Novel heteroaryl-triazole compounds as pesticides

Abstract

The present invention relates to novel heteroaryl-triazole compounds of general formula (I) in which the structural elements R1, R2, R3, R4 and R5 have the meanings described, to formulations and compositions containing said compounds, and to their use in controlling animal pests, including arthropods and insects, in plant protection, and in controlling ectoparasites on animals. [Formula 1] TIFF2022541807000134.tif61157

Description

Technical Field

[0001] The present invention relates to novel heteroaryl - triazole compounds, formulations and compositions containing such compounds, and their use in the control of animal pests including arthropods and insects in plant protection, and their use for the control of external parasites on animals.

Background Art

[0002] Certain heteroaryl - triazole and heteroaryl - tetrazole compounds have been disclosed in WO 2017 / 192385 regarding their use in the control of external parasites on animals, and in WO 2019 / 170626 and WO 2019 / 215198 regarding their use in the control of animal pests including arthropods and insects in the field of plant protection. Further, patent applications WO 2019 / 197468, WO 2019 / 201835, WO 2019 / 202077 and WO 2019 / 206799 disclose certain heteroaryl - triazole compounds regarding their use in the control of external parasites on animals and their use in the control of animal pests including arthropods and insects in the field of plant protection. WO 2020 / 002563, WO 2020 / 053364, WO 2020 / 053365, WO 2020 / 079198, WO 2020 / 094363 all describe azole - amide compounds that can be used as insecticides.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

[0004] Modern plant protection products and veterinary ectoparasiticides must meet many requirements, for example, in terms of effectiveness, persistence, spectrum, and resistance-breaking properties. There are problems with toxicity, the possibility of combination with other active compounds or formulation adjuvants that play a role, and the cost required for the synthesis of active compounds. Furthermore, resistance may occur. For all these reasons, the search for new crop protection compositions or veterinary ectoparasiticides cannot be considered complete, and there is a constant need for new compounds having improved properties at least in terms of individual aspects compared to known compounds.

[0005] An object of the present invention was to provide a compound that broadens the spectrum of pesticidal agents in various aspects. [Means for Solving the Problems]

[0006] Accordingly, the present invention provides a compound of general formula (I), [Chemistry]

[0007] In the formula (Constitution 1-1), R 1 is hydrogen, R 2 is phenyl or pyridine, where phenyl or pyridine may be substituted with 1 to 2 substituents, provided that the (one or more) substituents are not on any carbon adjacent to the carbon bonded to the C=O group and are each independently fluorine, chlorine, bromine, -CN, -NO 2 , -SF 5 , methyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, methoxy, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, difluoroethylthio, and trifluoroethylthio, and is selected from the group consisting of R 3 is C 1 -C 3 alkyl, R 4 is pyridine, pyrimidine or pyrazine, where pyridine, pyrimidine or pyrazine is substituted with CN.

[0008] R 5 is ethyl, iso-propyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, iso-propoxy, or halogen.

[0009] The compounds of formula (I) likewise include any diastereomers or enantiomers and E / Z isomers present, as well as salts and N-oxides of the compounds of formula (I), and their use for the control of animal pests.

[0010] The definitions of the preferred radicals of the formulas specified above and below are shown below.

[0011] Preferred ones (Configuration 2-1) for the compounds of formula (I) are provided, wherein R 1 is hydrogen, R 2 is 3-chloro-5-(trifluoromethyl)phenyl, 3-chloro-5-(difluoromethyl)phenyl, 3-chloro-5-(pentafluoroethyl)phenyl, 3-chloro-5-(trifluoromethoxy)phenyl, 3-chloro-5-(trifluoromethylthio)phenyl, 3-chloro-5-(difluoromethylthio)phenyl, 3-chloro-5-(difluoromethoxy)phenyl, 3-bromo-5-(trifluoromethoxy)phenyl, 3-bromo-5-chlorophenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3,5-bis(trifluoromethyl)phenyl, 3-cyano-5-(trifluoromethyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 5-bromopyridin-3-yl, 3-bromo-5-(trifluoromethyl)phenyl, 3-fluoro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 6-bromopyridin-2-yl, 5-(trifluoromethyl)pyridin-3-yl, 6-(trifluoromethyl)pyridin-2-yl, 2-chloro-6-(trifluoromethyl)pyridin-4-yl or 4-bromo-6-(trifluoromethyl)pyridin-2-yl, R 3 is methyl, R 4 is 5-cyanopyridin-2-yl, R 5 is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy, chlorine or bromine.

[0012] Preferred ones (configuration 2-2) for the compound of formula (I) are also provided, wherein, R 1 is hydrogen, R 2is 3-chloro-5-(trifluoromethyl)phenyl, 3-chloro-5-(difluoromethyl)phenyl, 3-chloro-5-(pentafluoroethyl)phenyl, 3-chloro-5-(trifluoromethoxy)phenyl, 3-chloro-5-(trifluoromethylthio)phenyl, 3-chloro-5-(difluoromethylthio)phenyl, 3-chloro-5-(difluoromethoxy)phenyl, 3-bromo-5-(trifluoromethoxy)phenyl, 3-bromo-5-chlorophenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3,5-bis(trifluoromethyl)phenyl, 3-cyano-5-(trifluoromethyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 5-bromopyridin-3-yl, 3-bromo-5-(trifluoromethyl)phenyl, 3-fluoro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 3-(difluoromethyl)-5-(trifluoromethoxy)phenyl, 3-(difluoromethoxy)-5-(difluoromethyl)phenyl, 6-bromopyridin-2-yl, 5-(trifluoromethyl)pyridin-3-yl, 6-(trifluoromethyl)pyridin-2-yl, 2-chloro-6-(trifluoromethyl)pyridin-4-yl or 4-bromo-6-(trifluoromethyl)pyridin-2-yl, R 3 is methyl, R 4 is 5-cyanopyridin-2-yl, R 5 is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy, chlorine or bromine.

[0013] In a more preferred embodiment, the present invention relates to a compound of formula (I’) in which R 3 is C 1 ~C 3 alkyl, particularly preferably methyl,

Chemical formula

[0014] wherein the structural element R1 , R 2 , R 4 and R 5 has the meaning given by configuration (1-1) or configuration (2-1) or configuration (2-2).

[0015] In a more preferred embodiment, the present invention relates to a compound of formula (I'') wherein R 3 is C 1 ~C 3 alkyl, particularly preferably methyl, [Chemical formula]

[0016] In the formula, the structural elements R 1 , R 2 , R 4 and R 5 has the meaning given by configuration (1-1) or configuration (2-1) or configuration (2-2).

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

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

[0019] In the formula, the structural elements R 3 , R 4 and R 5 has the meaning given by configuration (1-1) or configuration (2-1) or configuration (2-2), INT-1: Free amine of 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: Free amine of 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: 6-[5-[(1S)-1-aminoethyl]-3-tert-butyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile; INT-11: 6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile; and INT-12: 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile; and the hydrochloride salts of the free amines are included.

[0020] The present invention also encompasses the intermediates 3-chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (INT-9), 3-chloro-5-(difluoromethyl)benzoic acid (INT-10), 3-chloro-5-(pentafluoroethyl)benzoic acid (INT-13), 3-(trifluoromethoxy)-5-(difluoromethyl)benzoic acid (INT-14), and 3-(difluoromethoxy)-5-(difluoromethyl)benzoic acid (INT-15) and their salts.

[0021] The compounds of formula (I) may, depending on the nature of the substituents, be present in the form of stereoisomers, i.e., geometric and / or optical isomers or mixtures of isomers, in various compositions. Generally, only the compounds of formula (I) are discussed herein, but the present invention provides both the pure stereoisomers and any desired mixtures of these isomers.

[0022] However, according to the present invention, it is preferred to use the optically active stereoisomeric forms of the compounds of formula (I) and their salts.

[0023] Therefore, the present invention relates to both pure enantiomers and diastereomers and mixtures thereof for controlling animal pests including arthropods and especially insects.

[0024] Where appropriate, the compounds of formula (I) may exist in various polymorphic forms or as mixtures of various polymorphic forms. Both pure polymorphs and mixtures of polymorphs are provided by the present invention and can be used according to the present invention.

[0025] Definitions Those skilled in the art will recognize that, unless explicitly stated otherwise, the expressions "a" or "an" used in this application can mean "one", "one or more", or "at least one" depending on the context.

[0026] For all structures described herein, such as ring systems and groups, adjacent atoms must not be -O-O- or -O-S-.

[0027] Structures having possible carbon atoms (C atoms) of variables are, for more specifically defined as a result, in this application, C 炭素原子の下限 -C 炭素原子の上限 Structure (C LL -C UL Structure) can be referred to as. For example, an alkyl group may consist of 3 to 10 carbon atoms, in which case C 3 -C 10It corresponds to an alkyl. The ring structure composed of carbon atoms and heteroatoms can be referred to as an "LL-UL member" structure. An example of a 6-membered ring structure is toluene (a 6-membered ring structure substituted with a methyl group).

[0028] A substituent, for example, C LL -C UL The general term for an alkyl corresponds to a complex substituent, for example, C LL -C UL Cycloalkyl-C LL -C UL When it is at the end of an alkyl, the starting component of the complex substituent, for example, C LL -C UL Cycloalkyl can be mono-substituted or poly-substituted independently identically or differently by the latter substituent, for example, C LL -C UL alkyl. All general terms used in this application for chemical groups, cyclic systems, and cyclic groups can be more specifically defined by the addition of "C LL -C UL " or "LL~UL member".

[0029] In the definitions of the symbols shown in the above formula, generally, general terms representing the following substituents are used. Halogen refers to the 7th typical element, preferably fluorine, chlorine, bromine, and iodine, more preferably fluorine, chlorine, and bromine, and even more preferably fluorine and chlorine.

[0030] Examples of heteroatoms are N, O, S, P, B, and Si. Preferably, the term "heteroatom" refers to N, S, and O.

[0031] According to the present invention, "alkyl", by itself or as part of a chemical group, preferably represents a straight-chain or branched hydrocarbon 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. In particular, alkyls having 1 to 4 carbon atoms such as methyl, ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl or t-butyl are also preferred. The alkyl of the present invention may be substituted with one or more identical or different radicals.

[0032] According to the present invention, "alkenyl", by itself or as part of a chemical group, preferably represents a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one double bond, such as 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-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. In particular, alkenyl having 2 to 4 carbon atoms such as 2-propenyl, 2-butenyl or 1-methyl-2-propenyl is also preferred. The alkenyl of the present invention may be substituted with one or more identical or different radicals.

[0033] According to the present invention, "alkynyl", by itself or as part of a chemical group, preferably represents a linear or branched hydrocarbon having 2 to 6 carbon atoms and at least one triple bond, such as 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, 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. In particular, alkynyl having 2 to 4 carbon atoms such as ethynyl, 2-propynyl or 2-butynyl-2-propenyl is also preferred. The alkynyl of the present invention may be substituted with one or more identical or different radicals.

[0034] According to the present invention, "cycloalkyl", by itself or as part of a chemical group, preferably represents a monocyclic, bicyclic or tricyclic hydrocarbon 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. In particular, cycloalkyl having 3, 4, 5, 6 or 7 carbon atoms such as cyclopropyl or cyclobutyl is also preferred. The cycloalkyl of the present invention may be substituted with one or more identical or different radicals.

[0035] 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. In particular, alkylcycloalkyl having 4, 5 or 7 carbon atoms such as ethylcyclopropyl or 4-methylcyclohexyl is also preferred. The alkylcycloalkyl of the present invention may be substituted with one or more identical or different radicals.

[0036] 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. In particular, cycloalkylalkyl having 4, 5 or 7 carbon atoms such as cyclopropylmethyl or cyclobutylmethyl is also preferred. The cycloalkylalkyl of the present invention may be substituted with one or more identical or different radicals.

[0037] According to the present invention, "hydroxyalkyl" preferably represents 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. A hydroxyalkyl group having 1 to 4 carbon atoms is also preferred. The hydroxyalkyl group of the present invention may be substituted with one or more identical or different radicals.

[0038] According to the present invention, "alkoxy" preferably represents a straight-chain or branched O-alkyl having 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy and t-butoxy. An alkoxy group having 1 to 4 carbon atoms is also preferred. The alkoxy group of the present invention may be substituted with one or more identical or different radicals.

[0039] According to the present invention, "alkylthio" or "alkylsulfanyl" preferably represents a straight-chain or branched S-alkyl having 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, s-butylthio, and t-butylthio. An alkylthio group having 1 to 4 carbon atoms is also preferred. The alkylthio group of the present invention may be substituted with one or more identical or different radicals.

[0040] 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. An alkylsulfinyl group having 1 to 4 carbon atoms is also preferred. The alkylsulfinyl group of the present invention may be substituted with one or more identical or different radicals and can include both enantiomers.

[0041] 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. An alkylsulfonyl group having 1 to 4 carbon atoms is also preferred. The alkylsulfonyl group of the present invention may be substituted with one or more identical or different radicals.

[0042] According to the present invention, "cycloalkylthio" or "cycloalkylsulfanyl" preferably represents -S-cycloalkyl having 3 to 6 carbon atoms, such as cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio. A cycloalkylthio group having 3 to 5 carbon atoms is also preferred. The cycloalkylthio group of the present invention may be substituted with one or more identical or different radicals.

[0043] According to the present invention, "cycloalkylsulfinyl" preferably represents -S(O)-cycloalkyl having 3 to 6 carbon atoms, such as cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl. A cycloalkylsulfinyl group having 3 to 5 carbon atoms is also preferred. The cycloalkylsulfinyl group of the present invention may be substituted with one or more identical or different radicals and can include both enantiomers.

[0044] According to the present invention, "cycloalkylsulfonyl" preferably represents -SO 2 -cycloalkyl having 3 to 6 carbon atoms, such as cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl. A cycloalkylsulfonyl group having 3 to 5 carbon atoms is also preferred. The cycloalkylsulfonyl group of the present invention may be substituted with one or more identical or different radicals.

[0045] According to the present invention, "phenylthio" or "phenylsulfanyl" represents -S-phenyl, such as phenylthio. The phenylthio group of the present invention may be substituted with one or more identical or different radicals.

[0046] According to the present invention, "phenylsulfinyl" represents -S(O)-phenyl, such as phenylsulfinyl. The phenylsulfinyl group of the present invention may be substituted with one or more identical or different radicals and can include both enantiomers.

[0047] According to the present invention, "phenylsulfonyl" represents -SO 2 -phenyl, such as phenylsulfonyl. The phenylsulfonyl group of the present invention may be substituted with one or more identical or different radicals.

[0048] According to the present invention, "alkylcarbonyl" preferably represents a linear or branched alkyl-C(=O) having 2 to 7 carbon atoms, such as methylcarbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, s-butylcarbonyl and t-butylcarbonyl. An alkylcarbonyl having 1 to 4 carbon atoms is also preferred. The alkylcarbonyl of the present invention may be substituted with one or more identical or different radicals.

[0049] According to the present invention, "alkoxycarbonyl", alone or as a component of a chemical group, preferably represents a linear 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 with one or more identical or different radicals.

[0050] According to the present invention, "alkylaminocarbonyl" preferably represents a linear or branched alkylaminocarbonyl having 1 to 6 carbon atoms or 1 to 4 carbon atoms in the alkyl moiety, such as methylaminocarbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, s-butylaminocarbonyl and t-butylaminocarbonyl. The alkylaminocarbonyl group of the present invention may be substituted with one or more identical or different radicals.

[0051] 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 with one or more identical or different radicals.

[0052] According to the present invention, "aryl" preferably represents a monocyclic, bicyclic or polycyclic aromatic system having 6 to 14, particularly 6 to 10 ring carbon atoms, such as phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. Further, aryl also represents a polycyclic system such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, etc., in which the bonding site is on the aromatic system. The aryl group of the present invention may be substituted with one or more identical or different radicals.

[0053] An example of a substituted aryl is arylalkyl, which is likewise C 1 ~C 4 alkyl and / or C 6 ~C 14 and may be substituted by one or more identical or different radicals in the aryl moiety. Examples of such arylalkyl include benzyl and phenyl-1-ethyl.

[0054] According to the present invention, a "heterocycle" or "heterocyclic ring" represents a carbocyclic system having at least one ring, wherein at least one carbon atom is replaced by a heteroatom, preferably a heteroatom from the group consisting of N, O, S, P, B, Si, Se, and is saturated, unsaturated or heteroaromatic, and is unsubstituted or may be substituted, and the bonding site is on a ring atom. Unless otherwise defined, the heterocycle preferably contains 3 to 9 ring atoms, particularly 3 to 6 ring atoms, and the heterocycle preferably contains one or more, preferably 1 to 4, particularly 1, 2 or 3 heteroatoms from the group consisting of N, O and S, provided that two oxygen atoms must not be directly adjacent. The heterocycle usually contains 4 or fewer nitrogen atoms and / or 2 or fewer oxygen atoms and / or 2 or fewer sulfur atoms. When the heterocyclyl radical or heterocycle may be substituted, they may be fused to another carbocyclic or heterocyclic ring. In the case of a heterocyclyl which may be substituted, the present invention also encompasses polycyclic systems such as 8-azabicyclo[3.2.1]octanyl or 1-azabicyclo[2.2.1]heptyl. In the case of a heterocyclyl which may be substituted, the present invention also encompasses spiro ring systems such as 1-oxa-5-azaspiro[2.3]hexyl.

[0055] The heterocyclyl group of the present invention is, 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.

[0056] Particularly important is heteroaryl, i.e., heteroaromatic. According to the present invention, the term heteroaryl represents a heteroaromatic compound, i.e., a fully unsaturated aromatic heterocyclic compound corresponding to the above definition of a heterocycle. A 5- to 7-membered ring having 1 to 3, preferably 1 or 2, identical or different heteroatoms from the above groups is preferred. The heteroaryl of the present invention is, 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. The heteroaryl group of the present invention may be substituted with one or more identical or different radicals.

[0057] The "(optionally substituted)" group / substituent, for example, the substituted alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radicals, etc., means, for example, a substituted radical derived from an unsubstituted base structure, and the substituents, for example, one or more 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, carboxamide, SF 5 sulfonylamino, 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, C2 ~C 4 alkynyl, N-mono-C 1 ~C 4 alkylamino, N,N-di-C 1 ~C 4 alkylamino, N-C 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 alkenylcarbonyl, 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 4Alkylsulfinyl (C 1 ~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 including both enantiomers of alkylphosphinyl and C 1 ~C 4 including both enantiomers of alkylphosphonyl), N-C 1 ~C 4 Alkylaminocarbonyl, N,N-di-C 1 ~C 4 Alkylaminocarbonyl, N-C 1 ~C 4 Alkanoylaminocarbonyl, N-C 1 ~C 4 Alkanoyl-N-C 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-Aryl amino, benzyl amino, heterocyclyl and trialkylsilyl, substituents bonded via a double bond, for example, C 1 ~C 4 Selected from alkylidene (e.g., methylidene or ethylidene), oxo group, imino group and substituted imino group. When two or more radicals form one or more rings, these may be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example, include an aromatic ring, and may be further substituted. The substituents exemplified (the "first substituent level"), when containing a hydrocarbon component, for example, may have further substitution (the "second substituent level") by one or more substituents independently selected from halogen, hydroxyl, amino, nitro, cyano, isocyano, azide, acylamino, oxo group and imino group. The term "substituted (optionally substituted)" group preferably includes only one or two substituent levels.

[0058] The halogen-substituted chemical group or halogenated group (e.g., alkyl or alkoxy) of the present invention is mono- or poly-substituted with halogen up to the maximum possible number of substituents. Such groups are also called halo groups (e.g., haloalkyl). In the case of poly-substitution with halogen, the halogen atoms may be the same or different, and may all be bonded to one carbon atom, or may be bonded to a plurality of carbon atoms. Halogen is particularly fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, more preferably fluorine. More specifically, the halogen-substituted group is a monohalocycloalkyl such as 1-fluorocyclopropyl, 2-fluorocyclopropyl or 1-fluorocyclobutyl, a monohaloalkyl such as 2-chloroethyl, 2-fluoroethyl, 1-chloroethyl, 1-fluoroethyl, chloromethyl or fluoromethyl; trichloromethyl or trifluoromethyl or CF 2 CF 3such as perhaloalkyl, difluoromethyl, 2-fluoro-2-chloroethyl, dichloromethyl, 1,1,2,2-tetrafluoroethyl or 2,2,2-trifluoroethyl and the like. 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. Haloalkyl 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 is preferred. Haloalkyl having 1 or 2 carbon atoms and 1 to 5, identical or different halogen atoms selected from fluorine and chlorine, for example, especially difluoromethyl, trifluoromethyl or 2,2-difluoroethyl is particularly preferred. Further examples of halogen-substituted compounds are, for example, OCF 3 、OCHF 2 、OCH 2 F、OCF 2 CF 3 、OCH 2 CF 3 、OCH 2 CHF 2 and OCH 2 CH 2Haloalkylsulfanyl such as haloalkoxy of Cl etc., difluoromethylthio, trifluoromethylthio, trichloromethylthio, chlorodifluoromethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2,2,2-trifluoroethylthio or 2-chloro-1,1,2-trifluoroethylthio etc., haloalkylsulfinyl such as difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, chlorodifluoromethylsulfinyl, 1-fluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2,2-difluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl and 2-chloro-1,1,2-trifluoroethylsulfinyl etc., haloalkylsulfonyl such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoroethylsulfonyl etc.

[0059] In the case of a radical having a carbon atom, those having 1 to 4 carbon atoms, particularly 1 or 2 carbon atoms are preferred. Generally, halogen, for example, fluorine and chlorine, (C 1 ~C 4 )alkyl, preferably methyl or ethyl, (C 1 ~C 4 )haloalkyl, preferably trifluoromethyl, (C1 ~C 4 )alkoxy, preferably methoxy or ethoxy, (C 1 ~C 4 )substituents from the group of haloalkoxy, nitro and cyano are preferred. Here, the substituents methyl, methoxy, fluorine and chlorine are particularly preferred.

[0060] Substituted amino such as mono-substituted amino or di-substituted amino means a radical from the group of substituted amino radicals in which the nitrogen atom is N-substituted by one or two identical or different radicals from the group of alkyl, hydroxy, amino, alkoxy, acyl and aryl, preferably N-mono- and N,N-dialkylamino, (for example, 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 (for example, N-methoxymethylamino, N-methoxyethylamino, N,N-di(methoxymethyl)amino or N,N-di(methoxyethyl)amino), N-mono- and N,N-diarylamino, for example, optionally substituted aniline, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino and saturated N-heterocycles, where an alkyl radical having 1 to 4 carbon atoms is preferred, aryl is preferably phenyl or substituted phenyl, and for acyl, the definition given further below, preferably (C 1 ~C 4 )-alkanoyl is applied. The same applies to substituted hydroxylamino or hydrazino.

[0061] Substituted amino also includes quaternary ammonium compounds (salts) having four organic substituents on the nitrogen atom.

[0062] Optionally substituted phenyl is halogen, (C 1 ~C 4 )alkyl, (C 1 ~C 4 )alkoxy, (C 1 ~C4 )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 )alkylsulfinyl(C 1 ~C 4 )haloalkylsulfinyl, (C 1 ~C 4 )alkylsulfonyl(C 1 ~C 4 )haloalkylsulfonyl, cyano, isocyano and nitro, by the same or different radicals from the group consisting of, preferably, unsubstituted or mono-substituted or multi-substituted, preferably up to trisubstituted, preferably phenyl, for example, o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and 4-trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl, 4-heptafluorophenyl.

[0063] Optionally substituted cycloalkyl is preferably 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 ~C4 ) Haloalkyl and (C 1 ~C 4 ) A cycloalkyl unsubstituted or mono- or polysubstituted, preferably up to trisubstituted, by the same or different radicals from the group of haloalkoxy, in particular by one or two (C 1 ~C 4 ) alkyl radicals.

[0064] The compounds of the invention can occur in preferred embodiments. The individual embodiments described herein can be combined with each other. Combinations that are contrary to the laws of nature and which would therefore be excluded by a person skilled in the art based on their expertise are not included. For example, ring structures having three or more adjacent oxygen atoms are excluded.

[0065] Isomers Depending on the nature of the substituents, the compounds of formula (I) can be in the form of geometric isomers and / or optical active isomers or corresponding mixtures of isomers of different composition. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention encompasses both pure stereoisomers and any mixtures of these isomers.

[0066] Methods and uses The invention also relates to a method for controlling animal pests, which comprises acting a compound of formula (I) on the animal pests and / or their habitats. The control of animal pests is preferably carried out in agriculture and forestry, as well as in material protection. Preferably, methods for surgical or therapeutic treatment of the human or animal body, and diagnostic methods carried out on the human or animal body are excluded from this specification.

[0067] The invention further relates to the use of a compound of formula (I) as a pesticidal agent, in particular as a crop protection agent.

[0068] In the context of this application, the term "pesticidal agent" always also includes, in each case, the term "crop protection agent".

[0069] Compounds of formula (I) having good plant tolerance, convenient warm-blooded animal toxicity and good environmental compatibility are useful for protecting plants and plant organs from biotic and abiotic stress factors, increasing yields, improving the quality of harvested materials, and controlling animal pests encountered in agriculture, horticulture, animal husbandry, aquaculture, forestry, gardens and leisure facilities, protection of stored products and materials, and the health sector, in particular insects, arachnids, helminths, in particular nematodes, and molluscs.

[0070] Within the context of this patent application, the term "sanitation" is understood to mean any means, procedure and practice that aims to prevent diseases, in particular infectious diseases, protect the health of humans and animals, and / or protect the environment and / or maintain cleanliness. According to the invention, this particularly includes means for cleaning, disinfecting and sterilizing, for example, textile or hard surfaces, in particular surfaces of glass, wood, concrete, porcelain, ceramics, plastics or (one or more) metals, and means for ensuring that these are kept free of sanitary pests and / or their excreta. Preferably, surgical or therapeutic procedures applicable to the human or animal body and diagnostic procedures performed on the human or animal body are excluded from the scope of the invention in this regard.

[0071] Thus, the term "health sector" encompasses all areas, technical fields and industrial applications in which these sanitary means, procedures and practices are important with regard to sanitation, for example in kitchens, bakeries, airports, bathrooms, pools, department stores, hotels, hospitals, stables, animal husbandry, etc.

[0072] Therefore, the term "sanitary pest" is understood to mean one or more animal pests whose presence in the sanitary sector is problematic, particularly for health reasons. Thus, the main objective is to avoid or minimize the presence of sanitary pests in the sanitary sector and / or exposure to them. This can be achieved, in particular, by the application of pesticides which can be used both to prevent infestation and to combat existing infestations. Preparations which avoid or reduce exposure to pests can also be used. Sanitary pests include, for example, the organisms mentioned below.

[0073] Therefore, the term "sanitary protection" encompasses all actions for maintaining and / or improving these sanitary means, procedures and practices.

[0074] The compounds of formula (I) can preferably be used as pesticides. They are active against both normally sensitive and resistant species and against all or some stages of development. The above-mentioned pests include the following.

