RU2824488C2 - Novel heteroaryltriazole compounds as pesticides - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to novel heteroaryltriazole compounds of general formula (I), in which R¹ is hydrogen; R² is phenyl or pyridine, where phenyl or pyridine is optionally substituted with one or two substituents, provided that the substituent(s) is (are) on any of the carbon atoms adjacent to the carbon atom bonded to the C=O group, each independently selected from the group consisting of fluorine, chlorine, bromine, -CN, methyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, methoxy, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, difluoroethylthio and trifluoroethylthio; R³ is C₁-C₃ alkyl; R⁴ is pyridine or pyrimidine, where pyridine or pyrimidine is substituted with CN; R⁵ is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy or halogen. Invention also relates to intermediate compounds of formula (e), individual compounds

,

a composition for controlling undesirable animal pests, a pest control method, use of a compound of formula (I) or a composition based thereon for controlling animal pests, a method of protecting seeds or germinating plants from pests.

EFFECT: creation of new compounds for pest control of animals, for protection of plants and for control of ectoparasites in animals.

15 cl, 3 tbl, 197 ex

Description

The present invention relates to novel heteroaryltriazole compounds, to compositions and formulations containing such compounds, and to their use for controlling animal pests, including arthropods and insects, for plant protection, and to their use for controlling ectoparasites in animals.

Certain heteroaryltriazole and heteroaryltetrazole compounds are described for use in the control of ectoparasites in animals in WO 2017/192385 and for use in the control of animal pests, including arthropods and insects, in the field of plant protection in WO 2019/170626 and WO 2019/215198. In addition, patent applications WO 2019/197468, WO 2019/201835, WO 2019/202077 and WO 2019/206799 disclose certain heteroaryltriazole compounds for use in the control of ectoparasites in animals and for 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 describe azolamide compounds, all of which can be used as insecticides.

Modern plant protection products must meet many requirements, for example in terms of their effectiveness, duration and breadth of action and possible application. Questions of toxicity, compatibility with other active compounds or formulation auxiliaries, as well as the cost of synthesizing the active substances play a role. Resistance may also occur. For all these reasons, the search for new plant protection products cannot be considered complete, and there is still a need for new compounds that, in contrast to known compounds, have improved properties with respect to individual aspects.

The object of the present invention was to provide compounds that extend the spectrum of pesticides in various aspects.

Therefore, the present invention relates to compounds of formula (I)

in which (Implementation option 1-1):

R ¹ represents hydrogen;

R ² is phenyl or pyridine, wherein the phenyl or pyridine is optionally substituted with one or two substituents, provided that the substituent(s) is(are) not on any of the carbon atoms adjacent to the carbon atom bonded to the C=O group, each independently selected from the group consisting of fluorine, chlorine, bromine, -CN, -NO ₂ , -SF ₅ , methyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, methoxy, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, difluoroethylthio and trifluoroethylthio;

R ³ is C ₁ -C ₃ alkyl;

R ⁴ is pyridine, pyrimidine or pyrazine, wherein pyridine, pyrimidine or pyrazine is substituted with CN.

R ⁵ is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy or halogen.

The compounds of formula (I) likewise embrace any diastereomers or enantiomers and E/Z isomers that exist, as well as salts and N-oxides of the compounds of formula (I), and their use in the control of animal pests.

Preferred definitions of radicals for the formulas given above and below are given below.

Preferred (Embodiment 2-1) are compounds of formula (I), in which

R ¹ represents 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.

Preferred (Embodiment 2-2) are also compounds of formula (I), in which

R ¹ represents 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, 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.

According to another preferred embodiment, the present invention relates to compounds of formula (I'), in which R ³ is C ₁ -C ₃ alkyl, particularly preferably methyl, and

in which the structural elements R ¹ , R ² , R ⁴ and R ⁵ have the meanings given in embodiment (1-1) or in embodiment (2-1) or in embodiment (2-2).

According to another preferred embodiment, the present invention relates to compounds of formula (I''), in which R ³ is C ₁ -C ₃ alkyl, particularly preferably methyl, and

in which the structural elements R ¹ , R ² , R ⁴ and R ⁵ have the meanings given in embodiment (1-1) or in embodiment (2-1) or in embodiment (2-2).

According to another aspect, the present invention encompasses intermediates that can be used to prepare compounds of general formula (I), see above.

In particular, the present invention covers intermediate compounds of the general formula (e):

in which the structural elements R ³ , R ⁴ and R ⁵ have the meanings given in embodiment (1-1) or in embodiment (2-1) or in embodiment (2-2), including

free amine INT-1: 6-[5-[(1S)-1-aminoethyl]-3-ethyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile hydrochloride;

INT-2: 6-[5-[(1S)-1-aminoethyl]-3-isopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile;

free amine INT-3: 6-[5-[(1S)-1-aminoethyl]-3-cyclopropyl-1,2,4-triazol-1-yl]pyridine-3-carbonitrile hydrochloride;

INT-4: 6-[5-(1-aminoethyl)-3-(difluoromethyl)-1,2,4-triazol-1-yl]pyridine-3-carbonitrile;

INT-5: 6-[5-[(1S)-1-aminoethyl]-3-methoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile;

INT-6: 6-[5-[(1S)-1-aminoethyl]-3-ethoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile;

INT-7: 6-[5-[(1S)-1-aminoethyl]-3-isopropoxy-1,2,4-triazol-1-yl]pyridine-3-carbonitrile;

INT-8: 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 hydrochlorides of free amines.

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.

Depending on the nature of the substituents, the compounds of formula (I) may be in the form of stereoisomers, i.e. in the form of geometric and/or optically active isomers or corresponding mixtures of isomers in various compositions. The present invention encompasses both pure stereoisomers and any desired mixtures of these isomers, although, as a rule, only compounds of formula (I) are discussed herein.

However, in accordance with the invention, preference is given to the use of optically active stereoisomeric forms of the compounds of formula (I) and their salts.

Thus, the invention relates to both pure enantiomers and diastereomers and to mixtures thereof for controlling animal pests, including arthropods and especially insects.

If desired, the compounds of formula (I) may be present in different polymorphic forms or as a mixture of different polymorphic forms. Both pure polymorphs and mixtures of polymorphs are provided by the invention and may be used in accordance with the invention.

Definitions

It will be apparent to one skilled in the art that unless otherwise indicated, the singular form "a" or "an" as disclosed in this application encompasses, as appropriate, "one (1)", "one (1) or more", or "at least one (1)".

For all structures described in this application, both in cyclic systems and in groups, neither -O-O- nor -O-S- can be present as neighboring atoms.

Structures with a variable number of possible carbon atoms (C atoms) may be referred to in this application as Lower Limit C-Upper Limit C structures (Lower Limit C-Upper Limit C structures). For example, an alkyl group may consist of 3 to 10 carbon atoms, and then corresponds to C ₃ -C ₁₀ -alkyl. Ring structures of carbon atoms and heteroatoms may be referred to as "lower limit C-upper limit C" structures. An example of a 6-membered ring structure is toluene (a 6-membered ring structure substituted with a methyl group).

If a general term for a substituent, such as Cng-Cng-alkyl, is at the end of a complex substituent, such as Cng-Cng-cycloalkyl-Cng-Cng-alkyl, then the constituent at the beginning of the complex substituent, such as Cng-Cng-cycloalkyl, may be mono- or polysubstituted by identical or different, independently of each other, last substituents, such as Cng-Car-alkyl. All general terms used in this application for chemical groups, cyclic systems and cyclic groups may be expressed more specifically by adding "Cng-Cng" or "ng-cng-membered".

Unless otherwise specified, the definition of general terms also applies to these general terms in complex substituents. For example, the definition of Cng-Cng-alkyl also applies to Cng-Cng-alkyl as part of a complex substituent, e.g., Cng-Cng-cycloalkyl-Cng-Cng-alkyl.

