (purity: 98%; yield: 32%).

[0527] ESI mass [m / z]:487.0[M+H] + .

[0528] 1 H-NMR: See the NMR peak list in Table 1.

[0529] Synthesis of 3-chloro-N-{1-[3-iodo-1-pyrimidinyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(methylsulfonyl)benzamide (Example I-43) Phase 1 2-[1-[3-iodo-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione [ka]

[0530] To 11.2 g (30.2 mmol) of 2-[1-[3-(amino)-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione-hydrochloride (synthesized according to Example I-29 steps 1-3) in acetonitrile (448 mL) was added 181 g (676 mmol) of diiodomethane (argon atmosphere), then the reaction mixture was treated dropwise with 14.3 g (139 mmol) of tert-butyl nitrite at room temperature. The reaction mixture was then stirred at a temperature of 80° C. for 3 hours. The reaction mixture was treated with ethyl acetate and then extracted with a saturated NaCl solution. Afterwards, the solvent was evaporated under reduced pressure and the crude product was chromatographed on silica gel with a cyclohexane / acetone gradient to obtain 8.1 g (yield: 60%) of the racemic title compound.

[0531] ESI mass [m / z]:447.0[M+H] + .

[0532] Phase 2 1-(5-iodo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-12) [ka]

[0533] To 3.07 g (6.89 mmol) of 2-[1-[3-iodo-1-pyrimidinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (100 mL) was added 1.56 g (17.2 mmol) of hydrazine hydrate and the reaction mixture was heated to reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated to reflux for an additional 2 h, acetone (2 mL) was added and heating was continued for an additional 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give racemic 1-(5-iodo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethanamine (INT-12), which was used in step 3 without further purification.

[0534] ESI mass [m / z]:317.0[M+H] + .

[0535] Phase 3 3-Chloro-N-[1-(5-iodo-2-pyrimidin-2-yl-1,2,4-triazol-3-yl)ethyl]-5-methylsulfonyl-benzamide [ka]

[0536] To 100 mg (0.41 mmol) of 3-chloro-5-(sulfonylmethyl)-benzoic acid was added 75 mg (0.58 mmol) of N,N-diisopropylethylamine (Hunig's base) and 194 mg (0.51 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N′,N′-tetramethyluronium-hexafluoro-phosphate] (HATU) in 3.6 g (50 mmol) of N,N-dimethyl-formamide (DMF). The mixture was stirred at room t...

Claims

1. A compound of formula (I): 【Chemistry 1】 [In the formula, R １ is hydrogen; R ２ is 3-chloro-5-cyclopropylphenyl, 3-chloro-5-methylsulfonylphenyl, 3-chloro-5-(2,2,2-trifluoroethylsulfonyl)phenyl, 3-chloro-5-isopropylsulfonylphenyl, 3-cyclopropylsulfonyl-5-(trifluoromethyl)phenyl, 3-chloro-5-ethylsulfonylphenyl, 3-chloro-5-cyclopropylsulfonylphenyl, 3-ethylsulfonyl-5-(trifluoromethyl)phenyl, 3-cyclopropyl-5-(trifluoromethoxy)phenyl, 3-chloro-5-(difluoromethylsulfonyl)phenyl, 3-methylsulfonyl-5-(trifluoromethyl)phenyl, 3-chloro-5-(pentafluoro-λ6-sulfanyl)phenyl, 3-chloro-5-(1-cyanocyclopropyl)phenyl, 3-chloro-5-(trifluoromethylsulfonyl)phenyl, 3-methylsulfonyl-5-(trifluoromethoxy)phenyl, or 3-cyclopropylsulfonyl-5-(trifluoromethoxy)phenyl; R ３ is methyl; R ４ is 5-cyanopyridin-2-yl, pyrimidin-2-yl, 5-chloropyrimidin-2-yl or 5-chloropyridin-2-yl; and R ５ is cyclopropyl.

2. The following compound: 【Chemistry 2】 【change】 【change】

3. A compound of formula (e). 【Chemistry 3】 [In the formula, the structural element R ３ , R ４ and R ５ has the meaning given in claim 1.

4. compound 6-[5-[(1S)-1-aminoethyl]-3-ethyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile hydrochloride, (1S)-1-[1-(5-chloropyrimidin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride, (1S)-1-[1-(5-chloropyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethanamine, (1S)-1-[1-(5-chloropyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethanamine hydrochloride, or salts thereof, and in the case of amine hydrochlorides, the free amine.

5. A compound of the following formula (yf'): 【Chemistry 4】 wherein E' is hydrogen, chlorine or -CN, and A is N or CH, or a salt thereof.

6. 6. The compound according to claim 5, wherein the salt of the compound of formula (yf') is the hydrochloride salt.

7. The compound of claim 5, wherein the compound of formula (yf') is 5-[(1S)-1-aminoethyl]-1-(pyrimidin-2-yl)-1H-1,2,4-triazol-3-amine hydrochloride.

8. The compounds 3-cyclopropyl-5-(difluoromethyl)benzoic acid, 3-cyclopropyl-5-iodobenzoic acid, 3-chloro-5-[(difluoromethyl)sulfonyl]benzoic acid, 3-cyano-5-cyclopropylbenzoic acid, or 3-cyclopropyl-5-cyclopropylsulfonyl-benzoic acid, or salts thereof.

9. A formulation comprising at least one compound of formula (I) according to claim 1.

10. 10. The formulation according to claim 9, further comprising at least one bulking agent and / or at least one surfactant.

11. 11. Formulation according to claim 9 or 10, characterized in that the compound of formula (I) is mixed with at least one further active compound.

12. A method for controlling pests, excluding methods for treating the human or animal body by surgery or therapy and diagnostic methods carried out on the human or animal body, characterized in that a compound of formula (I) according to claim 1 or a formulation according to any one of claims 9 to 11 is applied to pests and / or their habitat.

13. 13. The method of claim 12, excluding methods of treatment of the human or animal body by surgery or therapy and diagnostic methods practiced on the human or animal body, wherein the pest is an animal pest and includes or is an insect, arachnid or nematode.

14. Use of a compound of formula (I) according to claim 1 or a formulation according to any one of claims 9 to 11 for the control of pest animals, excluding the use in methods for the treatment of the human or animal body by surgery or therapy and in diagnostic methods carried out on the human or animal body.

15. 15. The use according to claim 14, wherein the pest comprises or is an insect, arachnid or nematode, excluding uses in methods of treatment of the human or animal body by surgery or therapy and in diagnostic methods practiced on the human or animal body.

16. 16. Use according to claim 14 or 15 in crop protection, excluding uses in methods for the treatment of the human or animal body by surgery or therapy and in diagnostic methods performed on the human or animal body.

17. 16. Use according to claim 14 or 15 in the field of animal health, excluding use in methods of treatment of the human or animal body by surgery or therapy and in diagnostic methods carried out on the human or animal body.

18. A method for protecting a seed or a germinating plant from pests, excluding methods of treatment of the human or animal body by surgery or therapy and diagnostic methods practised on the human or animal body, comprising the method step of contacting a seed with a compound of formula (I) as defined in claim 1 or with a formulation as defined in any one of claims 9 to 11.

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