[0075] Pests of the phylum Arthropoda, in particular of the class Arachnida, such as species of the genus Acarus, such as Acarus siro, Aceria kuko, Aceria sheldoni, species of the genus Aculops, species of the genus Aculus, such as Aculus fockeui, Aculus schlechtendali, species of the genus Amblyomma, Amphitetranychus viennensis, species of the genus Argas, species of the genus Boophilus, species of the genus Brevipalpus, such as Brevipalpus phoenicis, Bryobia graminum, Bryobia praetiosa, species of the genus Centruroides, species of the genus Chorioptes, Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, species of the genus Dermacentor, species of the genus Eotetranychus, such as Eotetranychus hicoriae, Epitrimerus pyri, species of the genus Eutetranychus, such as Eutetranychus banksi, species of the genus Eriophyes) For example, Eriophyes pyri, Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., such as Hemitarsonemus latus (= Polyphagotarsonemus latus), Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., such as Oligonychus coffeae, Oligonychus coniferarum, Oligonychus ilicis, Oligonychus indicus, Oligonychus mangiferus, Oligonychus pratensis, Oligonychus punicae, Oligonychus yothersi, Ornithodorus spp., Ornithonyssus spp., Panonychus spp.) For example, Panonychus citri (= Metatetranychus citri), Panonychus ulmi (= Metatetranychus ulmi), Phyllocoptruta oleivora, Platytetranychus multidigituli, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., for example, Tarsonemus confusus, Tarsonemus pallidus, Tetranychus spp., for example, Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae, Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici;. From the class Chilopoda, for example, Geophilus spp., Scutigera spp.; Springtails (Collembola) or of the class Collembola, such as Onychiurus armatus; Sminthurus viridis; Millipedes (Diplopoda), such as Blaniulus guttulatus; Insects (Insecta), such as of the order Blattodea, such as Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophaea maderae, Loboptera decipiens, Neostylopyga rhombifolia, Panchlora spp., Parcoblatta spp., Periplaneta spp., such as Periplaneta americana, Periplaneta australasiae, Pycnoscelus surinamensis, Supella longipalpa; Coleoptera, such as Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethina tumida, Agelastica alni, Agrilus spp., such as Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus, Agrilus anxius, Agriotes spp., such as Agriotes linneatus, Agriotes mancus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anomala dubia, Anoplophora spp., such as Anoplophora glabripennis, Anthonomus spp., such as Anthonomus grandis, Anthrenus spp., Apion spp., Apogonia spp., Athous haemorrhoidales, Atomaria spp., such as Atomaria linearis, Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp.) For example, Bruchus pisorum, Bruchus rufimanus, Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., such as Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae, Chaetocnema spp., such as Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa, Cleonus mendicus, Conoderus spp., Cosmopolites spp., such as Cosmopolites sordidus, Costelytra zealandica, Ctenicera spp., Curculio spp., such as Curculio caryae, Curculio caryatrypes, Curculio obtusus, Curculio sayi, Cryptolestes 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., Dicladispa armigera, Diloboderus spp., Epicaerus spp., Epilachna spp., for example, Epilachna borealis, Epilachna varivestis, Epitrix spp., for example, Epitrix cucumeris, Epitrix 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., for example, Hypothenemus hampei, Hypothenemus obscurus, Hypothenemus pubescens, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., for example, Leucoptera coffeella, Limonius ectypus, Lissorhoptrus oryzophilus, Listronotus spp. (= Hyperodes spp.), Lixus spp., Luperodes spp., Luperomorpha xanthodera, Lyctus spp., Megacyllene spp.) For example, Megacyllene robiniae, Megascelis spp., Melanotus spp., such as Melanotus longulus oregonensis, Meligethes aeneus, Melolontha spp., such as Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Neogalerucella spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorhynchus spp., such as Otiorhynchus cribricollis, Otiorhynchus ligustici, Otiorhynchus ovatus, Otiorhynchus rugosostriarus, Otiorhynchus sulcatus, Oulema 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 chryso. Cephalus), Psylliodes punctulata, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum, Scolytus spp., for example, Scolytus multistriatus, Sinoxylon perforans, Sitophilus 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, 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;. Of the order Dermaptera, for example, Anisolabis maritime, Forficula auricularia, Labidura riparia; Of the order Diptera, for example, species of the genus Aedes, such as Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans, species of the genus Agromyza, such as Agromyza frontella, Agromyza parvicornis, species of the genus Anastrepha, species of the genus Anopheles, such as Anopheles quadrimaculatus, Anopheles gambiae, species of the genus Asphondylia, species of the genus Bactrocera, such as Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, species of the genus Chironomus, species of the genus Chrysomya, species of the genus Chrysops, Chrysozona pluvialis, species of the genus Cochliomya, species of the genus Contarinia) 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., 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, Echinocnemus spp., Euleia heraclei, Fannia spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp.)、Hydrellia griseola, Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp., for example, Liriomyza brassicae, Liriomyza huidobrensis, Liriomyza sativae, Lucilia spp., for example, Lucilia cuprina, Lutzomyia spp., Mansonia spp., Musca spp., for example, Musca domestica, Musca domestica vicina, Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomya or Pegomyia spp., for example, Pegomya betae, Pegomya hyoscyami, Pegomya rubivora, Phlebotomus spp., Phorbia spp., Phormia spp., Piophila casei, Platyparea poeciloptera, Prodiplosis spp., Psila rosae, Rhagoletis spp.) For example, Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax, Rhagoletis pomonella, Sarcophaga spp., Simulium spp., for example, Simulium meridionale, Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp., for example, Tipula paludosa, Tipula simplex, Toxotrypana curvicauda;. Hemiptera, such as Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp., such as Acyrthosiphon pisum, Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp., such as Amrasca bigutulla, Amrasca devastans, Anuraphis cardui, Aonidiella spp., such as Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata, Aphanostigma piri, Aphis spp.) For example, 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 viburniphila, Arboridia apicalis, Arytainilla spp., Aspidiella spp., Aspidiotus spp., for example, Aspidiotus nerii, Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp., for example, 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 mbila, Coccomytilus halli, Coccus spp., for example, Coccus hesperidum, Coccus longulus, Coccus pseudomagnoliarum, Coccus viridis, Cryptomyzus ribis, Cryptoneossa spp., Ctenarytaina spp., Dalbulus spp., Dialeurodes chittendeni, Dialeurodes citri, Diaphorina citri, Diaspis spp., Diuraphis spp., Doralis spp., Drosicha spp., Dysaphis spp.) For example, Dysaphis apiifolia, Dysaphis plantaginea, Dysaphis tulipae, Dysmicoccus spp., Empoasca spp., such as Empoasca abrupta, Empoasca fabae, Empoasca maligna, Empoasca solana, Empoasca stevensi, Eriosoma spp., such as Eriosoma 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., such as 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 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 ligustri, Myzus ornatus, Myzus persicae, Myzus nicotianae, Nasonovia ribisnigri, Neomaskellia spp., Nephotettix spp.) For example, Nephotettix cincticeps, Nephotettix nigropictus, Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp., Parabemisia myricae, Paratrioza spp., for example, Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., for example, Pemphigus bursarius, Pemphigus populivenae, Peregrinus maidis, Perkinsiella spp., Phenacoccus spp., for example, Phenacoccus... Phenacoccus 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., Pulvinaria spp., Pyrilla spp., Quadraspidiotus spp.) For example, Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus, Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., for example, Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum padi, Rhopalosiphum rufiabdominale, Saissetia spp., for example, Saissetia coffeae, Saissetia miranda, Saissetia neglecta, Saissetia oleae, Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sipha flava, Sitobion avenae, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp.) Toxoptera spp., such as Toxoptera aurantii, Toxoptera citricidus, Trialeurodes vaporariorum, Trioza spp., such as Trioza diospyri, Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.;. Of the Heteroptera, for example, species of the genus Aelia, Anasa tristis, species of the genus Antestiopsis, species of the genus Boisea, species of the genus Blissus, species of the genus Calocoris, Campylomma livida, species of the genus Cavelerius, species of the genus Cimex, for example, Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus, species of the genus Collaria, Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, species of the genus Dysdercus, species of the genus Euschistus, for example, Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius, species of the genus Eurydema, species of the genus Eurygaster, Halyomorpha halys, species of the genus Heliopeltis, Horcias nobilellus, species of the genus Leptocorisa)、Leptocorisa varicornis, Leptoglossus occidentalis, Leptoglossus phyllopus, Lygocoris spp., for example, Lygocoris pabulinus, Lygus spp., for example, Lygus elisus, Lygus hesperus, Lygus lineolaris, Macropes excavatus, Megacopta cribraria, Miridae, Monalonion atratum, Nezara spp., for example, Nezara viridula, Nysius spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., for example, Piezodorus guildinii, Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.;. Of the order Hymenoptera, for example, species of Acromyrmex spp., Athalia spp., such as Athalia rosae, Atta spp., Camponotus spp., Dolichovespula spp., Diprion spp., such as Diprion similis, Hoplocampa spp., such as Hoplocampa cookei, Hoplocampa testudinea, Lasius spp., Linepithema (Iridiomyrmex) humile, Monommium pharaonis, Paratrechina spp., Paravespula spp., Plagiolepis spp., Sirex spp., such as Sirex noctilio, Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa spp., such as Vespa crabro, Wasmannia auropunctata, Xeris spp.; Of the order Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; Of the order Isoptera, for example, species of the genus Coptotermes, such as Coptotermes formosanus, Cornitermes cumulans, species of the genus Cryptotermes, species of the genus Incisitermes, species of the genus Kalotermes, Microtermes obesi, species of the genus Nasutitermes, species of the genus Odontotermes, species of the genus Porotermes, species of the genus Reticulitermes, such as Reticulitermes flavipes, Reticulitermes hesperus; Of the order 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., for example, 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, Carposina niponensis, Cheimatobia brumata, Chilo spp.) For example, 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., for example, Cydia nigricana, Cydia pomonella, Dalaca noctuides, Diaphania spp., Diparopsis spp., Diatraea saccharalis, Dioryctria spp., for example, Dioryctria zimmermani, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia 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, Gracillaria spp., Grapholitha spp., for example, Grapholita molesta, Grapholita prunivora, Hedylepta spp., Helicoverpa spp., for example, Helicoverpa armigera, Helicoverpa zea, Heliothis spp., for example, Heliothis virescens, Hepialus spp., Hepialus humuli, Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Lampides spp., Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp.) For example, Leucoptera coffeella, Lithocolletis spp., such as Lithocolletis blancardella, Lithophane antennata, Lobesia spp., such as Lobesia botrana, Loxagrotis albicosta, Lymantria spp., such as Lymantria dispar, Lyonetia spp., such as Lyonetia clerkella, Malacosoma 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., such as Ostrinia nubilalis, Panolis flammea, Parnara spp., Pectinophora spp., such as Pectinophora gossypiella, Perileucoptera spp., Phthorimaea spp.) For example, Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycter spp., such as Phyllonorycter blancardella, Phyllonorycter crataegella, Pieris spp., such as Pieris rapae, Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella (= Plutella maculipennis), Podesia spp., such as Podesia syringae, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., such as Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., such as Schoenobius bipunctifer, Scirpophaga spp., such as Scirpophaga innotata, Scotia segetum, Sesamia spp., such as Sesamia inferens, Sparganothis spp., Spodoptera spp.) For example, Spodoptera eradiana, Spodoptera exigua, Spodoptera frugiperda, Spodoptera praefica, Stathmopoda spp., Stenoma spp., Stomopteryx subsecivella, Synanthedon spp., Tecia solanivora, Thaumetopoea spp., Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineo. la bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., for example, Trichoplusia ni, Tryporyza incertulas, Tuta absoluta, Virachola spp.; Of the order Orthoptera or Saltatoria, for example, Acheta domesticus, Dichroplus spp., Gryllotalpa spp., such as Gryllotalpa gryllotalpa, Hieroglyphus spp., Locusta spp., such as Locusta migratoria, Melanoplus spp., such as Melanoplus devastator, Paratlanticus ussuriensis, Schistocerca gregaria; Of the order Phthiraptera, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Phthirus pubis, Trichodectes spp.; Of the order Psocoptera, for example, Lepinotus spp., Liposcelis spp.; Of the order Siphonaptera, for example, Ceratophyllus spp., Ctenocephalides spp., such as Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis; Thrips, such as Anaphothrips obscurus, Baliothrips biformis, Chaetanaphothrips leeuweni, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi, Haplothrips spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp., such as Thrips palmi, Thrips tabaci; Zygentoma (= Thysanura), such as Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; Pests of Symphyla, such as species of Scutigerella spp., such as Scutigerella immaculata; Pests of the phylum Mollusca, such as those of the class Bivalvia, such as species of Dreissena spp.; and Furthermore, those of the class Gastropoda, such as species of Arion spp., such as Arion ater rufus, Biomphalaria spp., Bulinus spp., Deroceras spp., such as Deroceras laeve, Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.; Plant pests of the phylum Nematoda (i.e., plant-parasitic nematodes), in particular species of the genus Aglenchus, such as Aglenchus agricola, species of the genus Anguina, such as Anguina tritici, species of the genus Aphelenchoides, such as Aphelenchoides arachidis, Aphelenchoides fragariae, species of the genus Belonolaimus, such as Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni, species of the genus Bursaphelenchus, such as Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus, species of the genus Cacopaurus, such as Cacopaurus pestis, species of the genus Criconemella, such as Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconema xenoplax), species of the genus Criconemoides) For example, Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum, Ditylenchus spp., such as Ditylenchus dipsaci, Dolichodorus spp., Globodera spp., such as Globodera pallida, Globodera rostochiensis, Helicotylenchus spp., such as Helicotylenchus dihystera, Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp., such as Heterodera avenae, Heterodera glycines, Heterodera schachtii, Hirschmaniella spp., Hoplolaimus spp., Longidorus spp., such as Longidorus africanus, Meloidogyne spp., such as Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita, Meloinema spp., Nacobbus spp., Neotylenchus spp., Paralongidorus spp.) Paraphelenchus spp., Paratrichodorus spp., e.g., Paratrichodorus minor, Paratylenchus spp., Pratylenchus spp., e.g., Pratylenchus penetrans, Pseudohalenchus spp., Psilenchus spp., Punctodera spp., Quinisulcius spp., Radopholus spp., e.g., Radopholus 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., e.g., Tylenchulus semipenetrans, Xiphinema spp., e.g., Xiphinema index.

[0076] The compounds of formula (I) can be used, at a specific concentration or application rate, as herbicides, toxicity mitigators, growth regulators or agents for improving plant characteristics, as fungicides or agents for eradicating propagules, for example as fungicides, antifungal agents, bactericides, virucides (including agents against viroids), or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). If appropriate, they can also be used as intermediates or precursors for the synthesis of other active compounds.

[0077] Formulation / Use form The present invention further relates to formulations, in particular formulations for controlling unwanted animal pests. The formulations can be applied to animal pests and / or their habitats.

[0078] The formulations of the present invention can be provided to the end user in a "ready-to-use" form of use, i.e., the formulations can be applied directly to plants or seeds by means of a suitable device such as a spraying or spreading device. Alternatively, the formulations can be provided to the end user in the form of a concentrate which preferably has to be diluted with water before use. Thus, unless otherwise specified, the term "formulation" means such a concentrate, while the term "form of use" means a "ready-to-use" solution, i.e., usually such a diluted formulation, for the end user.

[0079] The formulations of the present invention can be prepared in a conventional manner, for example by mixing the compounds of the present invention with one or more suitable auxiliaries as disclosed herein.

[0080] The formulations comprise at least one compound of the present invention and at least one agriculturally suitable auxiliary, for example (one or more) carriers and / or (one or more) surfactants.

[0081] The carrier is generally an inert, solid or liquid, natural or synthetic, organic or inorganic substance. The carrier generally improves, for example, the application of a compound to a plant, plant part or seed. Examples of suitable solid carriers include, but are not limited to, ammonium salts, especially ammonium sulfate, ammonium phosphate and ammonium nitrate, natural rock powders such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, silica gel and natural rock powders such as microsilica, alumina and silicates. Examples of typically useful solid carriers for preparing granules include 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, but are not limited thereto. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof.Examples of suitable solvents include, for example, aromatic and non-aromatic hydrocarbons (e.g., cyclohexane, paraffin, alkylbenzene, xylene, toluene, tetrahydronaphthalene, alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride), alcohols and polyols (which may be substituted, etherified and / or esterified, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (e.g., dimethylformamide or fatty acid amides) and their esters, lactams (e.g., N-alkylpyrrolidone, especially N-methylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide), oils derived from plants or animals, nitriles (alkyl nitriles such as acetonitrile, propiononitrile, butyronitrile, etc., or aromatic nitriles such as benzonitrile), carbonate esters (cyclic carbonate esters such as ethylene carbonate, propylene carbonate, butylene carbonate, etc., or dialkyl carbonate esters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate, etc.) of classes of polar and non-polar organic chemical liquids. The carrier may also be a liquefied gas extender, i.e., a liquid that is a gas under standard temperature and pressure, such as an aerosol propellant such as a halogenated hydrocarbon, butane, propane, nitrogen and carbon dioxide.

[0082] Preferred solid carriers are selected from clay, talc and silica.

[0083] Preferred liquid carriers are selected from water, fatty acid amides and their esters, aromatic and non-aromatic hydrocarbons, lactams, lactones, carbonate esters, ketones, (poly)ethers.

[0084] The amount of the carrier is typically in the range of 1 to 99.99% by weight, preferably 5 to 99.9% by weight, more preferably 10 to 99.5% by weight, and most preferably 20 to 99% by weight of the formulation.

[0085] The liquid carrier is typically present in the range of 20 to 90% by weight, for example 30 to 80% by weight of the formulation.

[0086] 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.

[0087] When the formulation contains two or more carriers, the ranges outlined refer to the total amount of the carriers.

[0088] The surfactant can be an ionic (cationic or anionic), amphoteric or non-ionic surfactant, such as (one or more) ionic or non-ionic emulsifiers, (one or more) foaming agents, (one or more) dispersants, (one or more) wetting agents, (one or more) penetration enhancers and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, ethoxylated poly(alpha-substituted) acrylate derivatives, salts of lignosulfonic acid (such as sodium lignosulfonate), salts of phenolsulfonic acid or naphthalenesulfonic acid, polycondensates of ethylene oxide and / or propylene oxide with or without alcohols, fatty acids or fatty amines (e.g., polyoxyethylene fatty acid esters such as castor oil ethoxylate, polyoxyethylene fatty alcohol ethers such as alkylaryl polyglycol ethers), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyltaurates), phosphate esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols (fatty acid esters of glycerol, sorbitol or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (such as alkyl sulfonates, aryl sulfonates and alkylbenzene sulfonates), sulfonated polymers of naphthalene / formaldehyde, phosphate esters, protein hydrolysates, lignosulfite waste liquors and methylcellulose. Any reference to salts in this paragraph preferably refers to the respective alkali salts, alkaline earth salts and ammonium salts.

[0089] Preferred surfactants are selected from ethoxylated poly(alpha-substituted) acrylate derivatives, polycondensates of ethylene oxide and / or propylene oxide with alcohols, polyoxyethylene fatty acid esters, alkylbenzene sulfonates, sulfonated polymers of naphthalene / formaldehyde, polyoxyethylene fatty acid esters such as castor oil ethoxylate, sodium lignosulfonate and arylphenol ethoxylate.

[0090] The amount of surfactant is typically in the range of 5 to 40% by weight, for example 10 to 20% by weight, of the formulation.

[0091] Further examples of suitable auxiliaries are water repellents, desiccants, binders (adhesives, tackifiers, fixatives, such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids, such as cephalin and lecithin, and synthetic phospholipids, polyvinylpyrrolidone and tyrosin), thickeners and secondary thickeners (e.g., cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays, such as 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-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one), antioxidants, light stabilizers, especially UV stabilizers, or other agents that 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 defoamers and magnesium stearate), antifreeze agents, stickers, gibberellins and processing aids, mineral and vegetable oils, fragrances, waxes, nutrients (including micronutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic substances, penetrants, sequestering agents and complexing agents.

[0092] The choice of auxiliaries depends on the intended mode of application of the compounds of the invention and / or on the physical properties of the compound(s). Furthermore, the auxiliaries can be selected to impart specific properties (technical, physical and / or biological properties) to the formulation or to the use forms prepared therefrom. The choice of auxiliaries can make it possible to customize the formulation to specific requirements.

[0093] The formulation contains an insecticidal / acaricidal / nematicidal effective amount of the (one or more) compounds of the present invention. The term "effective amount" refers to an amount that is sufficient for controlling harmful insects / mites / nematodes on cultivated plants or for protecting materials and that does not cause substantial damage to the treated plants. Such amounts can vary widely and depend on various factors such as the insect / mite / nematode species to be controlled, the cultivated plant or material being treated, the climatic conditions, and the particular compound of the present invention being used. Usually, the formulations according to the present invention contain from 0.01 to 99% by weight, preferably from 0.05 to 98% by weight, more preferably from 0.1 to 95% by weight, even more preferably from 0.5 to 90% by weight, and most preferably from 1 to 80% by weight of the compounds of the present invention. The formulation can contain two or more compounds of the present invention. In such cases, the ranges outlined refer to the total amount of the compounds of the present invention.

[0094] The formulations of the present invention can be any conventional formulation type such as solutions (e.g., aqueous solutions), emulsions, water- and oil-based suspensions, powders (e.g., wettable powders, soluble powders), dusts, pastes, granules (e.g., soluble granules, spreading granules), suspoemulsion concentrates, natural or synthetic products impregnated with the compounds of the present invention, fertilizers, and microencapsulation into polymeric substances. The compounds of the present invention can be present in suspended, emulsified or dissolved form. Examples of specific suitable formulation types are solutions, aqueous solutions (e.g., SL, LS), dispersing agents (DC), suspensions and suspending agents (e.g., SC, OD, OF, FS), emulsions (e.g., EC), emulsions (e.g., EW, EO, ES, ME, SE), capsule agents (e.g., CS, ZC), pastes, troches, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), compression agents (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), pesticidal articles (e.g., LN), and gel formulations (e.g., GW, GF) for treating plant propagation materials such as seeds. These and further types of formulations are defined by the Food and Agriculture Organization of the United Nations (FAO). An overview is described in “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No.2, 6th Ed. May 2008, Croplife International.

[0095] Preferably, the formulation of the present invention is in one of the following forms: EC, SC, FS, SE, OD, WG, WP, CS, more preferably one of EC, SC, OD, WG, CS.

[0096] Further details regarding the types of formulations and examples of their preparation are shown below. When two or more compounds of the present invention are present, the approximate amount of the compounds of the present invention refers to the total amount of the compounds of the present invention. This applies with the necessary modifications for any further components of the formulation when two or more representatives of the above components, e.g., wetting agents, binders, are present.

[0097] i) Water-soluble agents (SL, LS) Dissolve 10 to 60% by weight of at least one compound of the present invention and 5 to 15% by weight of a surfactant (e.g., a polycondensate of ethylene oxide and / or propylene oxide with an alcohol) in an amount of water and / or a water-soluble solvent (e.g., an alcohol such as propylene glycol or a carbonate such as propylene carbonate) such that the total amount is 100% by weight. Dilute the concentrate with water before application.

[0098] ii) Dispersing agent (DC) Dissolve 5 to 25% by weight of at least one compound of the present invention and 1 to 10% by weight of a surfactant and / or a binder (e.g., polyvinylpyrrolidone) in an amount of an organic solvent (e.g., cyclohexanone) such that the total amount is 100% by weight. A dispersion is obtained by diluting with water.

[0099] iii) Emulsion (EC) Dissolve 15 to 70% by weight of at least one compound of the present invention and 5 to 10% by weight of a surfactant (e.g., a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate) in an amount of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon or a fatty acid amide) and, if necessary, an additional water-soluble solvent such that the total amount is 100% by weight. An emulsion is obtained by diluting with water.

[0100] iv) Emulsifying agent (EW, EO, ES) Dissolve 5 to 40% by weight of at least one compound of the present invention and 1 to 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 an alcohol) in 20 to 40% by weight of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon). Add this mixture to water in an amount such that the total amount is 100% by weight using an emulsifying device. The resulting formulation is a uniform emulsion. The emulsion may be further diluted with water before application.

[0101] v) Suspension and suspending agent v-1) Aqueous system (SC, FS) Using a suitable grinding device, such as a stirred ball mill, 20 to 60% by weight of at least one compound of the present invention is added with 2 to 10% by weight of a surfactant (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1 to 2% by weight of a thickener (e.g., xanthan gum) and water, and ground to obtain a fine active substance suspension. Water is added in an amount such that the total amount is 100% by weight. Dilution with water gives a stable suspension of the active substance. In the case of FS formulations, up to 40% by weight of a binder (e.g., polyvinyl alcohol) is added.

[0102] v-2) Oil-based (OD, OF) Using a suitable grinding device, such as a stirred ball mill, 20 to 60% by weight of at least one compound of the present invention is added with 2 to 10% by weight of a surfactant (e.g., sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1 to 2% by weight of a thickener (e.g., modified clay, especially Bentone, or silica) and an organic carrier, and ground to obtain a fine active substance oil suspension. An organic carrier is added in an amount such that the total amount is 100% by weight. Dilution with water gives a stable dispersion of the active substance.

[0103] vi) Water-dispersible granules and water-soluble granules (WG, SG) 1 to 90% by weight, preferably 20 to 80% by weight, most preferably 50 to 80% by weight of at least one compound of the present invention is added with a surfactant (e.g., sodium lignosulfonate and sodium alkylnaphthylsulfonate) and optionally a carrier material, finely ground, and converted into water-dispersible or water-soluble granules by applying typical techniques such as extrusion, spray drying, fluidized bed granulation, etc. The surfactant and the carrier material are used in amounts such that the total amount is 100% by weight. Dilution with water gives a stable dispersion or solution of the active substance.

[0104] vii) Water-dispersible powders and water-soluble powders (WP, SP, WS) 50 to 80% by weight of at least one compound of the present invention is added with 1 to 20% by weight of a surfactant (for example, sodium lignosulfonate, sodium alkylnaphthylsulfonate) and an amount of a solid carrier such as silica gel so as to make a total amount of 100% by weight, and pulverized with a rotor-stator mill. When diluted with water, a stable dispersion or solution of the active substance can be obtained.

[0105] viii) Gel agent (GW, GF) In a stirring ball mill, 5 to 25% by weight of at least one compound of the present invention is added with 3 to 10% by weight of a surfactant (for example, sodium lignosulfonate), 1 to 5% by weight of a binder (for example, carboxymethyl cellulose) and an amount of water so as to make a total amount of 100% by weight, and pulverized. Thereby, a fine suspension of the active substance can be obtained. When diluted with water, a stable suspension of the active substance can be obtained.

[0106] ix) Microemulsion agent (ME) 5 to 20% by weight of at least one compound of the present invention is added to 5 to 30% by weight of an organic solvent blend (for example, fatty acid dimethylamide and cyclohexanone), 10 to 25% by weight of a surfactant blend (for example, polyoxyethylene fatty alcohol ether and arylphenol ethoxylate), and an amount of water so as to make a total amount of 100% by weight. This mixture is stirred for 1 hour to spontaneously generate a thermodynamically stable microemulsion.

[0107] x) Microcapsule agent (CS) An oil phase containing 5 to 50% by weight of at least one compound of the present invention, 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and 2 to 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). Radical polymerization initiated by a radical initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase containing 5 to 50% by weight of at least one compound of the present invention, 0 to 40% by weight of a water-insoluble organic solvent (e.g., aromatic hydrocarbon), and an isocyanate monomer (e.g., diphenylmethane-4,4'-diisocyanate) is dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol), thereby forming polyurea microcapsules. The addition of a polyamine (e.g., hexamethylenediamine) may be used, resulting in the formation of polyurea microcapsules. The monomer is 1 to 10% by weight of the total CS formulation.

[0108] xi) Dusts (DP, DS) At least one compound of the present invention in an amount of 1 to 10% by weight is finely pulverized and intimately mixed with a solid carrier, such as fine kaolin, in an amount such that the total amount is 100% by weight.