It will be obvious to one skilled in the art that the examples given in this application should not be considered as limiting, but merely as describing in detail some specific embodiments of the present invention.

In defining the symbols given in the above formulas, general terms are used, which, as a rule, represent the following substituents:

Halogen comprises the elements of main group 7, preferably fluorine, chlorine, bromine and iodine, more preferably fluorine, chlorine and bromine, and still more preferably fluorine and chlorine.

Examples of heteroatom are N, O, S, P, B, Si. Preferably, the term heteroatom includes N, S and O.

According to the present invention, the term "alkyl" - alone or as a constituent chemical group - means a branched or unbranched hydrocarbon, preferably containing from 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-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. More preferred is alkyl containing from 1 to 4 carbon atoms, such as, inter alia, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. According to the present invention, alkyl may be substituted with one or more, identical or different substituents.

According to the present invention, the term "alkenyl" - alone or as a constituent chemical group, means a branched or unbranched hydrocarbon, preferably containing from 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, 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, 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. More preferred is alkenyl containing 2 to 4 carbon atoms, such as, inter alia, 2-propenyl, 2-butenyl or 1-methyl-2-propenyl. According to the present invention, alkenyl may be substituted with one or more, identical or different substituents.

According to the present invention, the term "alkynyl" - alone or as a constituent chemical group - means a branched or unbranched hydrocarbon, preferably containing from 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. More preferred is alkynyl containing from 2 to 4 carbon atoms, such as, inter alia, ethynyl, 2-propynyl or 2-butynyl-2-propenyl. According to the present invention, alkynyl can be substituted with one or more, identical or different substituents.

According to the present invention, the term "cycloalkyl" - alone or as a constituent chemical group - represents a mono-, bi- or tricyclic hydrocarbon, preferably containing from 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2.2.1]heptyl, bicyclo[2.2.2]octyl or adamantyl. More preferred is a cycloalkyl containing 3, 4, 5, 6 or 7 carbon atoms, such as, inter alia, cyclopropyl or cyclobutyl. According to the present invention, cycloalkyl may be substituted by one or more, identical or different substituents.

According to the present invention, the term "alkylcycloalkyl" represents a mono-, bi- or tricyclic alkylcycloalkyl, preferably containing from 4 to 10 or from 4 to 7 carbon atoms, such as methylcyclopropyl, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. More preferred is an alkylcycloalkyl containing 4, 5 or 7 carbon atoms, such as, inter alia, ethylcyclopropyl or 4-methylcyclohexyl. According to the present invention, alkylcycloalkyl may be substituted by one or more, identical or different substituents.

According to the present invention, the term "cycloalkylalkyl" represents a mono-, bi- or tricyclic cycloalkylalkyl, preferably containing from 4 to 10 or from 4 to 7 carbon atoms, such as cyclopropyl methyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. More preferred is a cycloalkylalkyl containing 4, 5 or 7 carbon atoms, such as, inter alia, cyclopropylmethyl or cyclobutylmethyl. According to the present invention, cycloalkylalkyl may be substituted by one or more, identical or different substituents.

According to the present invention, the term "hydroxyalkyl" represents a straight-chain or branched alcohol, preferably containing from 1 to 6 carbon atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. More preferred is a hydroxyalkyl group containing from 1 to 4 carbon atoms. The hydroxyalkyl groups according to the present invention may be substituted by one or more, identical or different substituents.

According to the present invention, the term "alkoxy" represents a straight or branched O-alkyl, preferably containing from 1 to 6 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy. More preferred is an alkoxy group containing from 1 to 4 carbon atoms. The alkoxy groups according to the present invention may be substituted by one or more, identical or different substituents.

According to the present invention, the term "alkylthio" or "alkylsulfanyl" represents a straight or branched S-alkyl, preferably containing from 1 to 6 carbon atoms, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio and tert-butylthio. More preferred is an alkylsulfanyl group containing from 1 to 4 carbon atoms. The alkylsulfanyl groups according to the present invention may be substituted by one or more, identical or different substituents.

According to the present invention, the term "alkylsulfinyl" represents a straight-chain or branched alkylsulfinyl group, preferably having 1 to 6 carbon atoms, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl and tert-butylsulfinyl. More preferred are alkylsulfinyl groups having 1 to 4 carbon atoms. The alkylsulfinyl groups according to the present invention may be substituted with one or more, identical or different, substituents.

According to the present invention, the term "alkyl sulfonyl" represents a straight-chain or branched alkyl sulfonyl group, preferably having 1 to 6 carbon atoms, such as methyl sulfonyl, ethyl sulfonyl, n-propyl sulfonyl, isopropyl sulfonyl, n-butyl sulfonyl, isobutyl sulfonyl, sec-butyl sulfonyl and tert-butyl sulfonyl. More preferred are alkyl sulfonyl groups having 1 to 4 carbon atoms. The alkyl sulfonyl groups according to the present invention may be substituted with one or more, identical or different, substituents.

According to the present invention, "cycloalkylthio" or "cycloalkylsulfanyl" is -S-cycloalkyl, preferably having from 3 to 6 carbon atoms, for example, cyclopropylthio, cyclobutylthio, cyclonylthio, cyclohexylthio. Also preferred are cycloalkylthio groups having from 3 to 5 carbon atoms. The cycloalkylthio groups according to the present invention may be substituted by one or more identical or different radicals.

According to the invention, "cycloalkylsulfinyl" is -S(O)-cycloalkyl, preferably having from 3 to 6 carbon atoms, for example, cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl,

cyclohexylsulfinyl. Preference is also given to cycloalkylsulfinyl groups having from 3 to 5 carbon atoms. The cycloalkylsulfinyl groups of the invention may be substituted by one or more identical or different radicals and may include both enantiomers.

According to the invention, "cycloalkylsulfonyl" is -SO ₂ -cycloalkyl, preferably having from 3 to 6 carbon atoms, for example, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl,

cyclohexylsulfonyl. Preference is also given to cycloalkylsulfonyl groups having from 3 to 5 carbon atoms. The cycloalkylsulfonyl groups according to the invention may be substituted by one or more identical or different radicals.

According to the invention, "phenylthio" or "phenylsulfanyl" is -S-phenyl, for example phenylthio. The phenylthio groups according to the invention can be substituted by one or more identical or different radicals.

According to the invention, "phenylsulfinyl" is -S(O)-phenyl, for example phenylsulfinyl. The phenylsulfinyl groups of the invention may be substituted by one or more identical or different radicals and include both enantiomers.

According to the invention, "phenylsulfonyl" is -SO ₂ -phenyl, for example phenylsulfonyl. The phenylsulfonyl groups of the invention may be substituted by one or more identical or different radicals.

According to the present invention, the term "alkylcarbonyl" represents a straight-chain or branched alkyl-C(=O), preferably containing 2 to 7 carbon atoms, such as methyl carbonyl, ethylcarbonyl, n-propylcarbonyl, isopropylcarbonyl, sec-butylcarbonyl and tert-butylcarbonyl. More preferred is alkylcarbonyl containing 1 to 4 carbon atoms. According to the present invention, alkylcarbonyl may be substituted by one or more, identical or different substituents.

According to the present invention, the term "alkoxycarbonyl" by itself or as a constituent chemical group is a straight or branched alkoxycarbonyl, preferably containing from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in the alkyl part, such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, sec-butoxycarbonyl and tert-butoxycarbonyl. According to the present invention, the alkoxycarbonyl group may be substituted by one or more, identical or different, substituents.

According to the present invention, the term "alkylaminocarbonyl" represents a straight-chain or branched alkylaminocarbonyl, preferably containing from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in the alkyl part, such as methylaminocarbonyl, ethyl aminocarbonyl, n-propylaminocarbonyl, isopropylaminocarbonyl, sec-butylaminocarbonyl and tert-butylaminocarbonyl. According to the present invention, the alkylaminocarbonyl group may be substituted by one or more, identical or different substituents.

According to the present invention, the term "N,N-dialkylaminocarbonyl" represents a straight-chain or branched N,N-dialkylaminocarbonyl, preferably containing from 1 to 6 carbon atoms or from 1 to 4 carbon atoms in the alkyl part, such as N,N-dimethylaminocarbonyl, N.N-diethylaminocarbonyl, N,N-di(n-propylamino)-carbonyl, N,N-di-(isopropylamino)-carbonyl and N,N-di-(sec-butylamino)-carbonyl. According to the present invention, the N,N-dialkylaminocarbonyl group may be substituted with one or more, identical or different substituents.

According to the present invention, the term "aryl" denotes a mono-, bi- or polycyclic aromatic system, preferably containing from 6 to 14, most preferably from 6 to 10 ring carbon atoms, such as phenyl, naphthyl, anthryl, phenanthrenyl, preferably phenyl. In addition, aryl embraces polycyclic systems such as tetrahydronaphthyl, indenyl, indanyl, fluorenyl, biphenyl, wherein the point of attachment is the aromatic system. According to the present invention, the aryl group can be substituted by one or more, identical or different substituents.

Examples of substituted aryls are arylalkyls which may similarly be substituted by one or more, identical or different, substituents on the C ₁ -C ₄ alkyl and/or C ₆ -C ₁₄ aryl moiety. Examples of such arylalkyls are, inter alia, benzyl and phenyl-1-ethyl.

According to the present invention, the term "heterocycle", "heterocyclic ring" or "heterocyclic ring system" represents a carbocyclic ring system with at least one ring in which at least one carbon atom is replaced by a heteroatom, preferably a heteroatom from the group N, O, S, P, B, Si, Se, and which is saturated, unsaturated or heteroaromatic, and may be unsubstituted or substituted, wherein the point of attachment is located at a ring atom. Unless otherwise specified, the heterocyclic ring preferably contains from 3 to 9 ring atoms, most preferably from 3 to 6 ring atoms, and one or more, preferably from 1 to 4, most preferably 1, 2 or 3 heteroatoms in the heterocyclic ring, preferably from the group N, O, and S, wherein, however, the two oxygen atoms should not be in immediate proximity. The heterocyclic ring generally contains no more than 4 nitrogen atoms and/or no more than 2 oxygen atoms and/or no more than 2 sulfur atoms. If the heterocyclic residue or heterocyclic ring is optionally substituted, it can be condensed with other carbocyclic or heterocyclic rings. In the case of an optionally substituted heterocyclyl, the present invention also encompasses polycyclic systems such as 8-aza-bicyclo[3.2.1]octanyl or 1-aza-bicyclo[2.2.1]heptyl. In the case of an optionally substituted heterocyclyl, the present invention also encompasses spirocyclic systems such as 1-oxa-5-aza-spiro[2.3]hexyl.

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

Of particular importance are heteroaryls and also heteroaromatic systems. According to the present invention, the term heteroaryl means heteroaromatic compounds, this means completely unsaturated aromatic heterocyclic compounds that fall under the above definition of heterocycles. Preferred are 5-7-membered rings with 1-3, preferably 1 or 2 identical or different heteroatoms from the above group. The heteroaryls according to the present invention are, for example, furyl, thienyl, pyrazolyl, imidazolyl, 1,2,3- and 1,2,4-triazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-, 1,3,4-, 1,2,4- and 1,2,5-oxadiazolyl, azepinyl, pyrrolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, 1,3,5-, 1,2,4- and 1,2,3-triazinyl, 1,2,4-, 1,3,2-, 1,3,6- and 1,2,6-oxazinyl, oxepinyl, thiepinyl, 1,2,4-triazolonyl and 1,2,4-diazepinyl. The heteroaryl groups according to the present invention may be further substituted with one or more identical or different substituents.

The term "in each case optionally substituted" means that a group/substituent, such as an alkyl, alkenyl, alkynyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, cycloalkyl, aryl, phenyl, benzyl, heterocyclyl and heteroaryl radical, is understood to mean, for example, a substituted radical derived from an unsubstituted parent structure, the substituents, for example one (1) substituent or more substituents, preferably 1, 2, 3, 4, 5, 6, or 7, being selected from the group consisting of amino, hydroxy, halogen, nitro, cyano, isocyano, mercapto, isothiocyanato, C ₁ -C ₄ -carboxy, urea, SF ₅ , aminosulfonyl, C ₁ -C ₄ alkyl, C ₃ -C ₄ -cycloalkyl, C ₂ -C ₄ -alkenyl, C ₃ -C ₄ -cycloalkenyl, C ₂ -C ₄ -alkynyl, N-mono-C ₁ -C ₄ -alkyl-amino, N,N-di-C ₁ -C ₄ -alkylamino, N-C ₁ -C ₄ -alkanoylamino, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyloxy, C ₂ -C ₄ -al kinyloxy, C ₃ -C ₄ -cycloalkoxy, C ₃ -C ₄ -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, _C2 - _C4- alkynylcarbonyl, C6-, _C10- , _{C14 -} arylcarbonyl, _C1 - _C4 -alkylsulfanyl, _C3 - _C4 -cycloalkylsulfanyl, _C1 - _C4 -alkylthio, _C2 - _C4 -alkenylthio, _C3 - _C4 -cycloalkenylthio, _C2 - _C4 -alkynylthio, _C1 - _C4 -alkylsulfenyl and _C1 - _C4 -alkylsulfinyl, wherein both enantiomers of the _C1 - _C4 -alkylsulfinyl group, _C1 - _C4 -alkylsulfonyl, N-mono- _C1 - _C4 -alkylaminosulfonyl, N,N-di- _C1 - _C4 -alkylaminosulfonyl, _C1 - _C4 -alkylphosphinyl, C ₁ -C ₄ -alkylphosphonyl, wherein for C ₁ -C ₄ -alkylphosphinyl or C ₁ -C ₄ -alkylphosphonyl both enantiomers are encompassed, N-C ₁ -C ₄ -alkyl-aminocarbonyl, N,N-di-C ₁ -C ₄ -alkyl-amino-carbonyl, N-C ₁ -C ₄ -alkanoyl-amino-carbonyl, N-C ₁ -C ₄ -alkanoyl-N-C ₁ -C ₄ -alkyl-aminocarbonyl, C ₆ -,C ₁₀ -,C ₁₄ -aryl, C ₆ -,C ₁₀ -,C ₁₄ -aryloxy, benzyl, benzyloxy, benzylthio, C ₆ -,C ₁₀ -,C ₁₄ -arylthio, C ₆ -,C ₁₀ -,C ₁₄ -arylamino, benzylamino, heterocyclyl and trialkylsilyl, substituents having a double bond, such as C ₁ -C ₄ -alkylidene (for example methylidene or ethylidene), oxo group, thioxo group, imino group, and also substituted imino group. If two or more groups form one or more rings, they can be carbocyclic, heterocyclic, saturated, partially saturated, unsaturated, for example also aromatic and further substituted. The substituents mentioned as examples ("substituents of the first level") can, if they have a hydrocarbon-containing part, be further optionally substituted ("substituents of the second level"), for example one or more substituents in each case independently of one another are selected from halogen, hydroxy, amino, nitro, cyano, isocyano, azido, acylamino, oxo group and imino group. Preferably, only first or second level substituents are encompassed by the term "(optionally) substituted" group.