[0109] xii) Granules (GR, FG) At least one compound of the present invention in an amount of 0.5 to 30% by weight is finely pulverized and associated with a solid carrier (e.g., silicate) in an amount such that the total amount is 100% by weight.

[0110] xiii) Ultra-low volume liquids (UL) At least one compound of the present invention in an amount of 1 to 50% by weight is dissolved in an organic solvent, such as aromatic hydrocarbon, in an amount such that the total amount is 100% by weight.

[0111] The formulation types i) to xiii) may 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 antifreezing agent.

[0112] mixture The compounds of formula (I) may also be used as mixtures with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiological substances, beneficial species, herbicides, fertilizers, bird repellents, plant strengtheners, sterilants, safeners, semiochemicals and / or plant growth regulators, thereby, for example, broadening the activity spectrum, extending the duration of action, increasing the rate of action, preventing repellency or preventing the development of resistance. Furthermore, combinations of such active compounds can improve the tolerance of plants to growth and / or abiotic factors, such as high or low temperatures, drought or high water content or soil salinity. It is also possible to improve flowering and fruiting performance, optimize germination ability and root development, promote harvesting and improve yields, influence ripening, improve the quality and / or nutritional value of the harvested product, extend the shelf life, and / or improve the processability of the harvested product.

[0113] Furthermore, the compounds of formula (I) can be present in mixtures with other active compounds or semiochemicals, such as 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 characteristics such as, for example, the growth, yield and quality of harvested material.

[0114] In certain embodiments according to the invention, the compounds of formula (I) are present in a use form prepared from these formulations in a formulation or a mixture with a further compound, preferably a compound described below.

[0115] If one of the compounds described below can occur in different tautomeric forms, these forms are also included, even if not explicitly mentioned in each case. Furthermore, all specified mixing partners may form salts with more suitable bases or acids, if their functional groups permit.

[0116] Insecticide / acaricide / nematicide The active compounds specified by the general name in this specification 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). The classification is based on the latest IRAC Mode of Action Classification Scheme at the time of filing of this patent application.

[0117] (1) An acetylcholinesterase (AChE) inhibitor, preferably a carbamate selected from aldicarb, aldicarb sulfoxide, benfuracarb, bendiocarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb; or an organophosphate selected from acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, kasugamycin, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, dimethoate-S-methyl, diazinon, dichlorvos / DDVP, dichlorvos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, etoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotepp, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion.

[0118] (2) A GABA-regulated chloride channel blocker, preferably a cyclodiene-organochlorine selected from chlordane and endosulfan; or a phenylpyrazole (fipronil) selected from ethiprole and fipronil.

[0119] (3) A sodium channel modulator, preferably a pyrethroid selected from 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)-(1R) isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, fluvalinate, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, monofluorothrin, permethrin, phenothrin [(1R)-trans isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) isomer], tralomethrin and transfluthrin; or DDT or methoxychlor.

[0120] (4) A nicotinic acetylcholine receptor (nAChR) competitive modulator, preferably a neonicotinoid selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam; or nicotine; or a sulfoximine selected from sulfoxaflor; or a butenolide selected from flupyradifurone; or a mesoionic compound selected from triflumizopyrim.

[0121] (5) A nicotinic acetylcholine receptor (nAChR) allosteric modulator (site I), preferably spinosyn selected from spinetoram and spinosad.

[0122] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, preferably abamectin / milbemycin selected from abamectin, emamectin benzoate, lepimectin, and milbemectin.

[0123] (7) Juvenile hormone mimics, preferably juvenile hormone analogs selected from hydroprene, kinoprene, and methoprene, or fenoxycarb, or pyriproxyfen.

[0124] (8) Various non-specific (multi-site) inhibitors, preferably alkyl halides selected from methyl bromide and other halogenated alkyls; or chloropicrin; or sulfuryl fluoride; or borax; or tartar emetic; or methyl isocyanate generators selected from diazomethane and metam.

[0125] (9) Chordotonal organ TRPV channel modulators, preferably pyridine azomethanes selected from pimetrozine and pyrifluquinazone, or pyropenes selected from afidopyropen.

[0126] (10) Mite growth inhibitors that affect CHS1, selected from clofentezine, hexythiazox, diflovidazin, and etoxazole.

[0127] (11) A microbial disruptor of the insect midgut membrane selected from Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and a B.t. plant protein selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, and Cry34Ab1 / 35Ab1.

[0128] (12) An inhibitor of mitochondrial ATP synthase, preferably an ATP disruptor selected from diafenthiuron, or an organotin compound selected from azocyclotin, cyhexatin, and fenbutatin oxide, or propargite or tetradifon.

[0129] (13) An uncoupler of oxidative phosphorylation through disruption of the proton gradient selected from chlorfenapyr, DNOC, and sulfotep.

[0130] (14) A nicotinic acetylcholine receptor channel blocker selected from bensultap, cartap hydrochloride, thiram, and thiosultap sodium.

[0131] (15) An inhibitor of chitin biosynthesis that affects CHS1, preferably a benzoylurea selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.

[0132] (16) An inhibitor of chitin biosynthesis selected from buprofezin, type 1.

[0133] (17) A molting disruptor selected from silafluofen (especially, namely Diptera).

[0134] (18) An ecdysone receptor agonist, preferably a diacylhydrazine selected from chromafenozide, halofenozide, methoxyfenozide and tebufenozide.

[0135] (19) An octopamine receptor agonist selected from amitraz.

[0136] (20) A mitochondrial complex III electron transport inhibitor selected from hydramethylnon, acequinocyl, fluacrypyrim and bifenazate.

[0137] (21) A mitochondrial complex I electron transport inhibitor, preferably a METI acaricide and insecticide selected from phenazakine, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).

[0138] (22) A voltage-dependent sodium channel blocker, preferably an oxadiazine selected from indoxacarb, or a semicarbazone selected from metaflumizone.

[0139] (23) An inhibitor of acetyl-CoA carboxylase, preferably a tetronic acid derivative and a tetramic acid derivative selected from spirodiclofen, spirotetramat, spirodiclofen, spirotetramat, spirodiclofen, spirotetramat.

[0140] (24) A mitochondrial complex IV electron transport inhibitor, preferably a phosphide selected from aluminum phosphide, calcium phosphide, phosphine and zinc phosphide, or a cyanide selected from calcium cyanide, potassium cyanide and sodium cyanide.

[0141] (25) Mitochondrial complex II electron transfer inhibitor, preferably a β-ketonitrile derivative selected from cyenopyrafen and siflumetofen, or a carboxanilide selected from piflubumide.

[0142] (28) Ryanodine receptor modulator, preferably a diamide selected from chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide and tetraniliprole.

[0143] (29) A chordotonal organ modulator (having an unspecified target site) selected from flonicamid.

[0144] (30) GABAergic chloride channel allosteric modulator, preferably a meta-diamide selected from bromfenanilide, or an isoxazole selected from flumetramide.

[0145] (31) Baculovirus, preferably a granulovirus (GV) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV), or a nucleopolyhedrovirus (NPV) selected from Anticarsia gemmatalis MNPV and Helicoverpa armigera NPV.

[0146] (32) A nicotinic acetylcholine receptor allosteric modulator (site II) selected from GS-omega / kappa HXTX-Hv1a peptide.

[0147] (33) Ascinopyril, afoxolaner, azadirachtin, benclothiaz, benzoximate, benzpyrimoxan, bromopropylate, chinomethionat, chloroprallethrin, cryolite, cyclobutrifluram, cycloxaprid, cyetpyrafen, cyhalodiamide, cyproflanilide (CAS 2375110-88-4), dichloromethothiaz, dicofol, dinapropylate, epsilon-methofluthrin, epsilon-momfluorothrin, flometokine, fluaazindoline, flupyrimin, flupyriprole (CAS 1771741-86-6), fluensulfone, flufenlim, fluopicoxystrobin, flupropacil, fluhexafon, fluopyram, flupyrimin, fluralaner, flufenoxyd, flupenthiopheneox, guazipyr, heptafenathrin, imidaclothiz, iprodione, isocycloseram, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, nicochlorpyrrole (CAS 1771741-86-6), oxazosulfyl, paikonjing, pyridalyl, pyrifluquinazon, pyriminostrobin, sarolaner, spidoxamat, spirodiclofen, tetramethylfluthrin, tetrachlorantraniliprole, tioxazafen, thiofluoximate, thicyclopyrazoflor, iodomethane, a further active compound selected from, further preparations based on Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), and furthermore the following compounds, 1-{2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO 2006 / 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 WO 2006 / 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 WO 2010 / 052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP 2647626) (CAS 1440516-42-6), PF1364 (known from JP 2010 / 018586) (CAS 1204776-60-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-1,1,1-trifluoro-propan-2-one (known from WO 2013 / 144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (WO 2010 / 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 CN 103232431) (CAS 1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxid-3-thietanyl)-benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxid-3-thietanyl)-benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxid-3-thietanyl)benzamide (known from WO 2013 / 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 International Publication No. WO 2013 / 162715 A2, International Publication No. WO 2013 / 162716 A2, US Patent Application Publication No. US 2014 / 0213448 A1) (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 CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (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 International Publication No. WO 2012 / 034403 A1) (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 International Publication No. WO 2011 / 085575 A1) (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) (CAS1108184-52-6); (2E)- and 2(Z)-2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN101715774A) (CAS1232543-85-9); 3-(2,2-Dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylic acid ester (known from CN103524422A) (CAS1542271-46-4), (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) (CAS1370358-69-2), 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-[1,2,4]Triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US Patent Application Publication No. 2014 / 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-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from International Publication No. 2007040280A1, International Publication No. 2007040282A1) (CAS 934001-66-8), N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from CN103265527A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decan-2,4-dione (known from International Publication No. 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-ethyl carbonate (known from International Publication No. 2010 / 066780A1, International Publication No. 2011151146A1) (CAS 1229023-00-0), N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from International Publication No. 2014 / 053450A1) (CAS 1594624-87-9), N-[2-(2,6-difluorophenyl)-2H-1,2,[[3-Triazol-4-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 A1) (CAS 1594637-65-6), N-[1-(3,5-difluoro-2-pyridinyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014 / 053450 A1) (CAS 1594626-19-3), (3R)-3-(2-chloro-5-thiazolyl)-2,3-dihydro-8-methyl-5,7-dioxo-6-phenyl-5H-thiazolo[3,2-a]pyrimidinium inner salt (WO 2018 / 177970 A1) (CAS 2246757-58-2), 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 WO 2018 / 177970 A1) (CAS 2246757-56-0), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-2-(methylsulfonyl)-propanamide (known from WO 2019 / 236274 A1) (CAS 2396747-83-2), N-[2-bromo-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-2-fluoro-3-[(4-fluorobenzoyl)amino]-benzamide (known from WO 2019059412 A1) (CAS 1207977-87-4).

[0148] Fungicide The active ingredients specified herein by common name are known, for example, as described in The Pesticide Manual (16th Ed. British Crop Protection Council) or can be searched for on the Internet (e.g., www.alanwood.net / pesticides).

[0149] All of the designated fungicidal mixture partners of classes (1) to (15) may form salts with suitable bases or acids, where possible, through their functional groups. All of the designated mixture partners of classes (1) to (15) may, where applicable, include tautomeric forms.

[0150] 1) Inhibitors of ergosterol biosynthesis, for example, (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropizine, (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-(1H-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.(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)methanol, (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)oxolan-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040)1-{[rel(2R,3R)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxolan-2-yl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041)1-{[rel(2R,3S)-3-(2-Chlorophenyl)-2-(2,4-difluorophenyl)oxolan-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) mefenoxazol, (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-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)-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-methylimidohydroxamic acid amide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.065) N'-(2,5-Dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.066) N'-(2,5-Dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.067) N'-(2,5-Dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.068) N'-(2,5-Dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.069) N'-(2,5-Dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.070) N'-(2,5-Dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.071) N'-(2,5-Dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidohydroxamic acid amide, (1.074) N'-[5-Bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidohydroxamic acid amide, (1.075) N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.076) N'-{5-Bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.077) N’-{5-Bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.078) N’-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.079) N’-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide, (1.080) N’-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidohydroxamic acid amide. , (1.081) Iprofen trifluconazole, (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.

[0151] 2) Inhibitors of the respiratory chain in Complex I or Complex II, for example, (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) flutriafol, (2.009) isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S,4R,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) pidiflumetofen, (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) Ipyrfluxam, (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-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (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, (2.038) 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-(difluoromethyl)-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.(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-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) Pyrapropion.

[0152] 3) Inhibitors of the respiratory chain in complex III, such as, (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) kresoxim-methyl, (3.005) cumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) fluopicoxystrobin, (3.012) flutriafol, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyra-metostrobin, (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) fenpicoxamid, (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) florpyrauxamid.

[0153] 4) Inhibitors of mitosis and cell division, for example, (4.001) Carbendazim, (4.002) Diethofencarb, (4.003) Etaboxam, (4.004) Fluopicolide, (4.005) Pencycuron, (4.006) Thiabendazole, (4.007) Thiram, (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)-6-methylpyridazine, (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-bromophenyl)-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-pyrazole-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-pyrazole-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine.

[0154] 5) Compounds that can exhibit activity at multiple sites, for example, (5.001) Bordeaux mixture, (5.002) captan, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) basic copper chloride, (5.009) copper sulfate (2+), (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) maneb, (5.014) mancozeb, (5.015) metiram, (5.016) metiram zinc, (5.017) copper oxine, (5.018) propineb, (5.019) sulfur and sulfur agents, for example, calcium polysulfide, (5.020) thiuram, (5.021) dinneb, (5.022) dithiram, (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.

[0155] 6) Compounds that can induce the host's defense, for example, (6.001) acibenzolar-S-methyl, (6.002) isothianyl, (6.003) probenazole, (6.004) thiazinyl.

[0156] 7) Inhibitors of the biosynthesis of amino acids and / or proteins, 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.

[0157] 8) ATP production inhibitors, for example, (8.001) Silthiopham.

[0158] 9) Cell wall synthesis inhibitors, for example, (9.001) Benalaxyl-M, (9.002) Dimethomorph, (9.003) Flumorph, (9.004) Iprovalicarb, (9.005) Mandipropamid, (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.

[0159] 10) Inhibitors of lipid and membrane synthesis, for example, (10.001) Propamocarb, (10.002) Propamocarb hydrochloride, (10.003) Tolfenpyrad-methyl.

[0160] 11) Melanin synthesis inhibitors, for example, (11.001) Tricyclazole, (11.002) 2,2,2-Trifluoroethyl {3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.

[0161] 12) Nucleic acid synthesis inhibitors, for example, (12.001) Benalaxyl, (12.002) Benalaxyl-M (Kiralaxyl), (12.003) Metalaxyl, (12.004) Metalaxyl-M (Mefenoxam).

[0162] 13) Signal transduction inhibitors, for example, (13.001) fluazinam, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

[0163] 14) Compounds that can act as uncoupling agents, for example, (14.001) fluazinam, (14.002) meptyldinocap.

[0164] 15) Further fungicides are selected from the group consisting of the following. (15.001) Abscisic acid, (15.002) Benziathiazole, (15.003) Benthiavalicarb, (15.004) Capsimycin, (15.005) Carboxin, (15.006) Chinomethionat, (15.007) Cufraneb, (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) Mildeiomycin, (15.018) Natamycin, (15.019) Nickel dimethyldithiocarbamate, (15.020) Nitrothalisopropyl, (15.021) Oxamocarb, (15.022) Oxathiapiprolin, (15.023) Oxyfenthiin, (15.024) Pentachlorophenol and salts, (15.025) Phosphoric acid and its salts, (15.026) Propamocarb fosetylate, (15.027) Pyriofenone (Clazafenone), (15.028) Tebufenozide, (15.029) Techlofthalam (15.030) Tolinifanide, (15.031) 1-(4-{4-[(5R)-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, (15.032) 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) Diphenylamine, (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(difluoromethyl)-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)piperazin-1-yl]ethanone, (15.038) 2-[6-(3-fluorophenyl)-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-chlorophenylmethanesulfonate, (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-chlorophenylmethanesulfonate, (15.041) ipfuphenoxine, (15.042) 2-{2-fluoro-6-[(8-fluoromethylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiprolin, (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}phenylmethanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3-(4,4,5-Trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinopharmine, (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]butyric 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) but-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) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamic acid tert-butyl, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidformamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimid-formamide), (15.(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-3,4-dihydroisoquinoline), (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}-cyclopropane-carboxamide), (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]-cyclopropane-carboxamide, (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-carboximidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-benzamide, (15.084) N-[(Z)-N-methoxy-C-methyl-carboximidoyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (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]-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)phen-yl]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]phen. N-[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]isoxazolidin-3-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]-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) N-{2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide.

[0165] Biological pest control agents as a mixture component The compounds of formula (I) can be combined with biological pest control agents.

[0166] Biological pest control agents include products formed by microorganisms, in particular bacteria, fungi, yeasts, plant extracts, and proteins and secondary metabolites.

[0167] Biological pest control agents include bacteria such as spore-forming bacteria, root-colonizing bacteria, and bacteria that act as biological insecticides, fungicides or nematicides.

[0168] Examples of the above bacteria that are used or can be used as biological pest control agents are as follows.

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

[0170] Examples of fungi and yeasts that are used or can be used as biological pest control agents are as follows.

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

[0172] Examples of viruses that are used or can be used as biological pest control agents are as follows.

[0173] Adoxophyes orana (apple leafroller) granulosis virus (GV), Cydia pomonella (codling moth) granulosis virus (GV), Helicoverpa armigera (cotton bollworm) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (Egyptian cottonworm) NPV.

[0174] Also included are bacteria and fungi that are added as "inoculants" to plants or plant parts or organs and promote plant growth and plant health because of their specific properties. Examples that may be mentioned are as follows.

[0175] 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., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp., Streptomyces spp.

[0176] Examples of products formed by microorganisms containing proteins and secondary metabolites that are used or can be used as plant extracts and biological pesticides are as follows.

[0177] Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Forune Aza, Fungastop, Head Up (extract of Chenopodium quinoa saponin), Pyrethrum / Pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem (trademark) insecticide", rotenone, ryania / ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract, particularly Brassica powder or mustard powder, and olive oil, particularly with a carbon chain length C 16 ~C 20 Biopesticidal / acaricidal active substances obtained from unsaturated fats / carboxylic acids having the following as active ingredients (for example, those contained in a product with the trade name FLiPPER (registered trademark)).

[0178] Toxicity mitigators as mixed components The compound of formula (I) can be combined with toxicity alleviating agents such as benoxacol, cloxintol (- mexyl), siometrinyl, cyprosulfamide, dichloramide, fenchlorazole (- ethyl), fenclorim, flurazole, flurxyphenium, furilazole, isoxadifen (- ethyl), mefenpyr (- diethyl), phthalic anhydride, oxabetrinyl, 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), etc.

[0179] Plants and plant parts All plants and plant parts can be processed according to the invention. Here, plants include desirable and undesirable wild plants or crop plants (including naturally occurring crop plants), such as cereals (wheat, rice, triticale, barley, rye, oats), maize, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, Brassica oleracea (e.g. cabbage) and other vegetable species, cotton, tobacco, rape, and furthermore all plants and plant parts such as fruit plants (apples, pears, citrus fruits and grapes which are fruits). Crop plants include transgenic plants and can be plants obtained by conventional breeding and optimization methods or by methods of biotechnology and genetic engineering or combinations of these methods, including plant varieties which may or may not be protected by varietal rights. Plants are to be understood as meaning all developmental stages from seeds, seedlings, young (immature) plants to mature plants. Plant parts are to be understood as meaning all parts and organs of the plant above and below ground, such as shoots, leaves, flowers and roots, and include by way of example 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 and vegetative and reproductive propagation material, such as seedlings, tubers, rhizomes, cuttings and seeds.

[0180] The treatment according to the invention of plants and plant parts with the compounds of the formula (I) is carried out either directly or by customary treatment methods, such as by dipping, spraying, evaporation, atomization, scattering, painting, injection, and in the case of propagation material, in particular in the case of seeds, by applying one or more coatings, by acting on the surroundings, the environment or the storage space with the compounds.

[0181] As already mentioned above, it is possible to treat all plants and parts thereof according to the present invention. In a preferred embodiment, wild plant species and plant cultivars, or those obtained by conventional biological breeding methods such as crossing or protoplast fusion, and parts thereof are also treated. In an even more preferred embodiment, transgenic plants and plant cultivars (genetically modified organisms) obtained by genetic engineering methods, optionally in combination with conventional methods, and parts thereof are treated. The terms "part" or "plant part" or "plant portion" have been described above. The present invention is particularly preferably used for treating plants of each commercially customary cultivar or cultivar in use. Plant cultivars are understood to mean plants having new characteristics "traits" and obtained by conventional breeding, mutagenesis or recombinant DNA techniques. They can be cultivars, varieties, biotypes or genotypes.

[0182] Transgenic Plants, Seed Treatments and Integration Events According to the present invention, the compounds of formula (I) can be advantageously used for treating transgenic plants, plant cultivars or plant parts that have received genetic material conferring advantageous and / or useful traits (characteristics) to these plants, plant cultivars or plant parts. Thus, the present invention is considered to be combinable with one or more recombinant traits or (one or more) transgenic events or combinations thereof. For the purposes 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 novel DNA sequence called an "event" and is characterized by a certain amount of genomic DNA flanking directly adjacent to both ends of the inserted recombinant DNA molecule and the inserted DNA. Such (one or more) traits or (one or more) transgenic events include, but are not limited to, pest resistance, water use efficiency, yield performance, drought tolerance, seed quality, improvement of nutritional quality, hybrid seed production, and herbicide tolerance, and the traits are measured relative to plants lacking such traits or transgenic events. Specific examples of such advantageous and / or useful traits (characteristics) are better plant growth, vigor, stress tolerance, standardization, lodging resistance, nutrient uptake, plant nutrition, and / or yield, in particular improved growth, increased tolerance to high or low temperatures, increased tolerance to drought or water or soil salinity, improved flowering performance, ease of harvesting, acceleration of ripening, increased yield, improvement of the quality and / or nutritional value of the harvested product, improvement of the storage life and / or processability of the harvested product, and resistance or increased resistance to animal and microbial pests such as insects, spiders, nematodes, mites, slugs and snails.

[0183] Among the DNA sequences encoding proteins conferring resistance or tolerance properties against such animal and microbial pests, especially insects, the genetic material derived from Bacillus thuringiensis encoding Bt proteins, which are widely described in the literature and well-known to those skilled in the art, is particularly mentioned. Also mentioned are proteins extracted from bacteria such as Photorhabdus (WO 97 / 17432 and WO 98 / 08932). In particular, CrylA, CryIAb, CryIAc, CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF proteins or their toxic fragments, as well as their hybrids or combinations, especially CrylF protein or hybrids derived from CrylF protein (e.g., hybrid CrylA-CrylF protein or its toxic fragment), CrylA type protein or its toxic fragment, preferably CrylAc protein or hybrids derived from CrylAc protein (e.g., hybrid CrylAb-CrylAc protein) or CrylAb or Bt2 protein or their toxic fragments, Cry2Ae, Cry2Af or Cry2Ag protein or their toxic fragments, CrylA.105 protein or its toxic fragment, VIP3Aa19 protein, VIP3Aa20 protein, VIP3A protein produced in the COT202 or COT203 cotton event, VIP3Aa protein or its toxic fragment as described in Estruch et al. (1996), Proc Natl Acad Sci US A. 28;93(11):5389-94, Cry protein as described in WO 2001 / 47952, insecticidal protein from Xenorhabdus as described in WO 98 / 50427, Serratia (especially from S. entomophila) or Photorhabdus species strains, e.g., Tc protein from Photorhabdus as described in WO 98 / 08932, are mentioned for Bt Cry or VIP proteins.Any variant or mutant of any one of the proteins described above, especially those whose sequences differ from any of the above-mentioned sequences, particularly those of their toxic fragments, by one or a few amino acids (1 to 10, preferably 1 to 5), or any transport peptide such as a plastid transport peptide, or those fused to another protein or peptide are also included herein.

[0184] Another particularly emphasized example of such properties is resistance conferred to one or more herbicides, such as imidazolinones, sulfonylureas, glyphosate or phosphinothricin. Among the DNA sequences encoding proteins that confer resistance to specific herbicides in transformed plant cells and plants, the bar or PAT genes described in WO 2009 / 152359 that confer resistance to glufosinate herbicides, or Streptomyces coelicolor genes, genes encoding suitable EPSPS (5-enolpyruvylshikimate-3-phosphate synthase) that confer resistance to herbicides targeting EPSPS, particularly herbicides such as glyphosate and its salts, genes encoding glyphosate-n-acetyltransferase, or genes encoding glyphosate oxidoreductase are particularly mentioned. Further preferred herbicide resistance traits include at least one ALS (acetolactate synthase) inhibitor (e.g., WO 2007 / 024782), mutant Arabidopsis ALS / AHAS genes (e.g., US Patent No. 6,855,533), genes encoding 2,4-D-monooxygenase that confer resistance to 2,4-D (2,4-dichlorophenoxyacetic acid), and genes encoding dicamba monooxygenase that confer resistance to dicamba (3,6-dichloro-2-methoxybenzoic acid).

[0185] An even more particularly emphasized example of such properties is an increase in resistance to phytopathogenic fungi, bacteria and / or viruses in plants, for example, systemic acquired resistance (SAR), systemins, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins.

[0186] Particularly useful transgenic events in transgenic plants or plant cultivars that can be preferably processed by the present invention include the following. Event 531 / PV-GHBK04 (cotton, insect control, described in WO 2002 / 040677), Event 1143-14A (cotton, insect control, not deposited, described in WO 2006 / 128569), Event 1143-51B (cotton, insect control, not deposited, described in WO 2006 / 128570), Event 1445 (cotton, herbicide tolerance, not deposited, described in US Patent Application Publication No. A2002-120964 or WO 2002 / 034946), Event 17053 (rice, herbicide tolerance, deposited as PTA-9843, described in WO 2010 / 117737), Event 17314 (rice, herbicide tolerance, deposited as PTA-9844, described in WO 2010 / 117735), Event 281-24-236 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in WO 2005 / 103266 or US Patent Application Publication No. A2005-216969), Event 3006-210-23 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in US Patent Application Publication No. A2007-143876 or WO 2005 / 103266), Event 3272 (maize, quality trait, deposited as PTA-9972, described in WO 2006 / 098952 or US Patent Application Publication No. A2006-230473), Event 33391 (wheat, herbicide tolerance, deposited as PTA-2347, described in WO 2002 / 027004), Event 40416 (maize, insect control - herbicide tolerance, deposited as ATCC PTA-11508, described in WO 11 / 075593), Event 43A47 (maize, insect control - herbicide tolerance, deposited as ATCC PTA-11509, described in WO 2011 / 075595), Event 5307 (maize, insect control, ATCCEvent ASR-368 (bentgrass, herbicide tolerance, deposited as ATCC PTA-4816, described in US Patent Application Publication No. A2006-162007 or International Publication No. WO 2004 / 053062), which is deposited as PTA-9561 and described in International Publication No. WO 2010 / 077816; Event B16 (maize, herbicide tolerance, not deposited, described in US Patent Application Publication No. A2003-126634); Event BPS-CV127-9 (soybean, herbicide tolerance, deposited as NCIMB No. 41603, described in International Publication No. WO 2010 / 080829); Event BLR1 (rape, restoration of male sterility, deposited as NCIMB 41193, described in International Publication No. WO 2005 / 074671); Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in US Patent Application Publication No. A2009-217423 or International Publication No. WO 2006 / 128573); Event CE44-69D (cotton, insect control, not deposited, described in US Patent Application Publication No. A2010-0024077); Event CE44-69D (cotton, insect control, not deposited, described in International Publication No. WO 2006 / 128571); Event CE46-02A (cotton, insect control, not deposited, described in International Publication No. WO 2006 / 128572); Event COT102 (cotton, insect control, not deposited, described in US Patent Application Publication No. A2006-130175 or International Publication No. WO 2004 / 039986); Event COT202 (cotton, insect control, not deposited, described in US Patent Application Publication No. A2007-067868 or International Publication No. WO 2005 / 054479); Event COT203 (cotton, insect control, not deposited, described in International Publication No. WO 2005 / 054480); Event DAS21606-3 / 1606 (soybean, herbicide tolerance, deposited as PTA-11028, described in International Publication No. WO 2012 / 033794); Event DAS40278 (maize, herbicide tolerance, ATCCDeposited as PTA-10244, described in International Publication No. WO 2011 / 022469), event DAS-44406-6 / pDAB8264.44.06.l (soybean, herbicide tolerance, deposited as PTA-11336, described in International Publication No. WO 2012 / 075426), event DAS-14536-7 / pDAB8291.45.36.2 (soybean, herbicide tolerance, deposited as PTA-11335, described in International Publication No. WO 2012 / 075429), event DAS-59122-7 (maize, insect control-herbicide tolerance, deposited as ATCC PTA 11384, described in US Patent Application Publication No. US 2006-070139), event DAS-59132 (maize, insect control-herbicide tolerance, not deposited, described in International Publication No. WO 2009 / 100188), event DAS68416 (soybean, herbicide tolerance, deposited as ATCC PTA-10442, described in International Publication No. WO 11 / 066384 or International Publication No. WO 2011 / 066360), event DP-098140-6 (maize, herbicide tolerance, deposited as ATCC PTA-8296, described in US Patent Application Publication No. US 2009-137395 or International Publication No. WO 08 / 112019), event DP-305423-1 (soybean, quality trait, not deposited, described in US Patent Application Publication No. US 2008-312082 or International Publication No. WO 2008 / 054747), event DP-32138-1 (maize, hybridization system, deposited as ATCC PTA-9158, described in US Patent Application Publication No. US 2009-0210970 or International Publication No. WO 2009 / 103049), event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US Patent Application Publication No. US 2010-0184079 or International Publication No. WO 2008 / 002872), event EE-I (eggplant, insect control, not deposited, described in International Publication No. WO 07 / 091277), event Fil17 (maize, herbicide tolerance, ATCCEvent FG72 (soybean, herbicide tolerance, deposited as PTA - 11041, described in WO 2011 / 063413), event GA21 (maize, herbicide tolerance, deposited as ATCC 209033, described in US Patent Application Publication No. A2005 - 086719 or WO 98 / 044140), event GG25 (maize, herbicide tolerance, deposited as ATCC 209032, described in US Patent Application Publication No. A2005 - 188434 or WO 98 / 044140), event GHB119 (cotton, insect control - herbicide tolerance, deposited as ATCC PTA - 8398, described in WO 2008 / 151780), event GHB614 (cotton, herbicide tolerance, deposited as ATCC PTA - 6878, described in US Patent Application Publication No. A2010 - 050282 or WO 2007 / 017186), event GJ11 (maize, herbicide tolerance, deposited as ATCC 209030, described in US Patent Application Publication No. A2005 - 188434 or WO 98 / 044140), event GM RZ13 (sugar beet, virus resistance, deposited as NCIMB - 41601, described in WO 2010 / 076212), event H7 - 1 (sugar beet, herbicide tolerance, deposited as NCIMB 41158 or NCIMB 41159, described in US Patent Application Publication No. A2004 - 172669 or WO 2004 / 074492), event JOPLIN1 (wheat, disease resistance, not deposited, described in US Patent Application Publication No. A2008 - 064032), event LL27 (soybean, herbicide tolerance, deposited as NCIMB41658, described in WO 2006 / 108674 or US Patent Application Publication No. A2008 - 320616), event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41660, described in WO 2006 / 108675 or US Patent Application Publication No. A2008 - 196127), event LLcotton25 (cotton, herbicide tolerance, ATCCEvent LLRICE06 (rice, herbicide tolerance, deposited as ATCC 203353, described in U.S. Patent No. 6,468,747 or International Publication No. WO 2000 / 026345), event LLRice62 (rice, herbicide tolerance, deposited as ATCC 203352, described in International Publication No. WO 2000 / 026345), event LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in U.S. Patent Application Publication No. US 2008 / 2289060 or International Publication No. WO 2000 / 026356), event LY038 (maize, quality trait, deposited as ATCC PTA-5623, described in U.S. Patent Application Publication No. US 2007 / 028322 or International Publication No. WO 2005 / 061720), event MIR162 (maize, insect control, deposited as PTA-8166, described in U.S. Patent Application Publication No. US 2009 / 300784 or International Publication No. WO 2007 / 142840), event MIR604 (maize, insect control, not deposited, described in U.S. Patent Application Publication No. US 2008 / 167456 or International Publication No. WO 2005 / 103301), event MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in U.S. Patent Application Publication No. US 2004 / 250317 or International Publication No. WO 2002 / 100163), event MON810 (maize, insect control, not deposited, described in U.S. Patent Application Publication No. US 2002 / 102582), event MON863 (maize, insect control, deposited as ATCC PTA-2605, described in International Publication No. WO 2004 / 011601 or U.S. Patent Application Publication No. US 2006 / 095986), event MON87427 (maize, pollination control, deposited as ATCC PTA-7899, described in International Publication No. WO 2011 / 062904), event MON87460 (maize, stress tolerance, ATCCEvent MON87701 (soybean, insect control, deposited as ATCC PTA-8194, described in International Publication No. WO 09 / 111263 or U.S. Patent Application Publication No. US 2011 / 0138504 A2), event MON87705 (soybean, quality trait - herbicide tolerance, deposited as ATCC PTA-9241, described in U.S. Patent Application Publication No. US 2010 / 0080887 or International Publication No. WO 10 / 037016), event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA-9670, described in International Publication No. WO 2011 / 034704), event MON87712 (soybean, yield, deposited as PTA-10296, described in International Publication No. WO 2012 / 051199), event MON87754 (soybean, quality trait, deposited as ATCC PTA-9 Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911, described in International Publication No. WO 2010 / 024976), Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911, described in U.S. Patent Application Publication No. US 2011-0067141 A2 or International Publication No. WO 2009 / 102873), Event MON88017 (maize, insect control - herbicide tolerance, deposited as ATCC PTA-5582, described in U.S. Patent Application Publication No. US 2008-028482 A1 or International Publication No. WO 2005 / 059103), Event MON88913 (cotton, herbicide tolerance, deposited as ATCC PTA-4854, described in International Publication No. WO 2004 / 072235 or U.S. Patent Application Publication No. US 2006-059590 A1), Event MON88302 (rape, herbicide tolerance, deposited as PTA-10955, described in International Publication No. WO 2011 / 153186), Event MON88701 (cotton, herbicide tolerance, deposited as PTA-11754, described in International Publication No. WO 2012 / 134808), Event MON89034 (maize, insect control, deposited as ATCC PTA-7455, described in International Publication No. WO 07 / 140256 or U.S. Patent Application Publication No. US 2008-260932 A1), Event MON89788 (soybean, herbicide tolerance, deposited as ATCC PTA-6708, described in U.S. Patent Application Publication No. US 2006-282915 A1 or International Publication No. WO 2006 / 130436), Event MSI 1 (rape, pollination control - herbicide tolerance, deposited as ATCC PTA-850 or PTA-2485, described in International Publication No. WO 2001 / 031042), Event MS8 (rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in International Publication No. WO 2001 / 041558 or U.S. Patent Application Publication No. US 2003-188347 A1), Event NK603 (maize, herbicide tolerance, deposited as ATCC PTA-2478, described in U.S. Patent Application Publication No. US 2007-292854 A1), Event PE-7 (rice, insect control, not deposited, described in International Publication No. WO 2008 / 114282), Event RF3 (rape, pollination control - herbicide tolerance,Deposited as ATCC PTA-730, described in International Publication No. WO 2001 / 041558 or US Patent Application Publication No. US 2003 / 188347), event RT73 (rape, herbicide tolerance, not deposited, described in International Publication No. WO 2002 / 036831 or US Patent Application Publication No. US 2008 / 070260), event SYHT0H2 / SYN-000H2-5 (soybean, herbicide tolerance, deposited as PTA-11226, described in International Publication No. WO 2012 / 082548), event T227-1 (sugar beet, herbicide tolerance, not deposited, described in International Publication No. WO 2002 / 44407 or US Patent Application Publication No. US 2009 / 265817), event T25 (maize, herbicide tolerance, not deposited, described in US Patent Application Publication No. US 2001 / 029014 or International Publication No. WO 2001 / 051654), event T304-40 (cotton, insect control-herbicide tolerance, deposited as ATCC PTA-8171, described in US Patent Application Publication No. US 2010 / 077501 or International Publication No. WO 2008 / 122406), event T342-142 (cotton, insect control, not deposited, described in International Publication No. WO 2006 / 128568), event TC1507 (maize, insect control-herbicide tolerance, not deposited, described in US Patent Application Publication No. US 2005 / 039226 or International Publication No. WO 2004 / 099447), event VIP1034 (maize, insect control-herbicide tolerance, deposited as ATCC PTA-3925, described in International Publication No. WO 2003 / 052073), event 32316 (maize, insect control-herbicide tolerance, deposited as PTA-11507, described in International Publication No. WO 2011 / 084632), event 4114 (maize, insect control-herbicide tolerance, deposited as PTA-11506, described in International Publication No. WO 2011 / 084621), event EE-GM3 / FG72 (soybean, herbicide tolerance, ATCC Accession No. PTA-11041) (event EE-GM1 / LL27 or event EE-GM2 / LL55 (International Publication No. WO 2011 / 063413A2) may overlap), event DAS-68416-4 (soybean, herbicide tolerance, ATCC Accession No. PTA-10442,International Publication No. WO 2011 / 066360 A1, Event DAS-68416-4 (soybean, herbicide tolerance, ATCC Deposit No. PTA-10442, International Publication No. WO 2011 / 066384 A1), Event DP-040416-8 (maize, insect control, ATCC Deposit No. PTA-11508, International Publication No. WO 2011 / 075593 A1), Event DP-043A47-3 (maize, insect control, ATCC Deposit No. PTA-11509, International Publication No. WO 2011 / 075595 A1), Event DP-004114-3 (maize, insect control, ATCC Deposit No. PTA-11506, International Publication No. WO 2011 / 084621 A1), Event DP-032316-8 (maize, insect control, ATCC Deposit No. PTA-11507, International Publication No. WO 2011 / 084632 A1), Event MON-88302-9 (rape, herbicide tolerance, ATCC Deposit No. PTA-10955, International Publication No. WO 2011 / 153186 A1), Event DAS-21606-3 (soybean, herbicide tolerance, ATCC Deposit No. PTA-11028, International Publication No. WO 2012 / 033794 A2), Event MON-87712-4 (soybean, quality trait, ATCC Deposit No. PTA-10296, International Publication No. WO 2012 / 051199 A2), Event DAS-44406-6 (soybean, stacked herbicide tolerance, ATCC Deposit No. PTA-11336, International Publication No. WO 2012 / 075426 A1), Event DAS-14536-7 (soybean, stacked herbicide tolerance, ATCC Deposit No. PTA-11335, International Publication No. WO 2012 / 075429 A1), Event SYN-000H2-5 (soybean, herbicide tolerance, ATCC Deposit No. PTA-11226, International Publication No. WO 2012 / 082548 A2), Event DP-061061-7 (rape, herbicide tolerance, no corresponding deposit number, International Publication No. WO 2012071039 A1), Event DP-073496-4 (rape, herbicide tolerance, no corresponding deposit number, US Patent Application Publication No. 2012131692), Event 8264.44.06.1 (soybean, stacked herbicide tolerance, Deposit No. PTA-11336, International Publication No. WO 2012075426 A2), Event 8291.45.36.2 (soybean, stacked herbicide tolerance, Deposit No. PTA-11335,International Publication No. WO 2012 / 075429 A2, Event SYHT0H2 (soybean, ATCC Deposit No. PTA-11226, International Publication No. WO 2012 / 082548 A2), Event MON88701 (cotton, ATCC Deposit No. PTA-11754, International Publication No. WO 2012 / 134808 A1), Event KK179-2 (alfalfa, ATCC Deposit No. PTA-11833, International Publication No. WO 2013 / 003558 A1), Event pDAB8264.42.32.1 (soybean, stacked herbicide tolerance, ATCC Deposit No. PTA-11993, International Publication No. WO 2013 / 010094 A1), Event MZDT09Y (maize, ATCC Deposit No. PTA-13025, International Publication No. WO 2013 / 012775 A1).

[0187] Furthermore, a list of such (one or more) transgenic events is provided by the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) and can be found on its website at aphis.usda.gov. For the purposes of this application, the state of such a list as of the filing date of this application is relevant.

[0188] The genes / events conferring the desired trait(s) 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), maize, soybean, potato, sugar beet, sugar cane, tomato, legumes and other types of vegetables, cotton, tobacco, oilseed rape and fruit plants (apple, pear, citrus fruits and grapes which are fruits), with maize, soybean, wheat, rice, potato, cotton, sugar cane, tobacco and oilseed rape being particularly important. Traits that are particularly emphasized are an increase in the tolerance of plants to insects, arachnids, nematodes and slugs and snails, and an increase in the tolerance of plants to one or more herbicides.

[0189] Examples of commercially available plants, plant parts, or plant seeds that can be preferably treated according to the present invention include those sold or distributed under the trade names of GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY®, VT DOUBLE PRO®, VT TRIPLE PRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEND™, INTACTA RR2 PRO®, VISTIVE GOLD®, and / or XTENDFLEX™, such as commercially available products of plant seeds.

[0190] Crop protection - Type of treatment The treatment of plants and plant parts with the compound of formula (I) can be carried out directly, or by acting on their surroundings, habitats or storage spaces, by conventional treatment methods, such as dipping, spraying, atomizing, perfusion, evaporation, dusting, atomizing, spreading, foaming, painting, spreading, injection, watering (dipping), drip irrigation, and in the case of propagation materials, especially in the case of seeds, further as powders for dry seed treatment, solutions for liquid seed treatment, water-soluble powders for slurry treatment, using film formation, coating with one or more coatings, etc. Furthermore, it is possible to apply the compound of formula (I) by the ultra-micro method, or to inject the application form or the compound of formula (I) itself into the soil.

[0191] A preferred direct treatment of plants is foliar application, i.e., the compound of formula (I) is applied to the leaves, and the treatment frequency and application amount should be adjusted according to the infestation level of the pest in question.

[0192] In the case of a compound that is active systemically, the compound of formula (I) also accesses the plant via the root system. The plant is then treated by the action of the compound of formula (I) on the plant's habitat. This can be done, for example, by dipping or by mixing into the soil or nutrient solution, i.e., by impregnating the liquid form of the compound of formula (I) into the plant's location (e.g., soil or hydroponic system), or by soil application, i.e., by introducing the compound of formula (I) according to the invention in solid form (e.g., in the form of granules) into the plant's location, or by drip application (often also called "chemigation"), i.e., by applying the compound of formula (I) according to the invention in liquid form from a defined surface or subsurface drip line in various amounts of water over a certain period at a defined location near the plant. In the case of rice crops, this can be done by metering and supplying the compound of formula (I) in solid application form (e.g., as granules) to the paddy field.

[0193] Digital technology The compounds of the invention can be used, for example, in combination with models incorporated into computer programs for site-specific crop management, satellite farming, precision farming or precision agriculture. Such models assist in the site-specific management of agricultural fields using data from various sources such as soil, weather, crops (e.g., type, growth stage, plant health), weeds (e.g., type, growth stage), diseases, pests, nutrients, water, moisture, biomass, satellite data, yield, etc., for the purpose of optimizing profitability, sustainability and environmental protection. In particular, such models can help to optimize agronomic decisions, control the accuracy of pesticide applications and record the operations performed.

[0194] As an example, the compounds of the invention can be applied to crop plants according to an appropriate dosage regimen when the model models the occurrence of pests and calculates that a threshold has been reached at which it is recommended to apply the compounds of the invention to the crop plants.

[0195] Commercially available systems that include agronomic models are, for example, FieldScripts™ by The Climate Corporation, Xarvio™ by BASF, AGLogic™ by John Deere, and the like.

[0196] The compounds of the present invention can also be used in combination with smart spraying equipment such as spot spraying or precision spraying equipment attached to or housed within farm vehicles such as tractors, robots, helicopters, airplanes, drones, and other unmanned aerial vehicles (UAVs). Such equipment typically includes an input sensor (such as a camera) and a processing unit configured to analyze the input data and provide a determination based on the analysis of the input data to apply the compounds of the present invention to crop plants (and respective weeds) in a specific and accurate manner. The use of such smart spraying devices typically requires a positioning system (such as a GPS receiver) for locating the recorded data and guiding or controlling the farm vehicle, a geographic information system (GIS) for representing information on an understandable map, and a suitable farm vehicle for performing the necessary farm operations such as spraying.

[0197] In one example, pests can be detected from the images collected by the camera. In one example, the pests can be identified and / or classified based on the image. 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.

[0198] Seed treatment The control of animal pests by treating plant seeds has long been known and is the subject of continuous improvement. However, seed treatment is associated with a series of problems that cannot necessarily be solved in a satisfactory way. Therefore, it is desirable to develop a method for protecting seeds and germinating plants that omits, or at least significantly reduces, the further application of pesticides during storage, after sowing or after the emergence of the plant. Furthermore, it is desirable to optimize the amount of active compound used so that the seeds and the plants during germination are optimally protected from attack by animal pests without damaging the plants themselves by the active compounds used. In particular, the seed treatment method should also take into account the inherent insecticidal or nematicidal properties of pest-resistant or transgenic plants with resistance in order to achieve optimal protection of the seeds and further the germinating plants using a minimum amount of pesticide.

[0199] Accordingly, the present invention also relates in particular to a method for protecting seeds and germinating plants from attack by pests by treating the seeds with one of the compounds of formula (I). The method according to the invention for protecting seeds and germinating plants from attack by pests further comprises a method of treating the seeds with the compound of formula (I) and the mixing component simultaneously or sequentially in a single operation. It also includes a method of treating the seeds with the compound of formula (I) and the mixing component at different times.

[0200] The present invention likewise relates to the use of a compound of formula (I) for treating seeds for protecting the seeds and the resulting plants from animal pests.

[0201] Furthermore, the present invention relates to seeds treated with a compound of formula (I) according to the invention for protecting against animal pests. The present invention also relates to seeds treated simultaneously with a compound of formula (I) and a mixing component. The present invention further relates to seeds treated at different times with a compound of formula (I) and a mixing component. In the case of seeds treated with a compound of formula (I) and a mixing component at different times, the individual substances may be present on the seeds in different layers. Here, the layers containing the compound of formula (I) and the mixing component may be separated by an intermediate layer. The present invention also relates to seeds to which the compound of formula (I) and the mixing component are applied as components of a coating or as one or more additional layers in addition to the coating.

[0202] Furthermore, the present invention relates to seeds which, after treatment with a compound of formula (I), undergo a film coating process to prevent dust abrasion of the seeds.

[0203] One of the advantages encountered with the systemic compounds of formula (I) is the fact that by treating the seeds, not only the seeds themselves but also the plants resulting therefrom are protected against animal pests after emergence. In this way, it is possible to omit the immediate treatment of the crop at sowing time or immediately thereafter.

[0204] The further advantage must be considered that by treating the seeds with a compound of formula (I), the germination and emergence of the treated seeds can be enhanced.

[0205] Similarly, it is considered advantageous that the compounds of formula (I) can also be used in particular for transgenic seeds.

[0206] Furthermore, the compounds of formula (I) can be used in combination with compositions or compounds of signal transduction technology, leading to better colonization by symbiotic organisms such as rhizobia, mycorrhizae and / or endophytes or fungi, and / or optimized nitrogen fixation.

[0207] The compounds of formula (I) are suitable for protecting the seeds of any plant variety used in agriculture, greenhouses, forests or horticulture. In particular, these take the form of seeds of cereals (e.g., wheat, barley, rye, millet and oats), maize, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, rapeseed, beet (e.g., sugar beet and fodder beet), peanuts, vegetables (e.g., tomatoes, cucumbers, legumes, cruciferous vegetables, onions and lettuce), fruit plants, lawns and ornamental plants. The treatment of the seeds of cereals (such as wheat, barley, rye and oats), maize, soybeans, cotton, canola, brassicas, vegetables and rice is particularly important.

[0208] As already mentioned above, the treatment of transgenic seeds with the compounds of formula (I) is also particularly important. This takes the form, in principle, of the seeds of plants containing at least one heterologous gene governing the expression of polypeptides having in particular insecticidal and / or nematicidal properties. The heterologous genes in transgenic seeds can be derived from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly suitable for the treatment of transgenic seeds containing at least one heterologous gene derived from a Bacillus sp. Particularly preferably, it is a heterologous gene derived from Bacillus thuringiensis.

[0209] In the context of the present invention, the compounds of formula (I) are applied to seeds. Preferably, the seeds are treated in a state sufficiently stable to avoid damage during the treatment. Generally, the seeds can be treated at any point in time between harvesting and sowing. The seeds commonly used are separated from the plant and the ear axis, husk, stem, outer skin, hair or pulp of the fruit have been removed. For example, it is possible to use seeds that have been harvested, washed and dried to a moisture content that allows storage. Alternatively, after drying, it is also possible to use seeds that have been treated, for example, with water and then dried again, such as priming. In the case of rice seeds, for example, it is also possible to use seeds that have been soaked in water to a specific stage of the rice embryo ("pigeon breast stage") to stimulate germination and more uniform emergence.

[0210] When treating seeds, generally, care must be taken so that the amount of the compound of formula (I) applied to the seeds and / or the amount of further additives is selected in such a way that the germination of the seeds is not adversely affected or the resulting plants are not damaged. This must be particularly ensured in the case of active compounds that can exhibit phytotoxic effects at certain application rates.

[0211] Generally, the compounds of formula (I) are applied to seeds in a suitable formulation. Formulations and methods suitable for seed treatment are known to those skilled in the art.

[0212] The compounds of formula (I) can be converted into conventional seed dressing formulations such as solutions, emulsions, suspensions, powders, foams, slurries or other coating compositions for seeds, and ULV formulations.

[0213] These formulations are prepared in a 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, defoamers, preservatives, second thickeners, adhesives, gibberellins and water.

[0214] The colorants that may be present in the seed dressing formulations that can be used according to the present invention are all colorants customary for the above purposes. It is possible to use either pigments that are slightly soluble in water or dyes that are soluble in water. Examples include dyes known by the names rhodamine B, C.I. Pigment Red 112, and C.I. Solvent Red 1.

[0215] The useful wetting agents that may be present in the seed dressing formulations that can be used according to the present invention are all substances that have been conventionally used in the formulations of pesticidal active compounds to promote wetting. It is preferred to use alkylnaphthalenesulfonates, such as diisopropyl- or diisobutylnaphthalenesulfonate.

[0216] The useful dispersants and / or emulsifiers that may be present in the seed dressing formulations that can be used according to the present invention are all nonionic, anionic, and cationic dispersants that have been conventionally used in the formulations of active pesticidal ingredients. It is preferred to use nonionic or anionic dispersants or a mixture of nonionic or anionic dispersants. Suitable nonionic dispersants include, in particular, ethylene oxide / propylene oxide block polymers, alkylphenol polyglycol ethers, and tristrillylphenol polyglycol ethers, as well as their phosphorylated or sulfated derivatives. Suitable anionic dispersants are, in particular, lignosulfonates, polyacrylates, and arylsulfonate / formaldehyde condensates.

[0217] The antifoaming agents that may be present in the seed dressing formulations that can be used according to the present invention are all foam-inhibiting substances that have been conventionally used in the formulations of active pesticidal ingredients. It is preferred to use silicone antifoaming agents and magnesium stearate.

[0218] The preservatives that may be present in the seed dressing formulations that can be used according to the present invention are all substances that can be used for the above purposes in pesticidal compositions. Examples include dichlorophene and benzyl alcohol hemi formal.

[0219] The second thickener that may be present in the seed dressing formulation usable according to the present invention is all substances that can be used for the above purposes in the pesticide composition. Cellulose derivatives, acrylic acid derivatives, xanthan, modified clay, and fine silica are preferred.

[0220] The adhesive that may be present in the seed dressing formulation usable according to the present invention is all conventional binders that can be used in seed dressing products. Polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and tyrosin can be mentioned as preferred ones.

[0221] The gibberellins that can be used according to the present invention and may be present in the seed dressing formulation are preferably gibberellin A1, A3 (= gibberellic acid), A4, and A7, and gibberellic acid is particularly preferably used. Gibberellins are known (see R. Wegler “Chemie der Pflanzenschutz - and Schadlingsbekampfungsmittel”, vol. 2, Springer Verlag, 1970, pp. 401 - 412).

[0222] The seed dressing formulation usable according to the present invention can be used to treat a wide variety of different types of seeds, either directly or after pre - diluting with water. For example, using a concentrate or a preparation obtainable therefrom by dilution with water, cereal seeds such as wheat, barley, rye, oats, and triticale, and also seeds of corn, rice, rapeseed, peas, beans, cotton, sunflower, soybean, and beet, or other wide - variety of different vegetable seeds can be dressed. The seed dressing formulation usable according to the present invention, or its diluted use form, can also be used to dress the seeds of transgenic plants.

[0223] For treating seeds in a seed dressing formulation that can be used according to the present invention, or in a form prepared therefrom by adding water, all mixing units that can normally be used in seed dressing are useful. Specifically, the procedure in seed dressing is to put the seeds into a mixer, operate batchwise or continuously, add a specific desired amount of the seed dressing formulation as it is or after pre-dilution with water, and mix everything until the formulation is evenly distributed on the seeds. Optionally, a drying operation is subsequently carried out.

[0224] The application rate of the seed dressing formulation that can be used according to the present invention can be varied within a relatively wide range. This is derived from the specific content of the compound of formula (I) in the formulation and the seeds. The application rate of the compound of formula (I) is generally 0.001 - 50 g per kg of seeds, preferably 0.01 - 15 g per kg of seeds.

[0225] Animal health In the field of animal health, i.e., the field of veterinary medicine, the compound of formula (I) is active against animal parasites, specifically ectoparasites or endoparasites. The term endoparasites includes in particular helminths and protozoa, such as coccidia. Ectoparasites are typically and preferably arthropods, especially insects or mites.

[0226] In the field of veterinary medicine, the compound of formula (I) has favorable toxicity in warm-blooded animals and is suitable for controlling parasites occurring in animal husbandry of livestock, breeding, zoos, laboratories, experiments and breeding animals. These are active against all or specific stages of parasite occurrence.

[0227] Agricultural livestock include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffalo, rabbits, reindeer, roe deer, especially cattle and pigs, or poultry such as turkeys, ducks, geese, especially chickens, or fish or crustaceans in, for example, aquaculture, or in some cases insects such as bees.

[0228] Livestock includes, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, or especially dogs, cats, etc.; cage birds; reptiles; amphibians or ornamental fish.