The halogen-substituted chemical groups or halogenated groups according to the invention (for example alkyl or alkoxy) are mono- or polysubstituted with halogen up to the maximum possible number of substituents. Such groups are also designated as halo groups (such as haloalkyl). In the case of multiple substitution with halogen, the halogen atoms may be the same or different and may all be attached to one or more carbon atoms. In this case, the halogen is most preferably fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine and particularly preferably fluorine. Most preferably, the halogen-substituted groups are monohalo cycloalkyl, such as 1-fluoro-cyclopropyl, 2-fluoro-cyclopropyl or 1-fluoro-cyclobutyl, monohaloalkyl, such as 2-chloro-ethyl, 2-fluoro-ethyl, 1-chloro-ethyl, 1-fluoro-ethyl, chloromethyl or fluoromethyl; perhaloalkyl such as trichloromethyl or trifluoromethyl or CF2CF3, polyhaloalkyl such as difluoromethyl, 2-fluoro-2-chloroethyl, dichloromethyl, 1,1,2,2-tetrafluoroethyl, or 2,2,2-trifluoroethyl. Other 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-tert-butyl. Preferred is a haloalkyl containing from 1 to 4 carbon atoms and from 1 to 9, preferably from 1 to 5 identical or different halogen atoms selected from fluorine, chlorine or bromine. Particularly preferred is a haloalkyl containing 1 or 2 carbon atoms and from 1 to 5 identical or different halogen atoms selected from fluorine or chlorine, such as, inter alia, difluoromethyl, trifluoromethyl or 2,2-difluoroethyl. Other examples _of halogen-substituted compounds are haloalkoxy, such as _OCF3 , _OCHF2 , OCH2F, _{OCF2CF3 , OCH2CF3} , _OCH2CHF2 and _OCH2CH2Cl , haloalkylsulfanyl, such as 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, 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, 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, haloalkylsulfonyl groups such as difluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl, chlorodifluoromethylsulfonyl, 1-fluoroethylsulfonyl, 2-fluoroethylsulfonyl, 2,2-difluoroethyl sulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl and 2-chloro-1,1,2-trifluoroethylsulfonyl.

In the case of radicals comprising carbon atoms, preference is given to those containing from 1 to 4 carbon atoms, most preferably 1 or 2 carbon atoms. Preferred, as a rule, are from the group comprising halogen, for example fluorine and chlorine, (C ₁ -C ₄ )alkyl, preferably methyl or ethyl, (C ₁ -C ₄ )haloalkyl, preferably trifluoromethyl, (C ₁ -C ₄ )alkoxy, preferably methoxy or ethoxy, (C ₁ -C ₄ )haloalkoxy, nitro and cyano. Particularly preferred substituents are methyl, methoxy, fluorine and chlorine.

Substituted amino, such as mono- or disubstituted amino, means a residue from the group of substituted amino residues which, for example, are N-substituted by one or two identical or different residues from the group consisting 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, such as optionally substituted aniline, acylamino, N,N-diacylamino, N-alkyl-N-arylamino, N-alkyl-N-acylamino, as well as saturated N-heterocycles; the alkyl radical preferably having from 1 to 4 carbon atoms; wherein aryl is preferably phenyl or substituted phenyl; wherein acyl is considered as defined below, preferably (C ₁ -C ₄ )alkanoyl. This accordingly applies to substituted hydroxylamino or hydrazino.

Substituted amino also includes quaternary ammonium compounds (salts) with four organic substituents at the nitrogen atom.

Optionally substituted phenyl is preferably phenyl which is unsubstituted or one or more times, preferably up to three times, substituted by the same or different radicals selected from the group consisting of halogen, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy, _C1 -C4-alkoxy- _C1 - _{C4 -} alkoxy _{, C1} - _C4 -alkoxy- _C1 -C4-alkyl, C1- _{C4 -} haloalkyl, _C1 - _C4 -haloalkoxy, _C1 - _C4 -alkylsulfanyl, _C1 - _C4 -haloalkylsulfanyl, cyano, isocyano and nitro, for example o-, m- and p-tolyl, dimethylphenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-trifluoromethyl- and -trichloromethylphenyl, 2,4-, 3,5-, 2,5- and 2,3-dichlorophenyl, o-, m- and p-methoxyphenyl, 4-heptafluorophenyl.

The optionally substituted cycloalkyl is preferably a cycloalkyl which is unsubstituted or substituted one or more times, preferably up to three times, by the same or different radicals selected from the group consisting of halogen, cyano, _C1 - _C4 -alkyl, _C1 - _C4 -alkoxy, _C1 - _C4 -alkoxy- _C1 - _C4 -alkoxy, _C1 - _C4 -alkoxy- _C1 - _C4 -alkyl, _C1 - _C4- haloalkyl and _C1 - _C4 -haloalkoxy, most preferably substituted by one or two _C1 - _C4 -alkyl groups.

The compounds according to the present invention may exist in preferred embodiments. In this case, the individual embodiments described in the present application may be combined with one another. Such combinations are not covered that contradict the laws of nature and that a person skilled in the art would exclude on the basis of his knowledge. For example, ring structures with three or more adjacent oxygen atoms are excluded.

Isomers

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

Methods and applications

The present invention also relates to methods for combating animal pests, in which the compounds of formula (I) act on animal pests and/or their habitat. The combating of animal pests is preferably carried out in agriculture and forestry, and in the protection of materials. Preferably, the present invention excludes methods for surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body.

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

In the context of the present invention, the term "pesticide" in each case also always includes the term "crop protection product".

Compounds of formula (I) having good plant tolerance, favorable homeothermal toxicity and good compatibility with the environment are suitable for protecting plants and plant organs from biotic and abiotic stresses, for increasing the harvested crop, for improving the quality of the harvested crop and for controlling animal pests, especially insects, arachnids, helminths, nematodes and molluscs, which are found in agriculture, horticulture, livestock farming, aquaculture, forestry, gardens and recreational environments, for protecting products and materials during storage, and in the hygiene sector.

In the context of the present invention, the term "hygiene" is understood as the totality of all measures, methods and applications that are aimed at achieving the goal of preventing diseases, in particular infectious diseases, and the health of people, animals and/or the environment, in order to achieve their and/or its cleanliness. In particular, they include measures for cleaning, disinfecting and sterilizing, for example, textile or hard surfaces, especially glass, wood, concrete, porcelain, ceramics, plastic products, as well as products made of metal (metals), as well as for cleaning from hygiene pests or their faecal substances. Again, methods of surgical or therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body are excluded in this regard.

The term "hygiene sector" therefore covers all areas, technical fields and commercial uses in which such measures, methods and applications with regard to hygiene are of importance, such as, for example, hygiene in kitchens, bakeries, airports, baths, swimming pools, department stores, hotels, hospitals, stables, animal keeping areas, etc.

The term "hygiene pest" therefore means one or more animal pests whose presence in the hygiene sector is problematic, in particular for health reasons. The main objective is therefore to prevent or minimise hygiene pests harmful to human health or contact with them in the hygiene sector. This can be done in particular by using a pest control agent, which can be used either preventively or only in the event of an infestation to control the pests. It is also possible to use agents that prevent and reduce contact with the pests. For example, the following organisms are mentioned as hygiene pests.

Thus, the term "hygienic protection" covers all actions to maintain such measures, methods and applications for hygiene.

The compounds of formula (I) can be used preferably as a pesticide. They are active against normally sensitive and resistant species and against all or some stages of development. The above pests include:

Pests from the phylum Arthropods, in particular from the Arachnida class, for example, Acarus spp., for example, Acarus siro, Aceria kuko, Aceria sheldoni, Aculops spp., Aculus spp., for example, Aculus fockeui, Aculus schlechtendali, Amblyomma spp., Amphitetranychus viennensis , Argas spp., Boophilus spp., Brevipalpus spp., for example, Brevipalpus phoenicis, Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp. , for example , Eotetranychus hicoriae, Epitrimerus pyri, Eutetranychus spp., например, Eutetranychus banksi, Eriophyes spp., например, Eriophyes pyri, Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., например, Hemitarsonemus latus (=Polyphagotarsonemus latus), Hyalomma spp., Ixodes spp ., Latrodectus spp., Loxosceles spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., for example, 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., picephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., e.g. Tarsonemus confusus, Tarsonemus pallidus, Tetranychus spp., e.g. Tetranychus canadensis, Tetranychus cinnabarinus, Tetranychus turkestani, Tetranychus urticae, Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici; from the class Labiopods, for example, Geophilus spp., Scutigera spp.;

from the order or class Forktail, for example, Onychiurus armatus; Sminthurus viridis;

from the class Diplopoda, for example, Blaniulus guttulatus;

from the class Insecta, for example, from the order Cockroaches, for example, Blatta orientalis, Blattella asahinai, Blattella germanica, Leucophaea maderae, Panchlo spp., Parcoblatta spp., Periplaneta spp., for example, Periplaneta americana, Periplaneta australasiae, Supella longipalpa;

from the order Coleoptera, e.g. Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Aethina tumida, Agelastica alni, Agrilus spp., e.g. Agrilus planipennis, Agrilus coxalis, Agrilus bilineatus, Agrilus anxius, Agriotes spp., e.g. Agriotes linneatus, Agriotes mancus, Agriotes obscurus, Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anomala dubia, Anoplophora spp., e.g. Anoplophora glabripennis, Anthonomus spp., e.g. Anthonomus grandis, Anthrenus spp., Apion spp., Apogonia spp., Athous haemorrhoidales, Atomaria spp., e.g. Atomaria linearis, Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp., e.g. Bruchus pisorum, Bruchus rufimanus, Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., e.g. Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae, Chaetocnema spp., e.g. Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa, Cleonus mendicus, Conoderus spp., Cosmopolites spp., e.g. Cosmopolites sordidus, Costelytra zealandica, Ctenicera spp., Curculio spp., e.g. Curculio caryae, Curculio caryatrypes, Curculio obtusus, Curculio sayi, Cryptolestes ferrugineus, Cryptolestes pusillus, Cryptorhynchus lapathi, Cryptorhynchus mangiferae, Cylindrocopturus spp., Cylindrocopturus adspersus, Cylindrocopturus furnissi, Dendroctonus spp., for example, Dendroctonus ponderosae Dermes, tes spp., Diabrotica spp., e.g. 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., e.g. Epilachna borealis, Epilachna varivestis, Epitrix spp., e.g. 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., e.g. Hypothenemus hampei, Hypothenemus obscurus, Hypothenemus pubescens, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., e.g. Leucoptera coffeella, Limonius ectypus, Lissorhoptrus oryzophilus, Listronotus (=Hyperodes) spp., Lixus spp., Luperodes spp., Luperomorpha xanthodera, Lyctus spp. , Megacyllene spp., e.g. Megacyllene robiniae, Megascelis spp., Melanotus spp., e.g. Melanotus longulus oregonensis, Meligethes aeneus, Melolontha spp., e.g. Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp. , Neogalerucella spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorhynchus spp., e.g. , Oulema melanopus, Oulema oryzae, Oxycetonia jucunda , Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp., e.g. Phyllotreta armoraciae, Phyllotreta pusilla, Phyllotreta ramosa, Phyllotreta striolata, Popillia japonica, Premnotrypes spp., Pro стад ияпапш truncatus, Psylliodes spp., например, Psylliodes affinis, Psylliodes chrysocephala, Psylliodes punctulata, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Rhynchophorus spp., Rhynchophorus ferrugineus, Rhynchophorus palmarum, Scolytus spp., например, Scolytus multistriatus, Sinoxylon perforans, Sitophilus spp., e.g. Sitophilus granarius, Sitophilus linearis, Sitophilus oryzae, Sitophilus zeamais, Sphenophorus spp., Stegobium paniceum, Sternechus spp., e.g. Sternechus paludatus, Symphyletes spp., Tanymecus spp., e.g. Tanymecus dilaticollis, Tanymecus indicus, Tanymecus palliatus, Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., e.g. Tribolium audax, Tribolium castaneum, Tribolium confusum, Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp., e.g. Zabrus tenebrioides ;

from the order Dermatoptera, for example, Anisolabis maritime, Forficula auricularia, Labi dura riparia;

from the order Diptera, for example, Aedes spp., for example, Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans, Agromyza spp., for example, Agromyza frontella, Agromyza parvicornis, Anastrepha spp., Anopheles spp., for example, Anopheles quadrimaculatus, Anopheles gambiae, Asphondylia spp., Bactrocera spp., e.g. Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomya spp., Chrysops spp., Chrysozona pluvialis , Cochliomya spp., Contarinia spp., e.g. Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, Contarinia schulzi, Contarinia sorghicola, Contarinia tritici, Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., e.g. Culex pipiens, Culex quinqueatus, Culicoides spp. ., Culiseta spp., Cuterebra spp., Dacus oleae, Dasineura spp., e.g. Dasineura brassicae, Delia spp., e.g. Delia antiqua, Delia coarctata, Delia florilega, Delia platura, Delia radicum, Dermatobia hominis, Drosophila spp., e.g. Drosphila 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., e.g. Lucilia cuprina, Lutzomyia spp., Mansonia spp., Musca spp., e.g. 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., e.g. Rhagoletis cingulata, Rhagoletis completa, Rhagoletis fausta, Rhagoletis indifferens, Rhagoletis mendax, Rhagoletis pomonella, Sarcophaga spp., Simulium spp., e.g. Simulium meridionale, Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp., e.g. Tipula paludosa, Tipula simplex, ToKcotrypana curvicauda;

from the order Hemiptera, for example, Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosiphon spp., for example, Acyrthosiphon pisum, Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleurocanthus spp., Aleyrodes proletella, Aleurolobus barodensis, othrixus floccosus, Allocaridara malayensis, Amrasca spp., e.g. Amrasca bigutulla, Amrasca devastans, Anuraphis cardui, Aonidiella spp., e.g. Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata, Aphanostigma piri, Aphis spp., e.g. 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., e.g. Aspidiotus nerii, Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp., e.g. Cacopsylla pyricola, Calligypona marginata, Capulinia spp., Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus aonidum, Chrysomphalus ficus, Ulina 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., for example, Empoasca abrupta, Empoasca fabae, Empoasca maligna, Empoasca solana, Empoasca stevensi, Eriosoma spp., for example, 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, Hyalopteras prani, Icerya spp., e.g. Icerya purchasi, Idioceras 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 omatus, 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, trioza spp., for example , Paratrioza cockerelli, Parlatoria spp., Pemphigus spp., e.g. Pemphigus bursarius, Pemphigus populivenae, Peregrinus maidis, Perkinsiella spp., Phenacoccus spp., e.g. 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 Ps. Eudococcus 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., e.g. Quadraspidiotus juglansregiae, Quadraspidiotus ostreaeformis, Quadraspidiotus perniciosus, Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., e.g. Rhopalosiphum maidis, Rhopalosiphum oxyacanthae, Rhopalosiphum padi, Rhopalosiphum rufiabdominale, Saissetia spp., e.g. Saissetia coffeae , Saissetia miranda, Saissetia neglecta, Saissetia oleae , Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sipha flava, Sitobion avenae, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., e.g. ToKcoptera aurantii, ToKcoptera citricidus, Trialeurodes vaporariorum, Trioza spp., e.g. Trioza diospyri, Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp. p .;

from the suborder Bugs, for example, Aelia spp., Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., for example, Cimex adjunctus, Cimex hemipterus, Cimex lectularius , Cimex pilosellus, Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., for example, Euschistus heros, Euschistus servus, Euschistus tristigmus, Euschistus variolarius, Eurydema spp., Eurygaster spp., Halyomorpha halys, Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis, Leptoglossus occidentalis, Leptoglossus phyllopus, Lygocoris spp., e.g. Lygocoris pabulinus, Lygus spp., e.g. Lygus elisus, Lygus hesperus, Lygus lineolaris, Macropes excavatus, Megacopta cribraria, Miridae, Monalonion atratum, Nezara spp., e.g. Nezara viridula, Nysius spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., e.g. Piezodorus guildinii, Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stage I is Nashi, Tibraca spp., Triatoma spp.;