[0229] According to certain embodiments, the compound of formula (I) is administered to mammals.

[0230] According to another certain embodiment, the compound of formula (I) is administered to birds, i.e., cage birds or especially poultry.

[0231] By using the compound of formula (I) to control animal parasites, it is intended to reduce or prevent diseases, mortality cases and performance degradation (in the case of meat, milk, wool, skin, eggs, honey, etc.), and as a result, more economical and simple animal breeding becomes possible and better animal health can be achieved.

[0232] As used herein in the context of animal health, the term "control" or "controlling" means that the compound of formula (I) is effective to reduce the occurrence of each parasite in an animal infected with said parasite to a harmless level. More specifically, as used herein, "control" means that the compound of formula (I) is effective to kill each parasite, inhibit its growth, or inhibit its proliferation.

[0233] Exemplary arthropods include, but are not limited to, the following.

[0234] Of the order Anoplurida, for example, species of the genus Haematopinus, Linognathus, Pediculus, Phtirus, and Solenopotes; Of the Mallophagida and of the suborders Amblycerina and Ischnocerina, for example, species of Bovicola spp., Damalina spp., Felicola spp.; Lepikentron spp., Menopon spp., Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella spp.; Of the order Diptera and the suborders Nematocerina and Brachycerina, for example, species of the genus Aedes, Anopheles, Atylotus, Braula, Calliphora, Chrysomyia, Chrysops, Culex, Culicoides, Eusimulium, Fannia, Gasterophilus, Glossina, Haematobia, Haematopota, Hippobosca, Hybomitra, Hydrotaea, Hypoderma, Lipoptena, Lucilia, Lutzomyia, Melophagus, Morellia, Musca, Odagmia, Oestrus, Philipomyia, Phlebotomus, Rhinoestrus, Sarcophaga, Simulium, Stomoxys, Tabanus, Tipula, Wilhelmia, Wohlfahrtia; Of the order Siphonapterida, for example, species of the genus Ceratophyllus, Ctenocephalides, Pulex, Tunga, Xenopsylla; Of the order Heteropterida, for example, species of the genus Cimex, Panstrongylus, Rhodnius, Triatoma; and harmful and sanitary pests of the order Blattarida.

[0235] Furthermore, in the case of arthropods, although not limited thereto, the following mites may be mentioned as examples.

[0236] Acari (Acarina) and Metastigmata, for example, Argasidae, such as Argas spp., Ornithodorus spp., Otobius spp.; Ixodidae, such as Amblyomma spp., Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Ixodes spp., Rhipicephalus (Boophilus) spp., Rhipicephalus spp. (formerly belonging to multi-host ticks); Mesostigmata, such as Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Tropilaelaps spp., Varroa spp.; Actinedida (Prostigmata), such as Acarapis spp., Cheyletiella spp., Demodex spp., Listrophorus spp., Myobia spp., Neotrombicula spp., Ornithocheyletia spp., Psorergates spp., Trombicula spp.; and Acaridida (Astigmata), such as 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..

[0237] Examples of parasitic protozoa include, but are not limited to, the following.

[0238] Subphylum Mastigophora (Flagellata), for example, Metamonada: of the order Diplomonadida, for example, Giardia spp., Spironucleus spp.; Parabasala: of the order Trichomonadida, for example, Histomonas spp., Pentatrichomonas spp., Tetratrichomonas spp., Trichomonas spp., Tritrichomonas spp; Euglenozoa: of the order Trypanosomatida, for example, 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.; Eimeriida, for example, Besnoitia spp., Cystoisospora spp., Eimeria spp., Hammondia spp., Isospora spp., Neospora spp., Sarcocystis spp., Toxoplasma spp.; Adeleida, for example, Hepatozoon spp., Klossiella spp.; Haemosporida, for example, Leucocytozoon spp., Plasmodium spp.; Piroplasmida, for example, Babesia spp., Ciliophora spp., Echinozoon spp., Theileria spp.; Vesibuliferida, for example, Balantidium spp., Buxtonella spp.; Microsporidia, such as species of the genus Encephalitozoon, Enterocytozoon, Globidium, Nosema, and, further, for example, Myxozoa spp.

[0239] Helminths pathogenic to humans or animals include, for example, Acanthocephala, Nematode, Pentastoma, and Platyhelmintha (e.g., Monogenea, cestodes, and trematodes).

[0240] Exemplary helminths include, but are not limited to, the following.

[0241] Monogenea: For example, species of the genus Dactylogyrus, Gyrodactylus, Microbothrium, Polystoma, Troglocephalus; Cestodes: Of the order Pseudophyllidea, for example, species of the genus Bothridium, Diphyllobothrium, Diplogonoporus, Ichthyobothrium, Ligula, Schistocephalus, Spirometra; Of the order Cyclophyllida, for example: species of Andyra spp., Anoplocephala spp., Avitellina spp., Bertiella spp., Cittotaenia spp., Davainea spp., Diorchis spp., Diplopylidium spp., Dipylidium spp., Echinococcus spp., Echinocotyle spp., Echinolepis spp., Hydatigera spp., Hymenolepis spp., Joyeuxiella spp., Mesocestoides spp., Moniezia spp., Paranoplocephala spp., Raillietina spp., Stilesia spp., Taenia spp., Thysaniezia spp., Thysanosoma spp.; Trematodes: of the subclass Digenea, such as: Austrobilharzia spp., Brachylaima spp., Calicophoron spp., Catatropis spp., Clonorchis spp., Collyriclum spp., Cotylophoron spp., Cyclocoelum spp., Dicrocoelium spp., Diplostomum spp., Echinochasmus spp., Echinoparyphium 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., 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: of the order Trichinellida, for example: Capillaria spp., Eucoleus spp., Paracapillaria spp., Trichinella spp., Trichomosoides spp., Trichuris spp.; of the order Tylenchida, for example: Micronema spp., Parastrongyloides spp., Strongyloides spp.; Order Rhabditina, for example species of Aelurostrongylus, Amidostomum, Ancylostoma, Angiostrongylus, Bronchonema, Bunostomum, Chabertia, Cooperia, Cooperioides, Crenosoma, Cyathostomum, Cyclococercus, Cyclodontostomum, Cylicocyclus, Cylicostephanus, Cylindropharynx, Cystocaulus, Dictyocaulus, Elaphostrongylus, Filaroides, Globocephalus, Graphidium, Gyalocephalus, Haemonchus, Heligmosomoides, Hyostrongylus, Marshallagia, Metastrongylus, Muellerius, Necator, Nematodirus, Neostrongylus) Nippostrongylus spp., Obeliscoides spp., Oesophagodontus spp., Oesophagostomum spp., Ollulanus spp.; Ornithostrongylus spp., Oslerus spp., Ostertagia spp., Paracooperia spp., Paracrenosoma spp., Parafilaroides spp., Parelaphostrongylus 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., Troglostrongylus spp., Uncinaria spp.;. Order Spirurida, for example species of 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.; 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., 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 Acanthocephala: For example, Macracanthorhynchus spp., Prosthenorchis spp. of the order Oligacanthorhynchida; Moniliformis spp. of the order Moniliformida, for example; For example, Filicollis spp. of the order Polymorphida; For example, Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp. of the order Echinorhynchida; Phylum Pentastoma: For example, Linguatula spp. of the order Porocephalida.

[0242] In the field of veterinary medicine and animal husbandry, the administration of the compound of formula (I) is carried out by methods generally known in the art, such as enteral, parenteral, transdermal or nasal, in the form of a suitable preparation. Administration can be carried out prophylactically, prophylactically against infection or therapeutically.

[0243] Accordingly, one embodiment of the present invention relates to a compound of formula (I) for use as a medicament.

[0244] Another aspect relates to a compound of formula (I) for use as an anti-endoparasitic agent.

[0245] Another specific aspect relates to a compound of formula (I) for use as an anthelmintic agent, more specifically as a nematicide, a flatwormicide, a hookwormicide or a pentastomicide.

[0246] Another specific aspect relates to a compound of formula (I) for use as an antiprotozoal agent.

[0247] Another aspect relates to a compound of formula (I) for use as an anti-external parasite agent, in particular an arthropodicide, more specifically an insecticide or an acaricide.

[0248] A further aspect of the 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 adjuvant (e.g., a surfactant), in particular a pharmaceutically acceptable excipient and / or a pharmaceutically acceptable adjuvant commonly used in veterinary formulations.

[0249] A related aspect of the invention is a method for preparing a veterinary formulation as described herein, comprising the step of mixing at least one compound of formula (I) with a pharmaceutically acceptable excipient and / or adjuvant, in particular a pharmaceutically acceptable excipient and / or adjuvant commonly used in veterinary formulations.

[0250] Another specific aspect of the invention is a veterinary formulation selected from the group consisting of an anti-external parasite formulation and an anti-internal parasite formulation, more specifically selected from the group consisting of an anthelmintic formulation, an antiprotozoal formulation, and an arthropodicide formulation, even more specifically selected from the group consisting of a nematicide formulation, a flatwormicide formulation, a hookwormicide formulation, a pentastomicide formulation, an insecticide formulation and an acaricide formulation, according to the aspects described above and their preparation methods.

[0251] Another aspect relates to a method for treating a parasitic infection, in particular an infection by a parasite selected from the group of external and internal parasites described herein, by applying an effective amount of a compound of formula (I) to an animal in need thereof, in particular a non-human animal.

[0252] Another aspect relates to a method for treating an infection by a parasite, particularly an infection by a parasite selected from the group of ectoparasites and endoparasites described herein, by applying a veterinary formulation as defined herein to an animal in need thereof, particularly a non-human animal.

[0253] Another aspect relates to the use of a compound of formula (I) in the treatment of an infection by a parasite, particularly an infection by a parasite selected from the group of ectoparasites and endoparasites described herein, in an animal, particularly a non-human animal.

[0254] In the context of the health of animals or the veterinary field, the term "treatment" includes prophylactic, anti-infective or therapeutic measures.

[0255] In certain embodiments, provided herein is a mixture of at least one compound of formula (I) with other active ingredients, particularly endoparasiticides and ectoparasiticides, for use in the veterinary field.

[0256] In the field of animal health, a "mixture" not only means that two (or more) different active ingredients are formulated into a co-formulation and thereby applied together, but also refers to a product containing separate formulations for each active compound. Thus, when applying three or more active compounds, all the active compounds may be formulated into a co-formulation, or all the active compounds may be formulated into separate formulations, and a mixed form in which some of the active compounds are formulated together and some of the active compounds are formulated separately is also feasible. Separate formulations allow for separate or sequential application of the active compounds in question.

[0257] The active compounds identified by their common names herein are known and are described, for example, in the Pesticide Manual (cited above) or can be searched for on the Internet (e.g., http: / / www.alanwood.net / pesticides).

[0258] Exemplary active ingredients from the group of ectoparasiticides as mixed partners include, but are not limited to, the insecticides and acaricides listed in detail above. For further active ingredients that can be used, they are described below according to the above classification based on the latest "IRAC Mode of Action Classification Scheme". (1) Acetylcholinesterase (AChE) inhibitors; (2) GABA-regulated chloride channel blockers; (3) Sodium channel modulators; (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators; (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators; (6) Glutamate-regulated chloride channel (GluCl) allosteric modulators; (7) Juvenile hormone mimics; (8) Various unspecified (multi-site) inhibitors; (9) Chordotonal organ modulators; (10) Mite growth inhibitors; (12) Inhibitors of mitochondrial ATP synthase, for example, ATP disruptors; (13) Uncouplers of oxidative phosphorylation by disrupting the proton gradient; (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 case of Diptera); (18) Ecdysone receptor agonists; (19) Octopamine receptor agonists; (21) Inhibitors of mitochondrial complex I electron transport; (25) Inhibitors of mitochondrial complex II electron transport; (20) Inhibitors of mitochondrial complex III electron transport; (22) Voltage-dependent sodium channel blockers; (23) Inhibitors of acetyl-CoA carboxylase; (28) Ryanodine receptor modulators; (30) GABAergic chloride channel allosteric modulators.

[0259] Active ingredients whose mode of action is unknown or unspecified, for example, fentrifanil, phenoxacrim, cycloprene, chlorobenzilate, chlordimeform, flubendiamine, dicyclanil, amidoflumet, quinomethionate, triarathene, crothiazoben, tetrasul, potassium oleate, petroleum, methoxadiazone, gossypol, flutenzin, bromopropylate, cryolite; Compounds of another class, such as butacarb, dimethilan, chlorethocarb, phosphocarb, pirimiphos (-ethyl), parathion (-ethyl), methacrifos, isopropyl o -salicylate, trichlorfon, sulprofos, propaphos, sebufos, pyridathion, protopate, dichlofenthion, dimethon -S -methylsulfone, isazophos, cyanofenphos, dialifos, carbophenothion, athidathion, alomphosvinphos (-methyl), azinphos (-ethyl), chlorpyrifos (-ethyl), phosmet, iodofenphos, dioxabenzophos, formothion, honohos, flupyrazophos, fensulfothion, etrimfos; Organochlorine compounds, such as camphechlor, lindane, heptachlor; or phenylpyrazole - based, such as acetoprole, pyrafluprole, pyriprole, vaniliprole, fipronil; or isoxazoline - based, such as sarolaner, afoxolaner, lotilaner, fluralaner; Pyrethroid - based, such as (cis -, trans -) metofluthrin, profuthrin, flufenprox, flubrocythrinate, fubfenprox, fenfluthrin, protrifenbute, pyresmethrin, RU15525, terallethrin, cis -resmethrin, heptafluthrin, bioethanomethrin, biopermethrin, fenpyrithrin, cis -cyphenothrin, cis -permethrin, cyfluthrin, cyhalothrin (lambda -), chlorvaporthrin, or halogenated hydrocarbon compounds (HCHs); Neonicotinoid - based, such as nithiazine; Dicloromezotiaz, triflumizopyrim; Macrolide - lactone - based, such as nemadectin, ivermectin, latidectin, moxidectin, selamectin, eprinomectin, doramectin, emamectin benzoate; milbemycin oxime; Triprene, epofenonan, diphenolan; Biological agents, hormones, or pheromones, for example, natural products, for example, thuringiensin, codlemone, or neem components; Dinitrophenol-based, for example, dinocap, dinobuton, binapacryl; Benzoylurea-based, for example, fluazuron, penfluron; Amidine derivatives, for example, chlormebuform, simiazole, demiditraz; Beehive Varroa mite killing agents, for example, organic acids, for example, formic acid, oxalic acid.

[0260] Exemplary active ingredients from the group of endoparasite killing agents as a mixing partner include, but are not limited to, anthelmintic active compounds and antiprotozoal active compounds.

[0261] Anthelmintic active compounds include, but are not limited to, the following nematicidal active compounds, trematocidal active compounds and / or cestocidal active compounds, etc.

[0262] Of the class of macrocyclic lactones, for example: eprinomectin, abamectin, nemadectin, moxidectin, doramectin, selamectin, lepimectin, latidectin, milbemycin, ivermectin, emamectin, milbemycin; Of the class of benzimidazoles and probenzimidazoles, for example: oxibendazole, mebendazole, triclabendazole, thiophanate, parbendazole, oxfendazole, netobimin, fenbendazole, febantel, thiabendazole, cyclobenzendazole, cambendazole, albendazole sulfoxide, albendazole, flubendazole; Of the class of depsipeptides, preferably of the class of cyclic depsipeptides, particularly of the class of 24-membered cyclic depsipeptides, for example: emodepside, PF1022A; Of the class of tetrahydropyrimidines, for example: morantel, pyrantel, oxantel; Imidazothiazoles of the class, for example: butamisole, levamisole, tetramisole; Aminophenylamidines of the class, for example: amidantel, deacylated amidantel (dAMD), tribendimidine; Aminoacetonitriles of the class, for example: monepantel; Paraherquamides of the class, for example: paraherquamide, derquantel; Salicylanilides of the class, for example: tribromsalan, bromoxanide, brotianide, clioxanide, closantel, niclosamide, oxyclozanide, rafoxanide; Substituted phenols of the class, for example: nitroxynil, bithionol, disophenol, hexachlorophene, niclofolan, meniclofolan; Organophosphates of the class, for example: trichlorfon, naphthalophos, dichlorvos / DDVP, crufomate, coumaphos, haloxon; Piperazinones / quinolines of the class, for example: praziquantel, epsiprantel; Piperazines of the class, for example: piperazine, hydroxizine; Tetracyclines of the class, for example: tetracycline, chlortetracycline, doxycycline, oxytetracycline, lymecycline; Various other classes, for example: bunamidine, niridazole, resorantel, omphalotin, oriptraz, nitrosquinate, nitroxynil, oxamniquine, mirazid, mirasil, lucanthone, hycanthone, hetrazan, emetine, diethylcarbamazine, dichlorophene, diamphenethide, clonazepam, bephenium, amoscanate, chlorthrion.

[0263] Antiprotozoal active compounds include, but are not limited to, the following active compounds.

[0264] Triazines of the class, for example: diclazuril, ponazuril, retrazuril, toltrazuril; Of the class of polyether ionophores, for example: monensin, salinomycin, maduramycin, narasin; Of the class of macrolides, for example: milbemycin, erythromycin; Of the class of quinolones, for example: enrofloxacin, pradofloxacin; Of the class of quinine, for example: chloroquine; Of the class of pyrimidines, for example: pyrimethamine; Of the class of sulfonamides, for example: sulfaquinoxaline, trimethoprim, sulfachloropyridazine; Of the class of thiamines, for example: amprolium; Of the class of lincosamines, for example: clindamycin; Of the class of carbanylides, for example: imidocarb; Of the class of nitrofurans, for example: nifurtimox; Of the class of quinazoline alkaloids, for example: halofuginone; Of various other classes, for example: oxamniquine, paromomycin; Of the class of vaccines or microbial antigens, 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.

[0265] All specified mixing partners may form salts with appropriate bases or acids, provided that their functional groups permit this.

[0266] Vector control The compounds of formula (I) can also be used for vector control. For the purposes of the present invention, vectors are arthropods, in particular insects or arachnids, which can transmit pathogens, such as viruses, helminths, unicellular organisms and bacteria, from a pathogen-carrying host (plant, animal, human, etc.) to a host. The pathogens can be transmitted to the host either mechanically (e.g., trachoma by non-biting flies) or by injection into the host (e.g., malaria parasites by mosquitoes).

[0267] Examples of vectors and the diseases or pathogens carried by vectors are as follows.

[0268] (1) Mosquitoes - Anopheles: malaria, filariasis; - Culex: Japanese encephalitis, filariasis, other viral diseases, transport of other helminths; - Aedes: yellow fever, dengue fever, other viral diseases, filariasis; - Simuliidae: transport of helminths (in particular Onchocerca volvulus); - Psychodidae: transmission of leishmaniasis; (2) Lice: skin infections, epidemic typhus; (3) Fleas: infectious diseases, spotted fever, tapeworms; (4) Flies: sleeping sickness (trypanosomiasis); cholera, other bacterial diseases; (5) Ticks: acariosis, epidemic typhus, rickettsialpox, tularemia, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borreliosis; (6) Ticks: Borrelioses, e.g., Lyme disease Borrelia (Borrelia burgdorferi sensu lato.), Borrelia duttoni, tick-borne encephalitis, Q fever (Coxiella burnetii), Babesia canis canis, ehrlichiosis.

[0269] Examples of vectors in the context of the present invention are insects that can transmit plant viruses to plants, such as aphids, flies, leafhoppers or thrips. Other vectors that can transmit plant viruses are mites, lice, beetles and nematodes.

[0270] Further examples of vectors in the context of the present invention are insects such as mosquitoes and arachnids that can transmit pathogens to animals and / or humans, in particular mosquitoes of the genus Aedes, Anopheles, e.g., A. gambiae, A. arabiensis, A. funestus, A. dirus (malaria) and Culex, flies of the genus Phlebotomus, Lutzomyia, lice, fleas, flies, mites and ticks.

[0271] If the compound of formula (I) is capable of disrupting resistance, vector control is also possible.

[0272] The compound of formula (I) is suitable for use in the prevention of diseases and / or pathogens transmitted by vectors. Accordingly, a further aspect of the present invention is the use of the compound of formula (I) for vector control, for example in agriculture, horticulture, gardens and leisure facilities, and further in the protection of materials and storage products.

[0273] Protection of industrial materials The compounds of formula (I) are suitable for protecting industrial materials from attack or destruction by insects of, for example, Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Hemiptera.

[0274] Industrial materials in the present context are understood to mean inanimate materials, such as preferably plastics, adhesives, ceramic sand, paper and cardboard, leather, wood, wood products and coatings compositions. The use of the invention for protecting wood is particularly preferred.

[0275] In a further embodiment, the compounds of formula (I) are used together with at least one further insecticide and / or at least one fungicide.

[0276] In a further embodiment, the compounds of formula (I) are present as ready-to-use pest control agents, i.e. they can be applied to the material in question without further modification. Suitable further insecticides or fungicides are in particular those mentioned above.

[0277] Surprisingly, it has also been found that the compounds of formula (I) can be used to protect objects in contact with salt water or brackish water, in particular ship hulls, screens, nets, buildings, moorings and signalling systems from fouling. Similarly, the compounds of formula (I) can be used as anti-adhesion agents, either alone or in combination with other active compounds.

[0278] Control of animal pests in the sanitary sector The compounds of formula (I) are suitable for the control of animal pests in the sanitary sector. In particular, the invention can be applied to the protection of the household, sanitary and storage product sectors in order to control insects, arachnids, fleas and mites encountered in closed spaces such as dwellings, factory halls, offices, vehicle cabins, livestock, etc. For controlling animal 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 susceptible and resistant species and against all stages of development.

[0279] These pests include, for example, pests of the class Arachnida, such as Scorpiones, Araneae and Opiliones, the classes Chilopoda and Diplopoda, and of the class Insecta, such as Blattodea, Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or Orthoptera, Siphonaptera and Zygentoma, as well as pests of the order Isopoda from the class Malacostraca.

[0280] They are used, for example, as granules or powders, in aerosol, pressure-free spray products, such as pump and atomizer sprays, automatic atomization systems, sprayers, foams, gels, evaporator products with evaporator tablets made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, insect-repellent papers, insect-repellent bags and insect-repellent gels, in bait for spreading or in bait stations.

[0281] Abbreviations and Symbols AcOH: acetic acid aq: aqueous solution br: broad Boc: tert-butyloxycarbonyl d: doublet DAST: diethylaminosulfur trifluoride DCC: N,N'-dicyclohexylcarbodiimide DCM: dichloromethane DIPEA: diisopropylethylamine DMF: N,N-dimethylformamide DMSO: dimethyl sulfoxide ee: enantiomeric excess eq: equivalent EtOAc: Ethyl acetate 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 M: Molar concentration m: Multiplicity MeCN: Acetonitrile MeOH: Methanol NMR: Nuclear magnetic resonance q: Quartet r.t.: Room temperature s: Singlet sat: Saturated T: Temperature t: Triplet T3P®: Propylphosphonic anhydride TLC: Thin layer chromatography THF: Tetrahydrofuran δ: Chemical shift Description of processes and intermediates The compounds of formula I and the compounds shown in Table 3 can be prepared as shown in Scheme 1 below, wherein R 1 , R 2 , R 3 , R 4 , and R 5 are as defined above or represent the corresponding fragments of the compounds shown in Table 3. X represents OH or Cl.

[0282] Scheme 1

Chemical formula

[0283] X = OH: React the triazole compound of formula (a) with the carboxylic acid (X = OH) of formula (b) to form the compound of formula I. For example, in a suitable solvent such as ethyl acetate or DMF, a mixture of the triazole of formula (a), the carboxylic acid (X = OH) of formula (b), a suitable coupling reagent such as T3P (registered trademark), HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA is mixed at a temperature in the range of about 0 to 100 °C to provide the compound of formula I, which is then isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

[0284] X = Cl: React the triazole compound of formula (a) with the carboxylic acid chloride (X = Cl) of formula (b) to form the compound of formula I. For example, in a suitable solvent such as dichloromethane or THF, a mixture of the triazole of formula (a), the carboxylic acid chloride (X = Cl) of formula (b), and a suitable base such as triethylamine or DIPEA is mixed at a temperature in the range of about 0 to 100 °C to obtain the compound of formula I, which is then isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

[0285] The carboxylic acid (X = OH) of formula (b) and the carboxylic acid chloride (X = Cl) of formula (b) are commercially available or can be synthesized by methods well known to those skilled in the art. The essential triazole compound of formula (a) can be prepared as shown in Scheme 2 below, where R 3 and R 4 are as described above, R 1 is C 1 ~C 6 alkyl, R 5 is C 1 ~C 3 alkyl or R 1 , R 3 , R 4 and R 5 represent the corresponding fragments of the compounds shown in Table 3. LG is a suitable leaving group (see also WO 2017192385).

[0286] Scheme 2 [Chemical formula]

[0287] React the amine of formula (c) with the substituted triazole of formula (d) to form the compound of formula (a). For example, in a suitable solvent such as acetonitrile or DMF, the triazole of formula (d), the amine of formula (c), and a mixture of a suitable base such as K 2 CO 3 , NaH or DIPEA are mixed at a temperature in the range of about 20 - 120 °C to obtain the compound of formula (a), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography.

[0288] Alternatively, react the substituted triazole of formula (d) with ammonia to form the compound of formula (e). For example, a solution of ammonia in a suitable solvent such as methanol and the substituted triazole of formula (d) are mixed in a sealed tube at a temperature in the range of about 0 - 25 °C to obtain the compound of formula (e), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as trituration. In a suitable solvent such as acetonitrile or DMF, the substituted triazole of formula (e), the compound of formula (f), and K 2 CO 3 or a suitable base such as DIPEA are mixed at a temperature in the range of about 20 - 120 °C to obtain the compound of formula (a), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography.

[0289] The amine of formula (c) and the compound of formula (f) are commercially available or can be synthesized by methods known to those skilled in the art. The essential triazole compound of formula (d) can be prepared as shown in Scheme 3 below, where R 3 and R 4 are as described above, R 5 is C 1 -C 3 alkyl, or R 3 , R 4 and R5 represents the corresponding fragment of the compound shown in Table 3, and LG is a suitable leaving group (see also International Publication No. WO 2017 / 192385).

[0290] Scheme 3

Chemical Formula

[0291] The amide of formula (h) is reacted with N,N-dimethylamidedimethylacetal (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 N,N-dimethylamidedimethylacetal of formula (g) are reacted in a suitable solvent such as CH 2 Cl 2 in an appropriate solvent such as to obtain a compound of formula (i). After removing the solvent, the compound of formula (i) is reacted with substituted hydrazine (j) in an appropriate solvent such as 1,4-dioxane, acetic acid or a mixture of such solvents at a temperature in the range of about 20 to 100 °C to obtain a compound of formula (d), which is then isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

[0292] The N,N-dimethylamidoacetal of formula (g), the amide of formula (h), and the hydrazine of formula (j) are commercially available or can be synthesized by methods known to those skilled in the art.

[0293] For example, for 5-bromo-2-hydrazinopyridine, see International Publication No. WO 2013 / 038362.

[0294] For 2-hydrazino-1,3-thiazole, see US Patent Application Publication No. US 2008 / 0234327, International Publication No. WO 2018 / 064119, International Publication No. WO 2008 / 144767, International Publication No. WO 2008 / 121861, International Publication No. WO 2004 / 046120.

[0295] The compounds of formula I and the examples shown in Table 3 can be prepared as shown in Scheme 4 below, where R 1 , R 2 , R 3 and R 4 are as defined above, and R 5 is C 1 - C 3 alkyl, or R 1 , R 2 , R 3 , R 4 and R 5 represent the corresponding fragments of the compounds shown in Table 3.