from the order Hymenoptera, for example, Acromyrmex spp., Athalia spp., for example, Athalia rosae, Atta spp., Camponotus spp., Dolichovespula spp., Diprion spp., for example, Diprion similis, Hoplocampa spp., for example, Hoplocampa cookei , Hoplocampa testudinea, Lasius spp., Linepithema (Iridiomyrmex) humile, Monomorium pharaonis, Paratrechina spp., Paravespula spp., Plagiolepis spp., Sirex spp., Solenopsis invicta, Tapinoma spp., Technomyrmex albipes, Urocerus spp., Vespa spp. eg Vespa crabro, Wasmannia auropunctata, Xeris spp.;

from the isopod order, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber;

from the order Termites, e.g. Coptotermes spp., e.g. Coptotermes formosanus, Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp., e.g. Reticulitermes flavipes, Reticulitermes hesperus;

from the order Lepidoptera butterflies, e.g. Achroia grisella, Acronicta major, Adoxophyes spp., e.g. Adoxophyes orana, Aedia leucomelas, Agrotis spp., e.g. Agrotis segetum, Agrotis ipsilon, Alabama spp., e.g. Alabama argillacea, Amyelois transitella, Anarsia spp., Anticarsia spp., e.g. 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., e.g. Chilo plejadellus, Chilo suppressalis, Choreutis pariana, Choristoneura spp., Chrysodeixis chalcites, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp., e.g. Cydia nigricana, Cydia pomonella, Dalaca noctuides, Diaphania spp., Diparopsis spp., Diatraea saccharalis, Dioryctria spp., e.g. Dioryctria zimmermani, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eldana saccharina, Ephestia spp., e.g. Ephestia elutella, Ephestia kuehniella, Epinotia spp., Epiphyas postvittana, Erannis spp., Erschoviella musculana, Etiella spp., Eudocima spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., e.g. Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., e.g. Grapholita molesta, Grapholita prunivora, Hedylepta spp., Helicoverpa spp., e.g. Helicoverpa armigera, Helicoverpa zea, Heliothis spp., e.g. Heliothis virescens , Hepialus spp., for example, Hepialus humuli, Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Lampides spp., Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., например, Leucoptera coffeella, Lithocolletis spp., например, Lithocolletis blancardella, Lithophane antennata, Lobesia spp., e.g. Lobesia botrana, Loxagrotis albicosta, Lymantria spp., e.g. Lymantria dispar, Lyonetia spp., e.g. 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., e.g. Ostrinia nubilalis, Panolis flammea, Parnara spp., Pectinophora spp., e.g. Pectinophora gossypiella, Perileucoptera spp., Phthorimaea spp., e.g. Phthorimaea operculella, Phyllocnistis citrella, Phyllonorycter spp., e.g. Phyllonorycter blancardella, Phyllonorycter crataegella, Pieris spp., e.g. Pieris rapae, Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella (=Plutella maculipennis), Podesia spp., e.g. Podesia syringae, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., e.g. Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., e.g. , Schoenobius bipunctifer, Scirpophaga spp., e.g. Scirpophaga innotata, Scotia segetum, Sesamia spp., e.g. Sesamia inferens, Sparganothis spp., Spodoptera spp., e.g. 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, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., e.g. Trichoplusia ni, Tryporyza incertulas, Tuta absoluta , Virachola spp.;

from the order Orthoptera or Orthoptera, e.g. Acheta domesticus, Dichroplus spp., Gryllotalpa spp., e.g. Gryllotalpa gryllotalpa, Hieroglyphus spp., Locusta spp., e.g. Locusta migratoria, Melanoplus spp., e.g. Melanoplus devastator, Paratlanticus ussuriensis, Schistocerca gregaria;

from the order Puff-eaters and lice, for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Phthirus pubis, Trichodectes spp.;

from the order Shenoptera, for example, Lepinotus spp., Liposcelis spp.;

from the order Fleas, for example, Ceratophyllus spp., Ctenocephalides spp., for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis;

from the order Fringedwings, e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips flavens, Frankliniella spp., e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi, Heliothrips spp., Hercinothrips femor alis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp., e.g. Thrips palmi, Thrips tabaci;

from the order Thysanura, for example, Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica;

from the class Symphyla, e.g. Scutigerella spp., e.g. Scutigerella immaculata;

pests of the phylum Mollusca, such as those of the class Bivalvia, such as Dreissena spp.,

and also from the class Gastropoda, for example, Arion spp., for example, Arion ater rufus, Biomphalaria spp., Bulinus spp., Deroceras spp., for example, Deroceras laeve, Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.;

Plant pests from the phylum Nematoda, i.e. plant-parasitic nematodes, in particular Aglenchus spp., for example, Aglenchus agricola, Anguina spp., for example, Anguina tritici, Aphelenchoides spp., for example, Aphelenchoides arachidis, Aphelenchoides fragariae, Belonolaimus spp., for example, Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni, phelenchus spp., e.g. Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus, Cacopaurus spp., e.g. Cacopaurus pestis, Criconemella spp., e.g. Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (=Mesocric onema xenoplax), Criconemoides spp., for example, Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum, Ditylenchus spp., for example, Ditylenchus dipsaci, Dolichodorus spp., Globodera spp., for example, Globodera pallida, Globodera rostochiensis, Helicotylenchus spp., for example, Heli cotylenchus dihystera, Hemicriconemoides spp., Hemicycliophora spp., Heterodera spp., e.g. Heterodera avenae, Heterodera glycines, Heterodera schachtii, Hirschmaniella spp., Hoplolaimus spp., Longidorus spp., e.g. Longidorus africanus, Meloidogyne spp., e.g. Meloidogyne chitwood i, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne incognita, Meloinema spp., Nacobbus spp., Neotylenchus spp., Paralongidorus spp., Paraphelenchus spp., Paratrichodorus spp., e.g. Paratricodorus minor, Paratylenchus spp., Pratylenchus spp., e.g. Pratylenchus penetrans, 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.

The compounds of formula (I) can, if desired, at certain concentrations or application rates, also be used as herbicides, protective agents, growth regulators or plant property improvers, as microbiocides or gametocides, for example as fungicides, antifungals, bactericides, viricides (including anti-viroid agents) or as agents against MLO (mycoplasma-like organisms) and RLO (rickettsia-like organisms). If appropriate, they can be used as intermediates or precursors for the synthesis of other active compounds.

Compositions/forms of application

The present invention also relates to compositions, in particular to compositions for combating unwanted animal pests. The composition can be applied to the animal pests and/or to their habitat.

The composition according to the invention may be provided to the end user in a "ready-to-use" form, i.e. the compositions may be applied directly to the plants or seeds using a suitable device, such as a spray or dusting device. Alternatively, the compositions may be provided to the end user in the form of concentrates, which must be diluted, preferably with water, before use. Thus, unless otherwise specified, the wording "formulation" means such a concentrate, whereas the wording "application form" means the end use in the form of a "ready-to-use" solution, i.e. typically such a diluted composition.

The composition of the present invention can be prepared by conventional methods, for example by mixing a compound of the present invention with one or more suitable excipients, such as those disclosed herein.

The composition comprises at least one compound according to the present invention and at least one auxiliary substance suitable for use in agriculture, such as carrier(s) and/or surfactant(s).

The carrier is a solid or liquid, natural or synthetic, organic or inorganic substance, usually inert. The carrier usually improves the application of the compounds, for example, to plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, in particular ammonium sulfates, ammonium phosphates and ammonium nitrates, natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomite, silica gel and synthetic rock flours such as finely divided silica, aluminum oxide and silicates. Examples of commonly used solid carriers for preparing granules include, but are not limited to, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules of inorganic and organic flour, and granules of organic material such as paper, sawdust, coconut shells, corn cobs and tobacco stalks. Examples of suitable liquid carriers include, but are not limited to, water, organic solvents and combinations thereof. Examples of suitable solvents include polar and non-polar organic chemical liquids, for example from the classes of aromatic and non-aromatic hydrocarbons (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene, tetrahydronaphthalene, alkylnaphthalenes, chlorinated aromatic compounds or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride), alcohols and polyols (which may optionally also be substituted, esterified and/or etherified, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone or cyclohexanone), esters (including fats and oils) and (poly)esters, unsubstituted and substituted amines, amides (such as dimethylformamide or fatty acid amides) and their esters, lactams (such as N-alkylpyrrolidones, in particular N-methylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide), oils of vegetable or animal origin, nitriles (alkyl nitriles such as acetonitrile, propionitrile, butyronitrile, or aromatic nitriles such as benzonitrile), carbonic esters (cyclic carbonic esters such as ethylene carbonate, propylene carbonate, butylene carbonate, or dialkyl carbonate esters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, dioctyl carbonate). The carrier may also be a liquefied gaseous filler, i.e. a liquid that is gaseous at standard temperature and pressure, such as aerosol propellants such as halocarbons, butane, propane, nitrogen, and carbon dioxide.

Preferred solid carriers are selected from clays, talc and silica.

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

The amount of the carrier is usually from 1 to 99.99% by weight, preferably from 5 to 99.9% by weight, more preferably from 10 to 99.5% by weight, and most preferably from 20 to 99% by weight of the composition.

Liquid carriers are typically present in the range of 20 to 90 wt.%, such as 30 to 80 wt.%, of the composition.

Solid carriers are typically present in the range of 0 to 50 wt.%, preferably 5 to 45 wt.%, such as 10 to 30 wt.% of the composition.

If the composition includes two or more carriers, the ranges given refer to the total number of carriers.

The surfactant may be an ionic (cationic or anionic), amphoteric or nonionic surfactant such as ionic or nonionic emulsifier(s), foaming agent(s), dispersant(s), wetting agent(s), penetration enhancer(s) and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid, ethoxylated derivatives of poly(alpha-substituted)acrylates, 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 ethers of fatty acids such as castor oil ethoxylate, polyoxyethylene ethers of fatty alcohols such as alkyl aryl polyglycol ethers), substituted phenols (preferably alkyl phenols or aryl phenols), salts of esters of sulfosuccinic acid, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty esters of polyols (such as fatty acid esters of glycerol, sorbitol or sucrose), sulfates (such as alkyl sulfates and alkyl ether sulfates), sulfonates (e.g. alkyl sulfonates, arylsulfonates and alkyl benzene sulfonates), sulfonated galenic naphtha/formaldehyde polymers, phosphoric acid esters, protein hydrolysates, lignosulfite waste solutions and methylcellulose. Any reference to salts in this paragraph preferably refers to the corresponding alkali metal, alkaline earth metal and ammonium salts.

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

The amount of surfactants is usually from 5 to 40 wt.%, for example from 10 to 20 wt.% of the composition.

Further examples of suitable auxiliary substances include water repellents, siccatives, binders (adhesive, tackifier, fixing agent such as carboxymethyl cellulose, natural and synthetic polymers in powder, granule or latex form such as gum arabic, polyvinyl alcohol and polyvinyl acetate, natural phospholipids such as cephalins and lecithins and the synthetic phospholipids polyvinylpyrrolidone and tylose), thickeners and secondary thickeners (such as cellulose ethers, acrylic acid derivatives, xanthan gum, modified clays such as those available under the name Bentone, and finely divided silica), stabilizers (e.g. cold stabilizers), preservatives (e.g. dichlorophene, benzyl alcohol hemiformal, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one), antioxidants, light stabilizers, in particular UV stabilizers, or other agents improving chemical and/or physical stability), dyes or pigments (such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue; organic dyes such as alizarin, azo and metal phthalocyanine dyes), antifoams (such as silicone antifoams and magnesium stearate), antifreezes, stickers, gibberellins and processing aids, mineral and vegetable oils, fragrances, waxes, nutrients (including trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts), protective colloids, thixotropic agents, penetrants, sequestrants and complexing agents.

The choice of excipients depends on the intended method of use of the compound of the invention and/or on the physical properties of the compound(s). In addition, excipients can be selected to impart specific properties (technical, physical and/or biological properties) to the preparations or forms of use obtained from them. The choice of excipients can allow the formulations to be adapted to specific needs.

The composition comprises an insecticidal/acaricidal/nematicidal effective amount of the compound(s) of the present invention. The term "effective amount" means an amount sufficient to control harmful insects/mites/nematodes on crop plants or to protect materials and not to cause significant damage to the treated plants. Such an amount may vary within a wide range and depends on various factors such as the species of insects/mites/nematodes to be controlled, the crop plant or material to be treated, the climatic conditions and the particular compound of the invention used. Typically, the composition of the present invention comprises 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, most preferably from 1 to 80% by weight of the compound of the present invention. It is possible that the composition comprises two or more compounds of the present invention. In such a case, the indicated ranges refer to the total number of compounds according to the present invention.

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

Preferably, the composition according to the invention is in the form of one of the following types: EC, SC, FS, SE, OD, WG, WP, CS, more preferably EC, SC, OD, WG, CS.

Further details of examples of formulation types and their preparation are given below. If two or more compounds of the present invention are present, the stated amount of compound of the present invention refers to the total amount of compounds of the present invention. This applies mutatis mutandis to any additional component of the formulation if two or more representatives of such component are present, for example, a wetting agent, a binder.

i) Water-soluble concentrates (SL, LS)

10-60 wt.% of at least one compound of the invention and 5-15 wt.% of a surfactant (e.g. polycondensates of ethylene oxide and/or propylene oxide with alcohols) are dissolved in such an amount of water and/or a water-soluble solvent (e.g. alcohols such as propylene glycol or carbonates such as propylene carbonate) to obtain a total amount of 100 wt.%. Before use, the concentrate is diluted with water.

ii) Dispersible concentrates (DC)

5-25 wt.% of at least one compound according to the invention and 1-10 wt.% of a surfactant and/or a binder (e.g. polyvinylpyrrolidone) are dissolved in such an amount of an organic solvent (e.g. cyclohexanone) as to obtain a total amount of 100 wt.%. Dilution with water gives a dispersion.

iii) Emulsifiable concentrates (EC)

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

iv) Emulsions (EW, EO, ES)

5-40 wt. % of at least one compound according to the present invention and 1-10 wt. % of a surfactant (e.g. a mixture of calcium dodecylbenzenesulfonate and castor oil ethoxylate or polycondensates of ethylene oxide and/or propylene oxide with or without alcohols) are dissolved in 20-40 wt. % of a water-insoluble organic solvent (e.g. an aromatic hydrocarbon). This mixture is added to such an amount of water using an emulsifier to obtain a total amount of 100 wt. %. The resulting composition is a homogeneous emulsion. Before application, the emulsion can be further diluted with water.

v) Suspensions and suspension concentrates

v-1) Water-based (SC, FS)

In suitable grinding equipment, such as a ball mill with a stirrer, 20-60% by weight of at least one compound according to the invention is ground with the addition of 2-10% by weight of a surfactant (e.g. sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2% by weight of a thickener (e.g. xanthan gum) and water to obtain a finely dispersed suspension of the active substance. Water is added in such an amount that the total amount is 100% by weight. Dilution with water gives a stable suspension of the active substance. For FS type formulations, up to 40% by weight of a binder (e.g. polyvinyl alcohol) is added.