[0296] Scheme 4

Chemical formula

[0297] React the amide of formula (n) with N,N-dimethylamidodimethylacetal of formula (g) to form a compound of formula (o), and then react this with a substituted hydrazine of formula (j) under acidic conditions to form a compound of formula I. For example, react the compound of formula (n) with N,N-dimethylamidodimethylacetal of formula (g) in a suitable solvent such as CH 2 Cl 2 etc. under reflux to obtain a compound of formula (o). After removing the solvent, react the compound of formula (o) 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 in the range of about 20 - 100 °C. Then, the obtained compound of formula I can be isolated and purified using techniques well-known in the art such as chromatography if necessary and desired.

[0298] The essential amide of formula (n) can be prepared as shown in Scheme 5 below, where R 2 and R 3 are as described above, and R 1 is C 1 - C 6 alkyl or H (see also WO 2017192385), or R 1 , R 2and R 3 represents the corresponding fragment of the compound shown in Table 3.

[0299] Scheme 5 [Chemical formula]

[0300] The aminoamide of formula (p) is reacted with the carboxylic acid of formula (b) to form the compound of formula (n). For example, in a suitable solvent such as ethyl acetate or DMF, a mixture of the aminoamide of formula (p), the carboxylic acid (b), a suitable coupling reagent such as T3P (registered trademark), HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA is mixed at a temperature in the range of about 0 - 100 °C to obtain the compound of formula (n), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography.

[0301] Alternatively, the amino acid of formula (q) is reacted with thionyl chloride in a suitable solvent such as MeOH at room temperature to obtain the aminoester of formula (r). The obtained aminoester (r) is reacted at room temperature in a suitable solvent such as acetic acid with an aldehyde or ketone, a suitable reducing agent such as sodium triacetoxyborohydride, and a dehydrating agent such as Na 2 SO 4 to obtain the compound of formula (s). Then, the obtained aminoester of formula (s) is reacted in a suitable solvent such as ethyl acetate at about 90 °C with the carboxylic acid of formula (b), a suitable coupling reagent such as T3P (registered trademark), and a suitable base such as DIPEA to obtain the amidoester of formula (t), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography. The obtained amidoester of formula (t) is reacted with magnesium nitride in a suitable solvent such as MeOH in a sealed tube at about 80 °C to obtain the compound of formula (n), which is then isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography or extraction.

[0302] The compounds of formula (b) and (q) are commercially available. The essential amino amide compound of formula (p) is commercially available or can be prepared as shown in Scheme 6 below, where R 1 , R 3 and Y are as described above or represent the corresponding fragments of the compounds shown in Table 3, and LG is a suitable leaving group (see also WO 2017 / 192385).

[0303] The compounds of formula (c) and (h) are commercially available.

[0304] The essential amine of formula (p) can be prepared as shown in Scheme 6 below, where R 1 and R 3 are as described above (see also WO 2017 / 192385) or represent the corresponding fragments of the compounds shown in Table 3.

[0305] Scheme 6

Chemical Structure

[0306] React the amine of formula (c) with the amide of formula (h) to form the compound of formula (p). For example, in a suitable solvent such as acetonitrile or DMF, mix the amine of formula (c), the amide of formula (h), and a mixture of a suitable base such as K 2 CO 3 or DIPEA at 25 - 80 °C to obtain the compound of formula (p), which can then be isolated and purified using techniques well-known in the art such as chromatography if necessary and desired.

[0307] In another approach, the compound of formula I can be prepared as shown in Scheme 7 below, where R 1 , R 2 , R 3 , R 4 are as defined above, R 5 is ethyl, isopropyl, tert-butyl, difluoromethyl or cyclopropyl, or R 1 , R2 , R 3 , R 4 and R 5 represent the corresponding fragments of the compounds shown in Table 3.

[0308] Scheme 7 [Chemical formula]

[0309] The amidine hydrochloride of formula (u) is reacted with the acid of formula (v). For example, in a suitable solvent such as acetonitrile or DMF, the amidine hydrochloride of formula (u), the carboxylic acid (v), a suitable coupling reagent such as HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA are mixed at a temperature in the range of about 0 to 100 °C to form the compound of formula (w), and then reacted with the substituted hydrazine of formula (j) under acidic conditions to form the compound of formula I, which is then isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

[0310] The amidine hydrochloride of formula (u), the carboxylic acid derivative of formula (v) and the hydrazine of formula (j) are commercially available or can be synthesized by methods known to those skilled in the art.

[0311] The compound of formula (j') can be prepared as shown in Scheme 8 below, wherein E is trifluoromethoxy, difluoromethoxy or trifluoromethylsulfanyl, LG is chlorine, fluorine, methylthio, methylsulfinyl or methylsulfonyl, and A is N or CH.

[0312] Scheme 8 [Chemical formula]

[0313] React a compound of formula (x) containing a leaving group (LG) (LG = methylsulfonyl; International Publication No. WO 2016 / 001266) with hydrazine hydrate to form a hydrazine of formula (j'). For example, react a mixture of the leaving group-containing compound (x) and hydrazine hydrate in a suitable solvent, such as methanol or ethanol, at 0 to 80 °C to obtain a compound of formula (j') or its hydrochloride, hydrobromide or methanesulfonate salt, and then isolate it and, if necessary and desired, purify it using techniques well known in the art.

[0314] The compound of formula (x) is commercially available or can be synthesized by methods known to those skilled in the art.

[0315] The compound of formula (zb) can be prepared as shown in Scheme 9 below, where R 1 , R 2 , R 3 and R 5 are as defined above or R 1 , R 2 , R 3 and R 5 represent the corresponding fragments of the compounds shown in Table 3. T is a pyridine or pyrimidine ring substituted with -NO 2 - group, -NH 2 - group or -NH-A- group. LG is a suitable leaving group and A represents CO-C 1 ~C 6 alkyl, CO-cyclopropyl, CO-(4-fluorophenyl).

[0316] Scheme 9

Chemical formula

[0317] The nitro compound of formula (y) is converted to the respective amino compound of the formula in the presence of hydrogen and palladium carbon in a suitable solvent such as THF or ethanol under reducing conditions (European Journal of Medicinal Chemistry, 158, 322 - 333; 2018), using tin(II) chloride and HCl in a suitable solvent such as ethanol (International Publication No. 2018085247), using iron powder and HCl in a suitable solvent such as ethanol (International Publication No. 2017216293), or using iron powder in a mixture of acetic acid and ethanol. The obtained amino compound (z) reacts with an acylation or benzoylation reagent A-LG of formula (za) in the presence of a suitable base such as DIPEA or potassium carbonate. Subsequently, the obtained compound of formula (zb) is purified, if necessary and desired, using techniques well-known in the art such as chromatography.

[0318] The carboxylic acid chlorides of formula (za) are commercially available or can be synthesized by methods known to those skilled in the art. The essential compounds of formula (y) can be obtained as described in Scheme 4.

[0319] The compound of formula (ze) can be prepared as shown in Scheme 10 below, wherein R 1 , R 2 , R 3 and R 5 are as previously defined, or R 1 , R 2 , R 3 and R 5 represent the corresponding fragments of the compounds shown in Table 3. T is pyridine or pyrimidine substituted with a -CO 2 alkyl group, -COOH or -CON(E 1 )E 2 group. E 1 and E 2 are independently selected from the group consisting of H, C 1 ~C 6 alkyl and cyclopropyl.

[0320] Scheme 10 [Chemical formula]

[0321] Saponify the ester compound of formula (zc) to obtain each carboxylic acid compound of formula (zd), and then perform an amide coupling step with the amine of formula (zx) to obtain the amide of formula (ze) by the latest method known to those skilled in the art.

[0322] For example, in a suitable solvent such as ethyl acetate or DMF, mix a mixture of the amine of formula (zx), carboxylic acid (zd), a suitable coupling reagent such as T3P (registered trademark), HATU or DCC / HOBt, and a suitable base such as triethylamine or DIPEA at a temperature in the range of about 0 to 100 °C to obtain the compound of formula (ze), and then isolate it and purify it using techniques well-known in the art such as chromatography if necessary and desired.

[0323] The amine of formula (zx) is commercially available or can be synthesized by methods known to those skilled in the art. The required compound of formula (zc) can be obtained as described in Scheme 4.

[0324] The compound of formula (e) can also be prepared as shown in Scheme 11 below, where R 1 , R 3 and R 4 are as defined above, R 5 is C 1 ~C 3 alkyl, or R 1 , R 3 , R 4 and R 5 represent the corresponding fragments of the compounds shown in Table 3.

[0325] Scheme 11 [Chemical formula]

[0326] React the amide of formula (zf) with N,N-dimethylamidedimethylacetal of formula (g) to form a compound of formula (zg), and then react this with a substituted hydrazine of formula (j) under acidic conditions to form a compound of formula (zh). For example, the compound of formula (zf) and N,N-dimethylamidedimethylacetal of formula (g) are reacted in a suitable solvent such as CH 2 Cl 2 etc. under reflux to obtain a compound of formula (zg). After removing the solvent, the compound of formula (zg) 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 in the range of about 20 - 80 °C. Then, the obtained compound of formula (zh) is isolated and, if necessary and desired, can be purified using techniques well-known in the art such as chromatography.

[0327] Treat the carbamate of formula (zh) with an acid to form the amine of formula (a). For example, the carbamate of formula (zh) and a suitable acid, such as hydrogen chloride or trifluoroacetic acid, are reacted in a suitable solvent such as dioxane, or in the case of trifluoroacetic acid without an additional solvent, at a temperature in the range of about 0 - 80 °C. Then, the obtained amine of formula (a) is isolated as the free amine or as their acid salts after base treatment, and if necessary and desired, can be purified using techniques well-known in the art such as chromatography.

[0328] The essential amide of formula (zf) and the hydrazine of formula (j) are commercially available or can be synthesized by the methods described in this application or methods known to those skilled in the art.

[0329] The compound of formula (zj) can be prepared as shown in Scheme 12 below, where R 1 , R 2 , R 3 and R 5 are as defined previously, or R 1 , R 2 , R 3 and R 5represents the corresponding fragment of the compound shown in Table 3, LG is a suitable leaving group such as chlorine, bromine or iodine, and Rz is an optionally substituted 5- to 6-membered heteroaryl or methylsulfonyl.

[0330] Scheme 12

Chemical formula

[0331] The required compound of formula (zi) can be obtained as described in Scheme 4.

[0332] For example, LG can generally be bromine which can be converted by a suitable nucleophile in a transition metal-catalyzed reaction with, for example, a substituted pyrazole or triazole or sulfinate according to a generally known procedure. For example, for bromine substitution with pyrazole, see page 37, Example 6, Step 1 of WO 2013 / 062981 A1.

[0333] The compound of formula (zl) can be prepared as shown in Scheme 13 below, where the formula, R 1 , R 2 , R 3 and R 5 are as defined above. Hal is chlorine, bromine or iodine.

[0334] Scheme 13

Chemical formula

[0335] The compound of formula (zk) can be further derived by halogenation of thiazole. The necessary methods are known to those skilled in the art. For example, chlorination is achieved using a halogenating agent such as N-chloro-succinimide in a suitable solvent such as DMF (synthesis of Example II-15 described in this application).

[0336] The compound of formula (zk) can be prepared as shown in Schemes 1-7 and 11.

[0337] Scheme 14 shows the preparation of 3-haloalkyltriazole-containing amine (e') used, for example, in the synthesis of Example I-9. R 5 is difluoromethyl and E' is CN.

[0338] Scheme 14 [Chemical formula]

[0339] In the first step, hydrazonamide (zn) is formed as described in European Patent No. 1099695. In the second step, (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH purchased from ABCR) and oxalyl chloride are used to prepare (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride according to Tetrahedron: Asymmetry, 21(8), 936 - 942, 2010. This reacts with hydrazonamide in the presence of a base such as pyridine as described in European Patent No. 1099695 to form a triazole of formula (zo), and partial or complete racemization is possible. In the third step, as described in International Publication No. 2018086605, the phthalimide protecting group is removed by reaction with hydrazine hydrate in a suitable solvent such as ethanol. In the final step, the resulting amine (e') is reacted with a carboxylic acid to form an exemplary compound, such as I-9 described in Scheme 1.

[0340] Scheme 15 shows the preparation of alkyltriazole-containing amine (e') used, for example, in the synthesis of Example I-6. R 5 is ethyl, isopropyl, or cyclopropyl, E' is CN, and Z is NH 2 or OC 1 ~C 6 alkyl.

[0341] Scheme 15 [Chemical]

[0342] React N-(tert-butoxycarbonyl)-L-alanine with an alkylamidine (where Z = NH 2 (in the case) or an alkyl imidate (where Z = OC 1 ~C 6 (in the case of alkyl) to form an intermediate of formula (zq), and then react this with a substituted hydrazine of formula (j'') to form an alkyltriazole of formula (zr). For example, when Z = NH 2 (compare J.Org.Chem.2011,76,1177 - 1179), react N-(tert-butoxycarbonyl)-L-alanine and an alkylamidine of formula (zp) at a temperature in the range of 0 - 50 °C in a suitable solvent such as DMF, in the presence of a suitable coupling reagent such as HATU and a suitable base such as triethylamine or DIPEA to form an acylamidine intermediate of formula (zq). After removal of the solvent, react the intermediate of formula (zq) with a substituted hydrazine of formula (j'') in a suitable solvent such as acetic acid at a temperature in the range of about 20 - 80 °C. Then, isolate the resulting alkyltriazole of formula (zr) and, if necessary and desired, purify it using techniques well-known in the art such as chromatography.

[0343] Z = OC 1 ~C 6 (in the case of alkyl), react N-(tert-butoxycarbonyl)-L-alanine and an alkyl imidate of formula (zp) or a suitable salt thereof at a temperature in the range of 0 - 25 °C in a suitable solvent such as THF, in the presence of a suitable coupling reagent such as HATU and a suitable base such as triethylamine or DIPEA to form an acyl imidate intermediate of formula (zq). When a substituted hydrazine of formula (j'') is added, the intermediate of formula (zq) reacts at a temperature in the range of 20 - 80 °C to give an alkyltriazole of formula (zr), which is then isolated and, if necessary and desired, purified using techniques well-known in the art such as chromatography.

[0344] The carbamate of formula (zr) is treated with an acid (e.g., 4N HCl in dioxane) to form the amine of formula (e’) as shown in Scheme 11.

[0345] The required alkylamidine and alkylimidate or its salt and the hydrazine of formula (j’’) are commercially available or can be synthesized by the methods described in this application or methods known to those skilled in the art.

[0346] Scheme 16 shows the preparation of the alkoxytriazole-containing amine (e1) used, for example, in the synthesis of Example I-10. Alkyl is methyl, ethyl or isopropyl, and E’ is CN.

[0347] Scheme 16

Chemical formula

[0348] The synthesis starts from the reaction of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl chloride with potassium thiocyanate (KSCN) in acetone to obtain the corresponding isocyanate intermediate (zs), which is then treated with the corresponding alcohol in the next step to obtain O-alkyl [(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate (zt). The reaction of the intermediate (zt) in ethanol with the hydrazine of formula (j’’) gives the cyclized product of formula (zu) described in Bioorganic & Medicinal Chemistry 26(2018)3321 - 3344. Deprotection of the amino group with hydrazine hydrate gives the primary amine of formula (e1). In the final step, the resulting amine is reacted with a carboxylic acid to form the exemplified compound, e.g., I-10 described in Scheme 1.

[0349] The compound of formula (zw) can be prepared as shown in Scheme 17 below, wherein Alk is C 1 ~C 6is alkyl, and R 4 is 5-cyanopyridin-2-yl, and R 5 is ethyl, n-propyl, isopropyl, cyclopropyl or t-butyl.

[0350] Scheme 17 [Chemical formula]

[0351] (αS)-1,3-Dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride is reacted with imidate (zq) or a suitable salt thereof to form an acyl imidate intermediate of formula (zv), which is then reacted with a hydrazine of formula (j) to obtain a triazole of formula (zw). For example, a mixture of the acid chloride and the imidate of formula (zv) is reacted at a temperature in the range of -20 to 25 °C in a suitable solvent such as THF. Then, the resulting intermediate of formula (zv) is reacted with the hydrazine of formula (j) at a temperature in the range of 0 to 80 °C in a suitable solvent such as THF. Then, the resulting triazole of formula (zw) is purified, if necessary and desired, using techniques well known in the art such as chromatography. The phthalimide protecting group can be removed using hydrazine as described in Scheme 14 to obtain the respective free amines.

[0352] The required acid chlorides may be obtained as described in Scheme 14, and the imidates of formula (zq) or their salts are either commercially available or may be synthesized by methods known to those skilled in the art.

[0353] Scheme 18 shows the preparation of a 3-halotriazole-containing amine (e') used, for example, in the synthesis of Example I-39, wherein R 5 is halogen and E' is CN.

[0354] Scheme 18 [Chemical formula]

[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 an N-acylated 1-N-Boc-2-methyl-isothiourea of formula (ya), and partial or complete racemization is possible. In the second step, as described in International Publication No. WO 2014 / 009425 A1, cyclization is carried out with hydrazine (j'') (for example, E' is CN) in the presence of a base such as pyridine to form a 1,2,4-triazole of formula (yb) containing an NH-Boc group. After N-Boc deprotection in the third step under acidic conditions (for example, 4N HCl in dioxane), a 3-amino-1,2,4-triazole hydrochloride of formula (yc) is formed, which can be treated in the fourth step with tert-butyl nitrile, followed by CuCl described by N. Desroy et al., J. Med. Chem. 2013, 56, 1418-1430 2 (R 5 =Cl), CuBr described by JP-Pat. 2010070503 A 2 (R 5 =Br), CuI / I described by K. Pchalek and M. P. Hay J. Org. Chem. 2006, 71, 6530-6535 2 mixture (R 5 =I), or treated with a copper halide as a salt such as diiodomethane (R 5 =I) described by N. R. Norcross et al. J. Med. Chem., 2016, 59(13), 6101-6120 to form a 3-halogen-substituted 1,2,4-triazole (yd). Alternatively, fluorine (R 5=F) can be introduced using HF instead of copper halide, as described, for example, by V. Krchnak and Z. Arnold in Coll. Czech. Chem. Commun., 1975, 40(5), 1390-1395. 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 International Publication No. WO 2018 / 086605. In the final step, the resulting amine (e’) is reacted with a carboxylic acid to form an exemplified compound, for example I-39 or I-48, as described in Scheme 1.

[0356] Preparation Example Synthesis of 3-chloro-N-{1-[1-(6-cyano-3-pyridinyl)-3-(difluoromethyl)-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide (Example I-9) Step 1 2-[6-Cyano-3-pyridinyl]hydrazide-2,2-difluoro-ethanimidic acid

Chemical Structure

[0357] To 2.33 g (17.4 mmol) of 5-hydrazinyl-2-pyridinecarbonitrile in methanol (30 mL), 3.15 g (24.3 mmol) of ethyl 2,2-difluoroethanecarboximidate (purchased from Enamine Building Blocks) was added, and the reaction mixture was stirred at room temperature overnight. The solvent was evaporated, and then the residue was stirred with n-hexane (30 mL) and ethyl acetate (3 mL). The brownish precipitate was separated and dried to obtain 3.38 g of 2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoro-ethanimidic acid (purity: 90.4%, yield: 83.0%).

[0358] ESI mass [m / z]: 211.1 [M+H] + Step 2 2-[1-[3-(Difluoromethyl)-1-(6-cyano-3-pyridinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione

Chem.

[0359] To 3.28 g (14.0 mmol) of 2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoro-ethanimidic acid in pyridine (20 mL), 3.32 g (14.0 mmol) of (αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride ((αS)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH purchased from ABCR) and prepared from oxalyl chloride: see D.A. Gruzdev et al., Tetrahedron: Asymmetry, 21(8), 936 - 942, 2010) was added and the reaction mixture was stirred at room temperature overnight. Then, water (200 mL) was added and the mixture was extracted with dichloromethane (200 mL). The organic phase was extracted twice with saturated NaHCO 3 aqueous solution (100 mL), dried over Na 2 SO 4 and evaporated under reduced pressure. The remaining solid residue was chromatographed on silica gel with a cyclohexane / acetone gradient to give 1.09 g of the racemic title compound (purity: 95.7%, yield: 18.8%) as a colorless solid.

[0360] ESI mass [m / z]: 395.2 [M + H] + Step 3 6-[5-(1-Aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-4)

Chem.

[0361] To 1.0 g (2.5 mmol) of 2-[1-[3-(difluoromethyl)-1-(6-cyano-3-pyridinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (20 mL), 577 mg (6.34 mmol) of hydrazine hydrate was added, and the reaction mixture was heated under reflux. After 30 minutes, a colorless precipitate was formed. The reaction mixture was stirred and heated under reflux for an additional 1 hour, acetone (15 mL) was added, and heating was continued for an additional 30 minutes. The reaction mixture was concentrated, and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to obtain 663 mg of 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (IT-4), which was used in Step 4 without purification.

[0362] ESI mass [m / z]: 265.2 [M+H] + 1 See Table 2 (INT-4) for the 1H-NMR peak list.

[0363] Step 4 3-chloro-N-{1-[1-(6-cyano-3-pyridinyl)-3-(difluoromethyl)-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide

Chemical formula

[0364] To 222 mg (0.84 mmol) of 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-4), 194 mg (0.84 mmol) of 3-chloro-5-(trifluoromethyl)benzoic acid, 141 mg (1.09 mmol) of N,N-diisopropylethylamine (Hünig's base) in N,N-dimethylformamide (DMF) (5 mL), and 383 mg (1.00 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium-hexafluorophosphate] (HATU) were added, and the reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, the solid residue was treated with dichloromethane, and then extracted with saturated NaHCO 3 aqueous solution and water. The organic phase was separated, dried over Na 2 SO 4 , and the solvent was evaporated under reduced pressure. The remaining solid residue was chromatographed on silica gel with a cyclohexane / acetone gradient, followed by dispersion with diethyl ether and filtration to obtain 259 mg of the racemic title compound (purity: 100%, yield: 65.4%).

[0365] ESI mass [m / z]: 471.1 [M+H] + 1 See Table 1 for the 1H-NMR peak list.

[0366] Synthesis of 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile (INT-2) Step 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 [Chemical formula]

[0367] Anhydrous CH 2 Cl2 A solution of 5.00 g (purity 95%, 21.6 mmol) of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid and 0.08 mL (1 mmol) of DMF 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 volatile substances were removed under reduced pressure, and the residue was used in the next step without further purification.

[0368] To a solution of 3.13 g (purity 95%, 21.6 mmol) of methyl 2-methylpropanimidate hydrochloride (1:1) in 40 mL of anhydrous THF, 15.1 mL (86.4 mmol) of anhydrous DIPEA was added 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 minutes. After stirring at 0 °C for 30 minutes, 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 minutes and at ambient temperature overnight. All volatile substances were removed under reduced pressure. 200 mL of water was added to the residue, and the mixture was extracted with 200 mL of EtOAc. The phases were separated, and the aqueous phase was extracted several times with EtOAc. The combined organic phases were washed with brine and dried over Na 2 SO 4 4. The solvent was removed under reduced pressure, and the residue was purified by silica chromatography (cyclohexane / ethyl acetate) to obtain 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.

[0369] ESI mass [m / z]: 387.5 [M+H] + Step 2 6-{5-[(1S)-1-Aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile (INT-2)

Chemical formula

[0370] 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 hours. 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 (purity 70%) of 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile.

[0371] ESI mass [m / z]: 257.2 [M+H] + Synthesis of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide (Example I-6) Step 1 tert-Butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate

Chemical formula

[0372] To a solution of 2.0 g (10.5 mmol) of N-(tert-butoxycarbonyl)-L-alanine in N,N-dimethylformamide (37.5 ml) were added 1.91 g (15.9 mmol) of cyclopropylamidine, 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 Na2 CO 3 A saturated aqueous solution of was added, and then the mixture was extracted with EtOAc. The combined organic layers were washed with water, 5% NaH 2 PO 4 aqueous solution, brine, and finally dried over Na 2 SO 4 . After filtration and evaporation of the solvent under vacuum, the crude product was purified by preparative HPLC (water / acetonitrile). The combined product fractions were evaporated to give the title compound (0.77 g, 21%).

[0373] ESI mass [m / z]: 355.3 [M+H] + 1 1H-NMR peak list (400.2 MHz, CD3CN): 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) Project 2 6-{5-[(1S)-1-Aminoethyl]-3-cyclopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride (1:1) (INT-3)

Chem.

[0374] 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 dioxane (22 ml) was treated with 4 N HCl in dioxane (10.9 ml). The reaction mixture was stirred overnight at room temperature. The resulting precipitate was separated by filtration and dried under air to give the title compound (0.71, 100%).

[0375] ESI mass [m / z]: 255.1 [M + H - HCl] + Step 3 3-Chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide

Chem.

[0376] To a solution of 100 mg (0.34 mmol) of 6-{5-[(1S)-1-aminoethyl]-3-cyclopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride (1:1) in anhydrous dichloromethane (4.65 ml) was added 0.01 ml (0.48 mmol) of N,N-diisopropylethylamine, followed by the addition of a solution of 0.06 ml (0.37 mmol) of 3-chloro-5-(trifluoromethyl)benzoyl chloride in 1.5 ml of anhydrous dichloromethane. The mixture was stirred overnight at room temperature. The reaction mixture was quenched with an aqueous solution of 5% Na 2 PO 4 and then extracted with dichloromethane. The organic phase was washed with Na 2 SO4 It was dried, filtered, the solvent was evaporated under vacuum, and the crude product was purified by preparative HPLC (water / acetonitrile, 0.1% formic acid). The combined product fractions were evaporated to give the title compound (115 mg, 73%).

[0377] ESI mass [m / z]: 461.2 [M+H] + 1 See Table 1 for the 1H NMR peak list.

[0378] Synthesis of 3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide (Example I-10) Step 1: O-methyl [(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate

Chemical formula

[0379] (2S)-2-(1,3-Dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid 1.0 g (4.6 mmol) in toluene (15 ml) was added with oxalyl chloride 0.80 ml (9.12 mmol) and 1 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. After this time, additional oxalyl chloride (0.5 ml) was added again, the reaction mixture was stirred for 3 hours and finally evaporated. The crude residue was dissolved in acetone (15 ml), then KSCN 0.44 g (4.56 mmol) was added as a solution in acetone (5 ml), and the mixture was stirred at 60 °C for 2 hours. Then, methanol 0.46 ml (11.4 mmol) was added, the mixture was stirred at 60 °C overnight, cooled to room temperature and evaporated under reduced pressure. The resulting residue was dissolved in EtOAc, washed with water and brine respectively, and finally the organic layer was dried over anhydrous Na 2 SO4 It was dried and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain the title compound (0.82 g, 59%).

[0380] ESI mass [m / z]: 293.1 [M+H] + Step 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

Chemical formula

[0381] To a solution of O-methyl [(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate 1.5 g (5.1 mmol) in ethanol (30 ml) was added 6-hydrazinonicotinonitrile 0.69 g (5.1 mmol), and the reaction mixture was stirred at 90 °C overnight. The mixture was cooled to room temperature and evaporated under reduced pressure, and the resulting residue was dissolved in EtOAc and washed with water and brine respectively. The organic layer was dried over anhydrous Na 2 SO 4 It was dried and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to obtain the title compound (1.23 g, 58%).

[0382] ESI mass [m / z]: 375.1 [M+H] + Step 3: 6-{5-[(1S)-1-aminoethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile (INT-5)

Chemical formula

[0383] 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 ethanol (30 ml) was added with 0.39 ml (8.01 mmol) of hydrazine hydrate, and the reaction mixture was heated at reflux temperature overnight. After the mixture was cooled to room temperature, acetone (10 ml) was added and it was heated again to reflux temperature for 3 hours. The resulting precipitate was filtered, and the filtrate was evaporated under reduced pressure to obtain a residue, which was used in the next step without further purification (1.05 g, purity 44%, yield 59%).

[0384] ESI mass [m / z]: 245.1 [M+H] + Step 4: 3-Chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide

Chemical formula

[0385] To a solution of 200 mg (0.82 mmol) of 6-{5-[(1S)-1-aminoethyl]-3-methoxy-1H-1,2,4-triazol-1-yl}nicotinonitrile in dichloromethane (4.5 ml) was added 0.74 ml (1.15 mmol) of N,N-diisopropylethylamine, followed by addition of a solution of 0.15 ml (0.90 mmol) of 3-chloro-5-(trifluoromethyl)benzoyl chloride in 1.5 ml of dichloromethane. The mixture was stirred at room temperature overnight. The reaction mixture was quenched with 5% Na 2 PO 4 aqueous solution and then extracted with dichloromethane. The organic phase was washed with Na 2 SO 4It was dried, filtered, and evaporated under reduced pressure. The crude substance was purified by preparative HPLC (water / acetonitrile, 0.1% formic acid). The combined product fractions were evaporated, and then the residue was purified by silica gel chromatography to obtain the title compound (75 mg, 20%).

[0386] ESI mass [m / z]: 451.2 [M+H] + 1 See Table 1 for the 1H NMR peak list.

[0387] Synthesis of 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride Step 1: tert-Butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate

Chemical Structure

[0388] N 2 To a solution of 2.00 g (10.6 mmol) of N-(tert-butoxycarbonyl)-L-alaninamide in 40 mL of CH 2 Cl 2 was added 2.1 mL (16 mmol) of N,N-dimethylformamide dimethylacetal. The solution was heated at reflux for 2 hours, and then 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 minutes. The solvent was removed under reduced pressure, saturated aqueous NaHCO 3 was added, and the mixture was repeatedly extracted with ethyl acetate. The combined organic layers were washed with brine and dried over Na 2 SO 4 and the solvent was removed under reduced pressure. The residue was purified by reverse-phase chromatography (H 2Purified by O / acetonitrile) to obtain 3.0 g of tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate.

Number

[0389] 1 H NMR (DMSO-d 6 , 400 MHz): 9.10 (s, 1 H), 8.57 (dd, 1 H), 8.21 (s, 1 H), 8.05 (d, 1 H), 7.52 (d, 1 H), 5.63 (m, 1 H), 1.43 (d, 3 H), 1.31 (s, 9 H). ESI mass [m / z]: 259.2 [M - C 4 H 8 + H] + Step 2: 6-{5-[(1S)-1-Aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride

Chemical

[0390] 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 a 4 M HCl solution in 1,4-dioxane. The mixture was stirred at 50 °C for 4 hours and at room temperature overnight. The solvent was removed under reduced pressure to obtain 2.81 g of a residue containing 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride. This was used without further purification.

[0391] 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 [M + H - HCl] + Synthesis of 5-(Difluoromethoxy)-2-hydrazinopyrimidine

Chem.

[0392] A solution of 5-(Difluoromethoxy)-2-(methylsulfanyl)pyrimidine (500 mg, 2.60 mmol) in 2 mL of ethanol was treated with 0.52 mL (11 mmol) of hydrazine hydrate. The mixture was heated and refluxed overnight. Then, the reaction mixture was cooled to 5 °C, and a white precipitate formed. The suspension was filtered, and the precipitate was washed with ethanol. The residue was dried under reduced pressure to obtain 125 mg of 5-(Difluoromethoxy)-2-hydrazinopyrimidine.

[0393] 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] + Synthesis of 3-Chloro-5-(difluoromethyl)benzoic acid (INT-10) Step 1: 3-Chloro-5-(difluoromethyl)benzonitrile

Chem.

[0394] A solution of 3-Chloro-5-formylbenzonitrile (5.00 g, 30.1 mmol) in CH 2 Cl 2A solution of 150 mL was treated with 5.84 g (36.2 mmol) of diethylaminosulfur trifluoride (DAST) and stirred at room temperature for 2 hours. The reaction was quenched by carefully adding the saturated solution. NaHCO 3 solution and the mixture were repeatedly extracted with CH 2 Cl 2 The combined organic layers were washed with brine and dried over Na 2 SO 4 . The solvent was removed under reduced pressure to obtain 5.31 g of 3-chloro-5-(difluoromethyl)benzonitrile, which was used without further purification.

[0395] EI mass [m / z]: 187 [M] + Step 2: 3-chloro-5-(difluoromethyl)benzoic acid (INT-10)

Chemical formula

[0396] A solution of 300 mg (1.59 mmol) of 3-chloro-5-(difluoromethyl)benzonitrile in a mixture of 6.5 mL of THF and 3.5 mL of methanol was treated with 1.92 g (23.9 mmol) of 50% aqueous sodium hydroxide solution. The mixture was heated to reflux and stirred at that temperature for 45 minutes. Then, all volatile substances were removed under reduced pressure. Water was added and the pH was adjusted to pH 1 using concentrated hydrochloric acid. The mixture was repeatedly extracted with EtOAc. The combined organic layers were washed with brine and dried over Na 2 SO 4 . The solvent was removed under reduced pressure to obtain 278 mg of 3-chloro-5-(difluoromethyl)benzoic acid, which was used in the synthesis of Example II-12 without further purification.

[0397] 1 1H NMR (DMSO-d 6 , 400 MHz): 13.65 (brs, 1 H), 8.06 (s, 2 H), 7.93 (s, 1 H), 7.14 (t, J = 55 Hz, 1 H). ESI mass [m / z]: 207.1 [M+H] + Synthesis of 3-chloro-5-(difluoromethyl)benzoic acid (INT-09) Step 1: O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate

Chem.

[0398] 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 dimethylcarbamoyl chloride were successively added 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, dried over Na 2 SO 4 and filtered. The filtrate was concentrated in vacuo to a volume of about 50 mL. The concentrate was diluted with 150 mL of n-hexane, the precipitate formed was filtered off, washed with 150 mL of a 1:1 mixture of diethyl ether and n-hexane, and dried in vacuo at 60 °C (1 torr, 3 h) to give 9.3 g (86%) of O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate as colorless crystals.

[0399] 1 1H NMR (400 MHz, CDCl 3 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 Gemini2000 machine).

[0400] Step 2: S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate

Chem.

[0401] 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 minutes with a Biotage Initiator microwave. The reaction mixture was brought to room temperature and diluted with 40 ml of water. The formed precipitate was filtered off, washed with hot water (about 70 °C) and n-hexane, and dried in vacuo at 60 °C (1 torr, 3 hours) to give 2.05 g (85%) of S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate as a white powder.

[0402] 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 Gemini2000 machine).

[0403] Step 3: 3-Chloro-5-sulfanylbenzoic acid

Chemical formula

[0404] A hot (about 70 °C) solution of 68.5 g (1.71 mol) of NaOH in 300 mL of water was added to a suspension of 27.5 g (114 mmol) of S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate in 700 mL of warm (about 40 °C) methanol. The reaction mixture was stirred under reflux (20 hours). The methanol was removed in vacuo, and the aqueous solution was washed with 2 x 200 mL of diethyl ether. The aqueous layer was separated and added dropwise to a suspension of 300 g of ice in aqueous concentrated HCl (cooled in an ice bath under argon). The formed solution was filtered off, washed with 2 x 50 mL of water and 50 mL of n-hexane, and dried in vacuo at 60 °C (1 torr, 3 hours) to give 21.2 g (98%) of 3-chloro-5-sulfanylbenzoic acid as a white powder.

[0405] 1 1H NMR (400 MHz, CDCl 3 ) 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 machine).

[0406] Step 4: 3-Chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (INT-09)

Chemical formula

[0407] Under an argon atmosphere, to a solution of 11.32 g (60 mmol) of 3-chloro-5-sulfanylbenzoic acid in anhydrous DMF, 12.44 g (90 mmol) of K 2 CO 3 and 18.3 g (120 mmol) of sodium chloro(difluoro)acetate were added successively. The reaction mixture was stirred at 95 - 100 °C for 3 hours. Caution: CO 2 evolved vigorously at 90 - 95 °C! The volatile substances were removed in vacuo, 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 200 mL of 5% hydrochloric acid. The suspension was stirred at room temperature for 20 hours, 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. Vacuum drying at 60 °C (1 torr, 3 hours) gave 11 g of the crude product (purity 85% by 1H and 19F 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.

[0408] 1 1H 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 (brs, 1H) (measured on a Varian Gemini 2000 machine).

[0409] Synthesis of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]ethyl}-1H-1,2,4-triazol-1-yl)-N-cyclopropyl-N-methylnicotinamide (Example II-38) Step 1: 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]ethyl}-1H-1,2,4-triazol-1-yl)nicotinic acid

Chemical Structure

[0410] A solution of 2.00 g (6.09 mmol) of N-[(2S)-1-amino-1-oxopropan-2-yl]-3,5-bis(trifluoromethyl)benzamide and 1.21 mL (9.14 mmol) of N,N-dimethylformamide dimethylacetal in 40 mL of dichloromethane was heated to reflux. After 1 hour, the reaction mixture was concentrated under reduced pressure. To the residue were added 1.89 g (9.95 mmol) of 6-hydrazinonicotinic acid hydrochloride (1:1) and 40 mL of acetic acid. The mixture was heated at 100 °C for 1 hour. The solvent was removed under reduced pressure. Water was added to the residue, and the mixture was repeatedly extracted with EtOAc. The combined organic layers were washed with brine and dried over Na 2 SO 4 and filtered. The filtrate was concentrated under reduced pressure to obtain 3.1 g of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]ethyl}-1H-1,2,4-triazol-1-yl)nicotinic acid, which was used without further purification.

[0411] ESI mass [m / z]: 474.2 [M + H] + Step 2: 6-(5-{(1S)-1-[3,5-Bis(trifluoromethyl)benzamide]ethyl}-1H-1,2,4-triazol-1-yl)-N-cyclopropyl-N-methylnicotinamide (Example II-38)

Chemical Structure

[0412] To a solution of 250 mg (0.52 mmol) of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamide]ethyl}-1H-1,2,4-triazol-1-yl)nicotinic acid and 38 mg (0.52 mmol) of N-methylcyclopropanamine in 5 mL of acetonitrile were added 0.50 mL (2.9 mmol) of N,N-diisopropylethylamine and 0.50 mL (0.85 mmol) of a 50% T3P (cyclic propane phosphonic anhydride) solution in EtOAc. The reaction mixture was stirred at room temperature overnight. It was then concentrated, and the residue was purified by silica chromatography (cyclohexane / EtOAc) to obtain 113 mg of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamide]ethyl}-1H-1,2,4-triazol-1-yl)-N-cyclopropyl-N-methylnicotinamide.

[0413] ESI mass [m / z]: 527.2 [M+H] + 1 Refer to Table 3 for the H NMR peak list.

[0414] Synthesis of 3-chloro-N-[(1S)-1-{1-[5-(isobutyrylamino)pyridin-2-yl]-1H-1,2,4-triazol-5-yl}ethyl]-5-(trifluoromethyl)benzamide (Example II-2) Step 1: N-{(1S)-1-[1-(5-aminopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethyl)benzamide

Chemical Structure

[0415] To a solution of 1.22 g (2.76 mmol) of 3-chloro-N-{(1S)-1-[1-(5-nitropyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide in a mixture of 65 mL of ethanol and 6.4 mL of acetic acid was added 0.62 g (11 mmol) of iron powder. The mixture was heated at 80 °C for 2 h. All volatile substances were removed under reduced pressure. Water and a saturated aqueous solution of NaHCO 3 were added to the residue. The layers were separated and the aqueous layer was extracted several times with ethyl acetate. The combined organic layers were washed with brine and dried over Na 2 SO 4 and filtered, and concentrated under reduced pressure to give 1.19 g of N-{(1S)-1-[1-(5-aminopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethyl)benzamide.

[0416] ESI mass [m / z]: 411.2 [M+H] + Step 2: 3-chloro-N-[(1S)-1-{1-[5-(isobutyrylamino)pyridin-2-yl]-1H-1,2,4-triazol-5-yl}ethyl]-5-(trifluoromethyl)benzamide (Example II-2)

Chemical formula

[0417] A solution of 80 mg (0.19 mmol) of N-{(1S)-1-[1-(5-aminopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethyl)benzamide in 0.3 mL of THF was treated at 0 °C with 20 μL (0.19 mmol) of isobutyryl chloride and 30 μL (0.21 mmol) of triethylamine. The reaction mixture was stirred at room temperature overnight. All volatile substances were removed under reduced pressure, and the residue was purified by silica chromatography (cyclohexane / EtOAc) to give 43 mg of 3-chloro-N-[(1S)-1-{1-[5-(isobutyrylamino)pyridin-2-yl]-1H-1,2,4-triazol-5-yl}ethyl]-5-(trifluoromethyl)benzamide.

[0418] ESI mass [m / z]: 481.2 [M+H] + 1 See Table 3 for the H NMR peak list.

[0419] Synthesis of N-{(1S)-1-[1-(5-bromo-1,3-thiazol-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethoxy)benzamide (Example II-15)

Chemical formula

[0420] 0.50 g (1.2 mmol) of 3-chloro-N-{(1S)-1-[1-(1,3-thiazol-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethoxy)benzamide and 0.73 g (4.1 mmol) of N-bromosuccinimide were dissolved in 37 mL of DMF and stirred at room temperature overnight. Since the conversion of the starting material was incomplete, an additional 0.73 g (4.1 mmol) of N-bromosuccinimide was added and stirring was continued for 5 hours. An aqueous sodium bisulfite solution was added, and the mixture was repeatedly extracted with EtOAc. The combined organic layers were washed with water, saturated NaHCO 3It was washed with aqueous solution and brine. All volatile substances were removed under reduced pressure, and the residue was purified by silica chromatography (cyclohexane / EtOAc) to obtain 457 mg of N-{(1S)-1-[1-(5-bromo-1,3-thiazol-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethoxy)benzamide.

[0421] ESI mass [m / z]: 497.9 [M+H] + 1 Refer to Table 3 for the 1H NMR peak list.

[0422] Synthesis of 3,5-di(trifluoromethyl)-N-{1-[3-chloro-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}-benzamide (Example I-39) Step 1 tert-Butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanyl-carboximidoyl]carbamate

Chemical formula

[0423] 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-hexafluorophosphate] (HATU) were added, and the reaction mixture was stirred at a temperature of 80 °C for 2 hours. Then, water was added, and the mixture was extracted with sodium bicarbonate solution and dichloromethane. The organic phase was separated, and Na 2 SO 4It was dried, filtered, and the solvent was evaporated. The remaining solid residue was purified by silica gel chromatography with a cyclohexane / acetone gradient to obtain 1.40 g of the racemic title compound (purity: 97.0%, yield: 69.6%).

[0424] ESI mass [m / z]: 392.2 [M+H] + 1 1H-NMR peak list (400 MHz, DMSO-d6, ppm) 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) Step 2 2-[1-[3-(N-Boc-amino)-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione

Chemical Structure

[0425] A solution of 2.1 g (5.36 mmol) of tert-butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanyl-carboximidoyl]carbamate in pyridine (20 ml) was added with 1.0 g (7.45 mmol) of 6-hydrazinyl-3-pyridinecarbonitrile, and the reaction mixture was stirred at 80 °C for 2 hours. Then, an additional 250 mg of tert-butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanyl-carboximidoyl]carbamate was added, and the reaction mixture was stirred at 80 °C for an additional 1 hour. Subsequently, the solvent was evaporated in vacuo, and the crude product was purified by chromatography on silica gel with a cyclohexane / ethyl acetate gradient to obtain 1.7 g (purity: 98.5%, yield: 67.9%) of the racemic title compound.

[0426] ESI mass [m / z]: 404.3 [M-H 2 C=(CH 3 ) 2 + 1 1H-NMR peak list (400 MHz, DMSO-d 6 , ppm) δ = 10.1893 (1.2); 8.7198 (1.0); 8.7155 (1.0); 8.4412 (0.7); 8.4357 (0.6); 8.4197 (0.7); 8.4142 (0.7); 7.8856 (1.0); 7.8642 (0.9); 7.8302 (9.0); 6.1248 (0.8); 6.1071 (0.8); 3.3201 (12.8); 2.5249 (0.7); 2.5113 (13.7); 2.5070 (27.3); 2.5026 (35.5); 2.4980 (25.3); 2.4936 (12.2); 1.9890 (0.4); 1.8230 (2.2); 1.8054 (2.2); 1.4459 (16.0); 1.3977 (14.0); -0.0002 (3.0) Step 3 2-[1-[3-Amino-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione-hydrochloride​ [Chemical formula]

[0427] 1.9 g (4.14 mmol) of 2-[1-[3-(N-Boc-amino)-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione was treated with a 4N HCl dioxane solution (50 ml), and the reaction mixture was stirred at room temperature for 18 h. Subsequently, the reaction mixture was concentrated, and the racemic solid residue was used for halogen introduction (Step 4) without purification.

[0428] ESI mass [m / z]: 360.3 [M-HCl] + 1 1H-NMR peak list (400 MHz, DMSO-d 6 , ppm) δ = 8.6984 (0.6); 8.6942 (0.7); 8.3712 (0.5); 8.3656 (0.4); 8.3496 (0.5); 8.3439 (0.5); 7.8431 (2.4); 7.8409 (2.4); 7.7665 (0.6); 7.7448 (0.6); 6.1130 (0.5); 6.0953 (0.5); 3.8452 (0.6); 3.5682 (16.0); 2.5245 (0.8); 2.5109 (17.6); 2.5066 (35.5); 2.5021 (46.5); 2.4976 (33.8); 2.4932 (16.7); 1.8297 (1.6); 1.8120 (1.6); -0.0002 (2.4) Step 4 2-[1-[3-chloro-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione [Chemical formula]

[0429] To 1.14 g (3.17 mmol) of 2-[1-[3-amino-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione hydrochloride in acetonitrile (91.2 ml), 725.1 mg (5.39 mmol) of Cu(II) chloride was added, and then the reaction mixture was treated dropwise with 458.0 mg (4.44 mmol) of tert-butyl nitrite at room temperature. Then, the reaction mixture was stirred at 70 °C for 1 hour, after which it was treated with ethyl acetate and then extracted with saturated NaHCO 3 solution and water. The organic phase was separated, dried over Na 2 SO 4 , filtered, and the solvent was evaporated. The crude product was purified by chromatography on silica gel with a cyclohexane / acetone gradient to give 670 mg (purity: 100%, yield: 55.7%) of the racemic title compound.

[0430] ESI mass [m / z]: 379.1 [M+H] + Step 5 6-[5-(1-Aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-11) [Chemical formula]

[0431] To 650.0 mg (1.71 mmol) of 2-[1-[3-chloro-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (36.1 mL), 390.5 mg (4.29 mmol) of hydrazine hydrate was added, and the reaction mixture was heated under reflux. After 30 minutes, a colorless precipitate was formed. The reaction mixture was stirred and heated under reflux for an additional 2 hours, acetone (10 mL) was added, and heating was continued for an additional 30 minutes. The reaction mixture was concentrated, and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to obtain racemic 6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-11), which was used in Step 6 without purification.

[0432] ESI mass [m / z]: 249.2 [M+H] + Step 6 3,5-Di(trifluoromethyl)-N-{1-[3-chloro-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}-benzamide (Example I-39)

Chemical formula

[0433] To 125.0 mg (0.50 mmol) of 6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-11), 146.6 mg (0.55 mmol) of 3,5-bis(trifluoromethyl)-benzoic acid, 100 mg (0.77 mmol) of N,N-diisopropylethylamine (Hünig's base) in acetonitrile (6.25 mL), and 258.3 mg (0.67 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N’,N’-tetramethyluronium-hexafluoro-phosphate] (HATU) were added, and the reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure, the solid residue was treated with dichloromethane, and then saturated NaHCO 3It was extracted with an aqueous solution and water. The organic phase was separated, dried with Na 2 SO 4 , and the solvent was evaporated under reduced pressure. The remaining brown oily substance was purified by preparative HPLC with a water / acetonitrile neutral gradient to obtain 106.0 mg of the racemic title compound (purity: 100%, yield: 39.3%).

[0434] ESI mass [m / z]: 489.1 [M+H] + 1 See Table 1 for the 1H NMR peak list.

[0435] Synthesis of 3,5-di(trifluoromethyl)-N-{1-[3-bromo-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}-benzamide (Example I-48) Step 1 2-[1-[3-bromo-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione

Chemical Structure

[0436] To 250.0 mg (0.69 mmol) of 2-[1-[3-amino-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione hydrochloride in acetonitrile (16.6 ml) was added 300.0 mg (1.34 mmol) of copper(II) bromide, and then the reaction mixture was treated dropwise with 110.0 mg (1.06 mmol) of tert-butyl nitrite at room temperature. The reaction mixture was then stirred at 70 °C for 1 hour, treated with ethyl acetate, and extracted with saturated NaHCO 3 solution and water. The organic phase was separated, dried with Na 2 SO 4It was dried, filtered, and the solvent was evaporated. The crude product was chromatographed on silica gel with a cyclohexane / acetone gradient to obtain 300 mg (purity: 96.2%) of the racemic title compound.

[0437] ESI mass [m / z]: 423.3 [M+H] + Step 2 6-[5-(1-Aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-12)

Chemical formula

[0438] To 300.0 mg (0.70 mmol) of 2-[1-[3-bromo-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (10 mL), 160.0 mg (1.75 mmol) of hydrazine hydrate was added, and the reaction mixture was heated under reflux. After 30 minutes, a colorless precipitate was formed. The reaction mixture was stirred and heated under reflux for an additional 2 hours, acetone (2 mL) was added, and heating was continued for an additional 30 minutes. The reaction mixture was concentrated, and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to obtain 210 mg (purity: 88%, yield: 88.9%) of racemic 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-12), which was used in the final Step 3 without further purification.

[0439] ESI mass [m / z]: 293.0 [M+H] + Step 3 3,5-Di(trifluoromethyl)-N-{1-[3-bromo-1-(3-cyano-pyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}-benzamide (Example I-48)

Chemical formula

[0440] To 173.8 mg (0.59 mmol) of 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-12), 170.0 mg (0.63 mmol) of 3,5-bis(trifluoromethyl)-benzoic acid, 115.9 mg (0.89 mmol) of N,N-diisopropylethylamine (Hünig's base), and 299.4 mg (0.78 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium-hexafluoro-phosphate] (HATU) in acetonitrile (6.25 mL) were added, and the reaction mixture was stirred overnight at room temperature. The reaction mixture was concentrated under reduced pressure, the solid residue was treated with dichloromethane, and then extracted with saturated NaHCO 3 aqueous solution and water. The organic phase was separated, dried over Na 2 SO 4 and the solvent was evaporated under reduced pressure. The remaining brown oily substance was purified by preparative HPLC with a gradient of water / acetonitrile to give 81.0 mg (purity: 94.8%, yield: 22.5%) of the racemic title compound.

[0441] ESI mass [m / z]: 535.0 [M+H] + 1 See Table 1 for the list of H NMR peaks.

[0442] Synthesis of 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoic acid Step 1: [3-Chloro-5-(methoxycarbonyl)phenyl]boronic acid

Chemical formula

[0443] To 30 mL of acetone containing 12 g (40 mmol) of methyl 3-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate and H 2To 30 mL of a suspension, 17.3 g (80.9 mmol) of sodium periodate and 6.24 g (80.9 mmol) of ammonium acetate were added. The mixture was stirred at 25 °C for 2 hours and then filtered through celite. The filtrate was evaporated. The residue was diluted with 200 mL of ethyl acetate and washed with 100 mL of H 2 O. The organic phase was washed with brine and dried over anhydrous Na 2 SO 4 , filtered, and concentrated in vacuo. 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 under reduced pressure to give 7 g of [3-chloro-5-(methoxycarbonyl)phenyl]boronic acid as a white solid.

[0444] 1 H-NMR (400 MHz, CDCl 3 ): δ = 8.72 (s, 1H), 8.35 (s, 1H), 8.27 (s, 1H), 4.02 (s, 3H). Refer to the signal of trace CHCl 3 at 7.25 ppm. Measured using a Varian 400MR NMR machine.

[0445] Step 2: Methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate

Chemical formula

[0446] In 500 mL of DMF, 13 g (61 mmol) of [3-chloro-5-(methoxycarbonyl)phenyl]boronic acid, 43.1 g (303 mmol) of trimethyl(trifluoromethyl)silane, 33.4 g (121 mmol) of Ag 2 CO 3 , 38.6 g (182 mmol) of K 3 PO 4 , 762 mg (6.06 mmol) of CuSCN, 2.2 g (12 mmol) of 1,10-phenanthroline, 46.7 g (1.46 mol) of sulfur, and 13 g of 4 Å molecular sieve were added under N2 It was stirred at 25 °C for 16 hours. The mixture was filtered through celite. The filtrate was diluted with 1.5 L of methyl tert-butyl ether and washed with 2 x 500 mL of H 2 O. The organic phase was washed with brine, dried over anhydrous Na 2 SO 4 and filtered, and concentrated in vacuo. The crude product was purified by silica gel MPLC (petroleum ether:ethyl acetate = 1:0 to 20:1) to obtain 5.5 g of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate as a pale yellow oil.

[0447] 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). Refer to the signal of trace CHCl 3 at 7.25 ppm. Measured using a Varian 400MR NMR machine.

[0448] Step 3: 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoic acid

Chemical formula

[0449] 5.5 g (20 mmol) of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate was dissolved in a mixture of 12 mL of tetrahydrofuran and 12 mL of H 2 O. 1.63 g (40.6 mmol) of NaOH was added to the mixture, which was then stirred at 25 °C for 2 hours. 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 phase was washed with brine, dried over anhydrous Na 2 SO 4It was dried, filtered, and concentrated in vacuo. The crude product was triturated with 50 mL of petroleum ether at 25 °C for 15 minutes. The mixture was filtered, and the residue was dried under reduced pressure to obtain 3.0 g of 3-chloro-5-(trifluoromethylsulfanyl)benzoic acid as a yellow solid.

[0450] 1 H-NMR (400 MHz, CDCl 3 ): δ = 11.28 (brs, 1H), 8.29 (s, 1H), 8.20 - 8.25 (m, 1H), 7.91 (s, 1H). Refer to the signal of trace CHCl 3 at 7.25 ppm. Measured using a Varian 400MR NMR machine.

[0451] ESI mass [m / z]: 254.8 [M - H] - The measurement by LC-MS was carried out using a mobile phase of acetonitrile and 10 mM aqueous ammonium bicarbonate solution, a linear gradient from 15% acetonitrile to 90% acetonitrile, a flow rate of 0.80 ml / min; equipment: Agilent 1200 and Agilent 6120. The column used for chromatography was a 2.1*50 mm Xbridge Shield RPC18 column (5 μm particles). The detection methods were diode array (DAD) and evaporative light scattering detection (ELSD), and negative electrospray ionization.

[0452] Synthesis of 3-chloro-5-(pentafluoroethyl)benzoic acid (Intermediate INT-13)

Chemical Structure

[0453] Step 1: Methyl 3-chloro-5-(pentafluoroethyl)benzoate To methyl 3-chloro-5-iodo-benzoate (18.5 g, 62.4 mmol) in DMF (180 mL) were added potassium pentafluoropropionate (22.7 g, 112.3 mmol) and CuI (23.7 g, 124.8 mmol), and the mixture was stirred at 160 °C for 2 h and monitored by TLC. Water (200 mL) and EtOAc (300 mL) were added to the reaction mixture, and the resulting suspension was filtered, and the organic phase was separated from the filtrate. The organic phase was washed with H 2 O (2 x 50 mL) and then concentrated. The residue was purified by column chromatography (SiO 2 , petroleum ether / ethyl acetate = 1 / 0 to 100 / 1). The title compound was obtained as a red oil (10.0 g, 32.2 mmol, yield 51.6%, purity 93.0%).

[0454] 1 H-NMR (400 MHz, CDCl 3 ): δ = 8.24 (s, 1H), 8.17 (s, 1H), 7.78 (s, 1H), 3.98 (s, 3H). Measured using a Bruker 400 MHz NMR machine.

[0455] Step 2: 3-chloro-5-(pentafluoroethyl)benzoic acid Methyl 3-chloro 5-(pentafluoroethyl)benzoate (10.0 g, 34.6 mmol) was dissolved in MeOH (50 mL). LiOH (1.66 g, 69.3 mmol) in H 2 O (50 mL) was added to the above solution, and the mixture was stirred at 25 °C for 5 h and monitored by TLC. Water (100 mL) was added to the reaction mixture, and the mixture was extracted with ethyl acetate (60 mL). The separated aqueous phase was acidified with 1N HCl to pH = 5 - 6, and then the solution was extracted with ethyl acetate (3 x 50 mL). The combined organic phases were washed with brine (30 mL), dried over sodium sulfate, filtered, and concentrated. The title compound was obtained as a white solid (8.00 g, 29.1 mmol, yield 84.0%).

[0456] 11H-NMR (400 MHz, MeOD): δ = 8.24 (s, 1H), 8.14 (s, 1H), 7.88 (s, 1H). Measured using a Bruker 400 MHz NMR machine.

[0457] ESI mass [m / z]: 272.9 [M] + Synthesis of 3-(difluoromethyl)-5-(trifluoromethoxy)benzoic acid (Intermediate INT-14) Step 1: 1-Bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene

Chemical formula

[0458] To a solution of 5.00 g (18.5 mmol) of 3-bromo-5-(trifluoromethoxy)benzaldehyde in 100 ml of CHCl₃, 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. The reaction mixture was stirred at room temperature for 2 hours. After this time, the reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄, filtered, and concentrated under reduced pressure. Analysis of the crude product by NMR revealed incomplete conversion of the starting material. Therefore, the residue was redissolved in 100 ml of CHCl₃ and 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. Stirring was continued until complete conversion of the starting material was observed by analytical HPLC. The reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 2 Cl 2 100 ml of the solution, 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. The reaction mixture was stirred at room temperature for 2 hours. After this time, the reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄ and concentrated under reduced pressure. Analysis of the crude product by NMR revealed incomplete conversion of the starting material. Therefore, the residue was redissolved in 100 ml of CHCl₃ and 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. Stirring was continued until complete conversion of the starting material was observed by analytical HPLC. The reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 3 with 2 Cl 2 and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄ and concentrated under reduced pressure. Analysis of the crude product by NMR revealed incomplete conversion of the starting material. Therefore, the residue was redissolved in 100 ml of CHCl₃ and 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. Stirring was continued until complete conversion of the starting material was observed by analytical HPLC. The reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 2 SO 4 ₄ and concentrated under reduced pressure. Analysis of the crude product by NMR revealed incomplete conversion of the starting material. Therefore, the residue was redissolved in 100 ml of CHCl₃ and 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. Stirring was continued until complete conversion of the starting material was observed by analytical HPLC. The reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 2 Cl 2 100 ml and 3.0 mL (23 mmol) of diethylaminosulfur trifluoride was added. Stirring was continued until complete conversion of the starting material was observed by analytical HPLC. The reaction mixture was quenched with saturated aqueous NaHCO₃ and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 3 with 2 Cl 2 and extracted with CHCl₃. The combined organic layers were dried over Na₂SO₄. 2 SO 4It was dried, filtered, and concentrated under reduced pressure to obtain 4.87 g of a residue containing 1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene. A part of this crude substance was purified by silica chromatography (cyclohexane / EtOAc) to obtain 1.78 g of pure 1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene. This was used in the following carbonylation reaction.

[0459] 1 H-NMR (DMSO-d 6 , 400 MHz): δ = 7.92 (s, 1 H), 7.88 (s, 1 H), 7.65 (s, 1 H), 7.10 (t, J = 55 Hz, 1 H). EI mass [m / z]: 290, 292 [M] + Step 2: Methyl 3-(difluoromethyl)-5-(trifluoromethoxy)benzoate

Chemical formula

[0460] To a solution of 1.78 g (6.11 mmol) of 1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene in 45 mL of methanol were added 1.51 g (18.3 mmol) of sodium acetate and 0.15 g (0.18 mmol) of dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) acetone adduct. Then, this solution was stirred at 80 °C for 16 hours in an autoclave under a carbon monoxide (5 bar) atmosphere. After this time, complete conversion of the starting material to methyl 3-(difluoromethyl)-5-(trifluoromethoxy)benzoate was observed. The reaction mixture was used directly in the next step.

[0461] EI mass [m / z]: 270 [M] + Step 3: 3-(Difluoromethyl)-5-(trifluoromethoxy)benzoic acid

Chemical formula

[0462] To the solution from the initial step, 70 mL of THF and 5.3 mL of 45% aqueous sodium hydroxide solution were added. The mixture was heated under reflux for 45 minutes and then acidified to pH 1 - 2 using concentrated hydrochloric acid. A precipitate was formed and removed by filtration. The filtrate was evaporated to dryness. Water was added to the residue and the mixture was repeatedly extracted with diethyl ether. The combined organic layers were washed with brine and dried over Na 2 SO 4 , filtered, and concentrated under reduced pressure to obtain 1.44 g of methyl 3-(difluoromethyl)-5-(trifluoromethoxy)benzoate.

[0463] 1 H-NMR (DMSO-d 6 , 400 MHz): δ = 13.8 (brs, 1 H), 8.15 (s, 1 H), 7.98 (s, 1 H), 7.89 (s, 1 H), 7.20 (t, J = 55 Hz, 1 H). ESI mass [m / z]: 254.8 [M - H] - Synthesis of 3-(difluoromethoxy)-5-(difluoromethyl)benzoic acid (Intermediate INT-15)

Chemical Structure

[0464] Step 1: Methyl 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate

Chemical Structure

[0465] 3-(Difluoromethoxy)-5-(methoxycarbonyl)benzoic acid (known from International Publication No. WO 2012 / 019428) (7.38 g, 30 mmol) was suspended in dry toluene (30 mL). Oxalyl chloride (5.71 g, 45 mmol) was added all at once, followed by the addition of 1 drop of DMF at room temperature. The reaction mixture was stirred at room temperature for 12 hours and then at 60 - 70 °C for 2 hours. The reaction mixture was evaporated to give 7.9 g of crude methyl 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate, which was used without further purification.

[0466] Step 2: Methyl 3-(difluoromethoxy)-5-formylbenzoate

Chemical formula

[0467] 2,6-Lutidine (3.38 g, 3.68 mL, 31.5 mmol) and 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate (7.94 g, 30 mmol) from Step 1 were dissolved in anhydrous THF (100 mL), Pd / C (alpha, dry, 10%, 430 mg) was added, and the mixture was hydrogenated for 48 hours (H 2 in a balloon). The resulting precipitate was filtered off, washed with diethyl ether (200 mL), saturated NaHCO 3 aqueous solution (30 mL) was added to the filtrate, and the mixture was stirred at room temperature for 12 hours. The solution was diluted with further diethyl ether (300 mL) and water (300 mL). The organic layer was separated and washed with water (2 × 300 mL), aqueous citric acid solution (5%, 200 mL), water (300 mL), and brine (300 mL). The volatile substances were removed in vacuo to give crude methyl 3-(difluoromethoxy)-5-formylbenzoate (4.1 g, yield 59%).

[0468] 1 1H-NMR (400 MHz, CDCl 3): δ = 10.05 (d, J = 0.7 Hz, 1H), 8.41 - 8.35 (m, 1H), 8.07 - 8.00 (m, 1H), 7.86 - 7.79 (m, 1H), 6.62 (t, J = 72.4 Hz, 1H), 3.98 (d, J = 0.7 Hz, 3H). Measured using a Varian Gemini 2000 machine.

[0469] Step 3: Methyl 3-(difluoromethoxy)-5-(difluoromethyl)benzoate

Chem.

[0470] Crude methyl 3-(difluoromethoxy)-5-formylbenzoate (4 g, 17.38 mmol) was dissolved in DCM (100 mL), and the solution was cooled to -20 °C. DAST (5.60 g, 34.8 mmol) was added all at once, and the reaction mixture was stirred for 12 hours (slowly warming the temperature to room temperature). The reaction mixture was poured into a saturated aqueous solution of NaHCO 3 (200 mL), DCM (100 mL) was added, and then the organic layer was separated, washed with water (100 mL), and dried over Na 2 SO 4 . Volatiles were removed in vacuo to give 4.5 g of crude methyl 3-(difluoromethoxy)-5-(difluoromethyl)benzoate as a brown oil.

[0471] 1 1H-NMR (400 MHz, CDCl 3 ): δ = 8.04 (t, J = 1.4 Hz, 1H), 7.92 - 7.87 (m, 1H), 7.48 (s, 1H), 6.68 (t, J = 55.9 Hz, 1H), 6.59 (t, J = 72.6 Hz, 1H), 3.96 (s, 3H). Measured using a Varian Gemini 2000 machine.

[0472] Step 4: 3-(Difluoromethoxy)-5-(difluoromethyl)benzoic acid

Chem.

[0473] A solution of LiOH (1.43 g, 34 mmol) in water (10 mL) was added to a solution of crude methyl 3-(difluoromethoxy)-5-(difluoromethyl)benzoate (4.3 g, 17 mmol) from Step 3 in a mixture of THF (35 mL) and MeOH (35 mL). The reaction mixture was stirred at room temperature for 2 hours. Volatiles were removed in vacuo, water (100 mL) was added, and the resulting mixture was extracted with diethyl ether (100 mL). The separated aqueous layer was added dropwise to dilute HCl (5%, 100 mL). The precipitate was filtered off, washed with water, dried at 100 °C for 2 hours, and finally sublimed at 105 °C (0.1 torr) to give the title compound (3.2 g, 79% yield).

[0474] 1 H-NMR (DMSO-d 6 , 400 MHz): δ = 13.62 (s, 1H), 7.99 (t, J = 1.3 Hz, 1H), 7.82 (s, 1H), 7.70 - 7.62 (m, 1H), 7.42 (t, J = 73.3 Hz, 1H), 7.15 (t, J = 55.4 Hz, 1H). Measured using a Varian Gemini2000 machine.

[0475] Analysis data of the compound Determination of [M + H] + or M - by LC-MS under acidic chromatographic conditions was carried out using 1 ml of formic acid per liter of acetonitrile and 0.9 ml of formic acid per liter of Millipore water as the eluent. A Zorbax Eclipse Plus C18 50 mm * 2.1 mm column was used. The temperature of the column oven was 55 °C.

[0476] Equipment: LC-MS3: Waters UPLC with SQD2 mass spectrometer and SampleManager autosampler. Linear gradient, 0.0 - 1.70 minutes, 10% acetonitrile - 95% acetonitrile, isocratic at 95% acetonitrile from 1.70 - 2.40 minutes, flow rate 0.85 ml / min.

[0477] LC-MS6 and LC-MS7: Agilent 1290 LC, Agilent MSD, HTS PAL autosampler. Linear gradient, 0.0 - 1.80 minutes, 10% acetonitrile - 95% acetonitrile, isocratic at 95% acetonitrile from 1.80 - 2.50 minutes, flow rate 1.0 ml / min.

[0478] Determination of [M+H] by LC-MS under neutral chromatography conditions + was performed using acetonitrile and Millipore water containing 79 mg / l ammonium carbonate as the eluent.

[0479] Determination of [M+H] by LC-MS under neutral chromatography conditions + was performed using acetonitrile and Millipore water containing 79 mg / l ammonium carbonate as the eluent.

[0480] Equipment: LC-MS4: Waters IClass Acquity with QDA mass spectrometer and FTN autosampler (column Waters Acquity 1.7μm 50mm*2.1mm, oven temperature 45°C). Linear gradient, 0.0 - 2.10 minutes, 10% acetonitrile - 95% acetonitrile, isocratic at 95% acetonitrile from 2.10 - 3.00 minutes, flow rate 0.7 ml / min.

[0481] LC-MS5: Agilent 1100 LC system equipped with an MSD mass spectrometer and an HTS PAL autosampler (column: Zorbax XDB C18 1.8 μm 50 mm * 4.6 mm, oven temperature 55 °C). Linear gradient, 0.0 - 4.25 minutes, 10% acetonitrile - 95% acetonitrile, 4.25 - 5.80 minutes isocratic 95% acetonitrile, flow rate 2.0 ml / min.

[0482] 1 The determination of 1H NMR data was performed using a Bruker Avance III 400 MHz equipped with a 1.7 mm TCI cryoprobe, a Bruker Avance III 600 MHz equipped with a 5 mm multinuclear cryoprobe, or a Bruker Avance NEO 600 MHz equipped with a 5 mm TCI cryoprobe, with tetramethylsilane as the reference (0.0), and the solvent CD 3 CN, CDCl 3 or D 6 -DMSO.

[0483] The NMR data of the selected examples are listed either in the conventional form (δ value, multiplicity splitting, number of hydrogen atoms) or as an NMR peak list.

[0484] NMR peak list method of the selected examples 1 1H NMR data are 1 described in the form of a 1H NMR peak list. For each signal peak, first the δ value (ppm) is listed, and then the signal intensity is listed in parentheses. The pairs of δ value - signal intensity numbers for different signal peaks are listed separated from each other by a semicolon.

[0485] Thus, the peak list of an example takes the following form.

[0486] δ 1 (intensity 1 ); δ 2 (intensity 2 );........; δ i (intensity i);......;δ n (Strength n ) The intensity of sharp signals correlates with the height (cm) of the signals in the printed example of the NMR spectrum and indicates the true ratio of signal intensities. In the case of broad signals, the center and relative intensities of several peaks or signals can be indicated in comparison with the strongest signal in the spectrum.

[0487] 1 For calibration of the chemical shift of the 1H NMR spectrum, especially for spectra measured in DMSO, the chemical shift of tetramethylsilane and / or the solvent is used. Thus, the tetramethylsilane peak may or may not be present in the NMR peak list.

[0488] 1 The list of 1H NMR peaks is similar to a conventional 1 1H NMR printout and thus usually includes all the peaks enumerated in conventional NMR interpretation.

[0489] Furthermore, similar to a conventional 1 1H NMR printout, they may show solvent signals, signals of stereoisomers of the target compound provided by the present invention as well, and / or peaks of impurities.

[0490] In the report of compound signals within the delta range of the solvent and / or water, the 1 list of 1H NMR peaks of the present inventors shows standard solvent peaks, for example, the peak of DMSO in DMSO-d 6 6 and the peak of water, which usually have relatively high intensities on average.

[0491] The peaks of stereoisomers of the target compound and / or the peaks of impurities usually have relatively lower intensities on average than the peaks of the target compound (for example, having a purity of more than 90%).

[0492] Such stereoisomers and / or impurities may be typical of a particular preparation process. Thus, their peaks can serve to identify the reproducibility of the preparation process of the inventors with reference to a "by-product fingerprint".

[0493] One of ordinary skill in the art, who calculates the peaks of the target compound (accompanied by not only MestreC and ACD simulations but also empirically evaluated expected values) by known methods, can isolate the peaks of the target compound, if necessary, using an additional intensity filter, if appropriate. This isolation would be similar to the peak picking that is appropriate in conventional 1 1H NMR interpretation.

[0494] 1 Further details of the 1H NMR peak list can be found in Research Disclosure Database Number 564025.

[0495] The compounds according to the invention described in Table 1 below are preferred compounds of formula (I) according to the invention obtained according to the above preparation examples or similarly. [Chemical formula] [Table 1] TIFF0007691973000074.tif232157TIFF0007691973000075.tif221156TIFF0007691973000076.tif228158TIFF0007691973000077.tif221155TIFF0007691973000078.tif237157TIFF0007691973000079.tif224158TIFF0007691973000080.tif236157TIFF0007691973000081.tif236158TIFF0007691973000082.tif238157TIFF0007691973000083.tif221156TIFF0007691973000084.tif236157TIFF0007691973000085.tif239156TIFF0007691973000086.tif238157TIFF0007691973000087.tif238157TIFF0007691973000088.tif212155TIFF0007691973000089.tif218155TIFF0007691973000090.tif236156TIFF0007691973000091.tif221156TIFF0007691973000092.tif191156

Table 2

[0496] Furthermore, the present invention provides the following compounds.

Table 3

[0497] Biological Example Rhipicephalus (Boophilus) microplus - Injection Test (BOOPMI Injection) Solvent: Dimethyl Sulfoxide To produce a suitable preparation of the active compound, 10 mg of the active compound is dissolved in 0.5 mL of the solvent, and the concentrate is diluted with the solvent to the desired concentration.

[0498] 1 μL of the compound solution is injected into the abdomen of 5 adult engorged female ticks (Rhipicephalus (Boophilus) microplus). The ticks are transferred to a replica plate and incubated in an artificial climate chamber.

[0499] After 7 days, oviposition of fertile eggs is monitored. Eggs that do not appear fertile are stored in the artificial climate chamber until they hatch, which takes about 42 days. 100% effectiveness means that all eggs are not fertilized, and 0% means that all eggs are fertilized.

[0500] In this test, for example, the following compounds from the preparation examples showed 100% good activity at an application rate of 20 μg / tick. I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-30, I-31, I-32, I-33, I-34, I-35, I-37, I-38, I-39, I-40, II-1, II-2, II-3, II-4, II-5, II-7, II-8, II-9, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-18, II-19, II-20, II-21, II-22, II-23, II-24, II-25, II-26, II-27, II-28, II-29, II-30, II-31, II-32, II-33, II-34, II-36, II-37, II-38, II-39, II-40, II-41, II-43, II-44, II-46, II-47, II-48, II-49, II-50, II-51, II-52, II-53, II-54, II-55, II-56, II-57, II-59, II-60, II-61, II-62, II-63, II-64, II-65, II-66, II-67, II-68, II-69, II-70, II-71, II-72, II-73, II-74, II-75.

[0501] In this test, for example, the following compounds from the preparation examples showed 0% good activity at an application rate of 20 μg / tick. II-42, II-58.

[0502] In this test, for example, the following compounds from the preparation examples showed 100% good activity at an application rate of 4 μg / tick. I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-13, I-14, I-15, I-16, I-17, I-19, I-21, I-24, I-25, I-26, I-27, I-28, I-30, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-61, I-62, II-1, II-2, II-3, II-5, II-7, II-8, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-18, II-19, II-20, II-21, II-22, II-23, II-25, II-26, II-27, II-28, II-29, II-30, II-31, II-33, II-34, II-36, II-37, II-38, II-39, II-40, II-41, II-43, II-44, II-46, II-47, II-48, II-49, II-50, II-51, II-52, II-53, II-54, II-55, II-57, II-59, II-60, II-61, II-62, II-63, II-64, II-65, II-66, II-67, II-69, II-70, II-71, II-72, II-73, II-74, II-75, II-79, II-81, II-82, II-83, II-91, II-92, II-93, II-94, II-96, II-97, II-98, II-99, II-100, II-101, II-102, II-104, II-105, II-106, II-107, II-109, II-111, II-112, II-113, II-116, II-117.

[0503] In this test, for example, the following compounds from the preparation examples showed 80% good activity at an application rate of 4 μg / tick. I-22, I-23, I-59, II-24, II-32, II-42, II-56, II-68, II-77, II-80, II-89, II-95, II-108.

[0504] Cattle tick (Rhipicephalus (Boophilus) microplus) - in vitro contact test with cattle tick larvae (Parkhurst strain resistant to synthetic pyrethroids) (BOOPMI contact) Dissolve 9 mg of the compound in 1 mL of acetone and dilute with acetone to the desired concentration. Fill 250 μL of the test solution into a 25 mL glass test tube and distribute it evenly on the inner wall by rotating and tilting on a shaker (2 hours at 30 rpm). With a compound concentration of 900 ppm, an inner surface of 44.7 cm 2 and uniform distribution, a dose of 5 μg / cm 2 was achieved.

[0505] After the solvent has evaporated, fill each test tube with 20 - 50 cattle tick larvae (Rhipicephalus microplus), close with a perforated lid, and incubate in a horizontal position in an incubator at a relative humidity of 85% and 27 °C. After 48 hours, determine the efficacy. Gently tap the larvae onto the bottom of the tube and record the negative geotactic behavior. Larvae that climb up to the top of the vial in a manner comparable to untreated control larvae are marked as surviving, larvae that do not climb as well as untreated control larvae but move non - cooperatively or only twitch their legs are marked as moribund, and larvae that remain at the bottom of the tube and do not move at all are counted as dead.

[0506] The compound shows good efficacy against cattle ticks when at least 80% efficacy is monitored at a compound concentration of 5 μg / cm 2 . 100% efficacy means that all larvae are dead or moribund, and 0% means that none of the larvae are dead or moribund.

[0507] In this test, for example, the following compounds from the preparation examples are at 5 μg / cm 2showed 100% good activity at an application rate of (=500 g / ha). I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-19, I-21, I-24, I-...

Claims

1. A compound of formula (I), 【Chemical Formula 1】 wherein, R １ is hydrogen, R ２ is 3-chloro-5-(difluoromethyl)phenyl, 3-chloro-5-(pentafluoroethyl)phenyl, 3-chloro-5-(trifluoromethoxy)phenyl, 3-chloro-5-(trifluoromethylthio)phenyl, 3-chloro-5-(difluoromethylthio)phenyl, 3-chloro-5-(difluoromethoxy)phenyl, 3-bromo-5-(trifluoromethoxy)phenyl, 3-bromo-5-chlorophenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3-cyano-5-(trifluoromethyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 5-bromopyridin-3-yl, 3-fluoro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 3-(difluoromethyl)-5-(trifluoromethoxy)phenyl, 3-(difluoromethoxy)-5-(difluoromethyl)phenyl, 6-bromopyridin-2-yl, 5-(trifluoromethyl)pyridin-3-yl, 6-(trifluoromethyl)pyridin-2-yl, 2-chloro-6-(trifluoromethyl)pyridin-4-yl or 4-bromo-6-(trifluoromethyl)pyridin-2-yl, R ３ is C １ to C ３ alkyl, and R ４ is pyridine, pyrimidine or pyrazine, where pyridine, pyrimidine or pyrazine is substituted with CN, R ５ is a compound of formula (I) which is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy or halogen.

2. wherein, R １ is hydrogen, R ２ is 3-chloro-5-(difluoromethyl)phenyl, 3-chloro-5-(pentafluoroethyl)phenyl, 3-chloro-5-(trifluoromethoxy)phenyl, 3-chloro-5-(trifluoromethylthio)phenyl, 3-chloro-5-(difluoromethylthio)phenyl, 3-chloro-5-(difluoromethoxy)phenyl, 3-bromo-5-(trifluoromethoxy)phenyl, 3-bromo-5-chlorophenyl, 3,5-dichlorophenyl, 3,5-dibromophenyl, 3-cyano-5-(trifluoromethyl)phenyl, 3,5-bis(difluoromethoxy)phenyl, 5-bromopyridin-3-yl, 3-fluoro-5-cyanophenyl, 3-bromo-5-cyanophenyl, 3-(difluoromethyl)-5-(trifluoromethoxy)phenyl, 3-(difluoromethoxy)-5-(difluoromethyl)phenyl, 6-bromopyridin-2-yl, 5-(trifluoromethyl)pyridin-3-yl, 6-(trifluoromethyl)pyridin-2-yl, 2-chloro-6-(trifluoromethyl)pyridin-4-yl or 4-bromo-6-(trifluoromethyl)pyridin-2-yl, R ３ is methyl, R ４ is 5-cyanopyridin-2-yl, R ５ is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy, chlorine or bromine, the compound according to claim 1.

3. A compound of formula (e), 【Chemical 2】 [wherein the structural elements R ３ , R ４ and R ５ have the meanings described in claim 1 or claim 2] or its hydrochloride salt.

4. 6-[5-[(1S)-1-aminoethyl]-3-ethyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-isopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-methoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-ethoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-isopropoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-[(1S)-1-aminoethyl]-3-tert-butyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, 6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile or 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile, the compound according to Claim 3 or its hydrochloride salt.

5. A compound 【Chemical Formula 3】 or [Chemical Formula 4]

6. Compounds 3-chloro-5-(pentafluoroethyl)benzoic acid, 3-(trifluoromethoxy)-5-(difluoromethyl)benzoic acid, and 3-(difluoromethoxy)-5-(difluoromethyl)benzoic acid and their salts.

7. A formulation comprising at least one compound of formula (I) according to any one of Claims 1 to 2.

8. The formulation according to Claim 7, further comprising at least one bulking agent and / or at least one surfactant.

9. The formulation according to Claim 7 or 8, characterized in that the compound of formula (I) is present in a mixture with at least one further active compound. **Claim 10**: A method for controlling pests, characterized in that the compound of formula (I) according to any one of claims 1 to 2 or the formulation according to any one of claims 7 to 9 enables action on pests and / or their habitats, while methods for treating the body of a human or animal by surgery or therapy and diagnostic methods performed on the body of a human or animal are excluded. **Claim 11** The method according to claim 10, wherein the pest is an animal pest, including insects, arachnids or nematodes, or the pest is an insect, arachnid or nematode, while methods for treating the body of the human or animal by surgery or therapy and diagnostic methods performed on the body of the human or animal are excluded. **Claim 12** Use of a compound of formula (I) according to any one of claims 1 to 2 or a formulation according to any one of claims 7 to 9 for controlling animal pests, while use of methods for treating the body of the human or animal by surgery or therapy and diagnostic methods performed on the body of the human or animal is excluded. **Claim 13** The use according to claim 12, wherein the animal pest includes insects, arachnids or nematodes, or the animal pest is an insect, arachnid or nematode, while use of methods for treating the body of the human or animal by surgery or therapy and diagnostic methods performed on the body of the human or animal is excluded. **Claim 14** Use according to claim 12 or 13 in crop protection, while use of methods for treating the body of the human or animal by surgery or therapy and diagnostic methods performed on the body of the human or animal is excluded. **Claim 15** Use according to claim 12 or 13 in the field of animal health, while use of methods for treating the body of the human or animal by surgery or therapy and diagnostic methods performed on the body of the human or animal is excluded. A method for protecting seeds or germinating plants from pests, comprising the method step of contacting said seeds with a compound of formula (I) according to any one of claims 1 to 2 or a formulation according to any one of claims 7 to 9, while excluding methods of treating the human or animal body by surgery or therapy and diagnostic methods performed on the human or animal body, a method for protecting seeds or germinating plants from pests.

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