v-2) Oil based (OD, OF)

In suitable grinding equipment, such as a ball mill with a stirrer, 20-60% by weight of at least one compound according to the invention is ground with the addition of 2-10% by weight of a surfactant (for example sodium lignosulfonate and polyoxyethylene fatty alcohol ether), 0.1-2% by weight of a thickener (for example modified clay, in particular benton or silicon dioxide) and an organic carrier to obtain a finely dispersed oil suspension of the active substance. The organic carrier is added in such an amount that the total amount is 100% by weight. Dilution with water gives a stable dispersion of the active substance.

vi) Water-dispersible granules and water-soluble granules (WG, SG)

1-90% by weight, preferably 20-80%, most preferably 50-80% by weight of at least one compound according to the present invention are finely ground with the addition of a surfactant (e.g. sodium lignosulfonate and sodium alkyl naphthyl sulfonates) and a potential carrier material and converted into water-dispersible or water-soluble granules by typical technical devices such as, for example, extrusion, spray drying, fluidized bed granulation. The surfactant and the carrier material are used in such an amount that the total amount is 100% by weight. Dilution with water produces a stable dispersion or solution of the active substance.

vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)

50-80 wt. % of at least one compound according to the invention are ground in a rotor-stator mill with the addition of 1-20 wt. % of a surfactant (e.g. sodium lignosulfonate, sodium alkylnaphthyl sulfonates) and such an amount of a solid carrier, e.g. silica gel, to obtain a total amount of 100 wt. %. Dilution with water gives a stable dispersion or solution of the active substance.

viii) Gel (GW, GF)

In a ball mill with stirring, 5-25 wt. % of at least one compound according to the invention is ground with the addition of 3-10 wt. % of a surfactant (e.g. sodium lignosulfonate), 1-5 wt. % of a binder (e.g. carboxymethylcellulose) and such an amount of water that the total amount is 100 wt. %. The result is a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.

ix) Microemulsion (ME)

5-20 wt.% of at least one compound of the invention are added to 5-30 wt.% of a mixture of organic solvents (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt.% of a mixture of surfactants (e.g. polyoxyethylene fatty alcohol ether and arylphenol ethoxylate) and such an amount of water that the total amount is 100 wt.%. This mixture is stirred for 1 hour to spontaneously obtain a thermodynamically stable microemulsion.

x) Microcapsules (CS)

An oil phase comprising 5-50 wt. % of at least one compound of the invention, 0-40 wt. % of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon), 2-15 wt. % of acrylic monomers (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 comprising 5-50 wt. % of at least one compound of the invention, 0-40 wt. % of a water-insoluble organic solvent (e.g., an aromatic hydrocarbon) and an isocyanate monomer (e.g., diphenylmethene-4,4'-diisocyanates) are dispersed in an aqueous solution of a protective colloid (e.g., polyvinyl alcohol), which results in the formation of polyurea microcapsules. Optionally, the addition of a polyamine (e.g., hexamethylenediamine) is also used, which results in the formation of polyurea microcapsules. The monomers constitute 1-10 wt. % of the total CS composition.

xi) Dust powders (DP, DS)

1-10 wt.% of at least one compound of the invention is finely ground and thoroughly mixed with such an amount of a solid carrier, for example finely ground kaolin, to obtain a total amount of 100 wt.%.

xii) Granules (GR, FG)

0.5-30 wt.% of at least one compound according to the invention is finely ground and bound with such an amount of a solid carrier (for example, a silicate) that the total amount is 100 wt.%.

xiii) Ultra Low Volume (UL) Liquids

1-50 wt.% of at least one compound according to the invention are dissolved in such an amount of an organic solvent, for example an aromatic hydrocarbon, that the total amount is 100 wt.%.

The compositions of types i) to xiii) may optionally contain additional auxiliary substances such as 0.1-1 wt. % preservatives, 0.1-1 wt. % antifoams, 0.1-1 wt. % dyes and/or pigments and 5-10 wt. % antifreezes.

Mixtures

The compounds of formula (I) can also be used in the form of a mixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiological preparations, beneficial species, herbicides, fertilizers, bird repellents, phytotonics, sterilizers, safeners, semi-chemicals and/or plant growth regulators, in order to thus, for example, broaden the spectrum of action, prolong the duration of action, increase the speed of action, prevent repellency or prevent the development of resistance. In addition, such combinations of active compounds can improve plant growth and/or resistance to abiotic factors, such as high or low temperatures, drought or increased water content or soil salinity. It is also possible to improve flowering and fruiting rates, optimize germination and root system development, facilitate harvesting and increase yields, influence ripening, improve the quality and/or nutritional value of harvested products, extend shelf life and/or improve the technological properties of harvested products.

Furthermore, the compounds of formula (I) may be present in a mixture with other active compounds or semi-chemicals, such as attractants and/or bird repellents and/or plant activators and/or growth regulators and/or fertilizers. Similarly, the compounds of formula (I) may be used to improve plant properties, such as, for example, growth, yield and quality of harvested material.

According to a particular embodiment of the present invention, the compounds of formula (I) are present in the compositions or application forms prepared from these compositions, in admixture with additional compounds, preferably those described below.

If one of the compounds mentioned below can occur in different tautomeric forms, these forms are also included, even if they are not explicitly mentioned in each case. In addition, all the named mixing partners can, if their functional groups so permit, optionally form salts with suitable bases or acids.

Insects/acariids/nematodes

The active compounds listed here under their common names are known and described, for example, in the Pesticide Manual ("The Pesticide Manual" 16th Ed., British Crop Protection Council 2012) or can be found on the Internet (e.g. http://www.alanwood.net/pesticides). The classification is based on the IRAC action classification scheme in force at the time of filing of this patent application.

(1) Acetylcholinesterase (AChE) inhibitors, preferably carbamates selected from alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, triazamate, trimethacarb, CMC and xylylcarb, or organophosphates selected from acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demetona-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprofos, famfour, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imitsiaphos, isofenphos, methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion-methyl, fento ali, forate, phosalon, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenophos, propetamphos, os, pyraclofos, pyridafention, quinalphos, sulfotep, tebupyrimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon and vamidothion.

(2) GABA-dependent chloride channel blockers, preferably cyclodiene-organochlorine compounds selected from chlordane and endosulfan, or phenylpyrazoles (fiproles) selected from ethiprole and fipronil.

(3) Sodium channel modulators, preferably pyrethroids selected from the group consisting of acrinathrin, allethrin, d-cis-trans-allethrin, d-trans-allethrin, bifenthrin, bioallethrin, s-cyclopentenyl isomer of bioallethrin, 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, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, cadetrin, momfluorothrin, permethrin, phenothrin [(1R)-trans-isomer], prallethrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer)], tralomethrin and transfluthrin, or DDT, or methoxychlor.

(4) Competitive modulators of the nicotinic acetylcholine receptor (nAChR), preferably neonicotinoids selected from acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine, or sulfoximines selected from sulfoxaflor, or butenolides selected from flupyradifurone, or mesoionics selected from triflumezopyrim.

(5) Allosteric modulators of the nicotinic acetylcholine receptor (nAChR) (site I), preferably spinosyns selected from spinetoram and spinosad.

(6) Allosteric modulators of glutamate-gated chloride channels (GluCl), preferably avermectins/milbemycins selected from abamectin, emamectin benzoate, lepimectin and milbemectin.

(7) Juvenile hormone mimetics, preferably juvenile hormone analogues selected from hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.

(8) Various non-specific (multiple) inhibitors, preferably alkyl halides selected from methyl bromide and other alkyl halides, or chloropicrin, or sulfuryl fluoride, or borax, or cream of tartar, an emetic, or methyl isocyanate generators selected from diazomet and metam.

(9) Modulators of the TRPV channels of the chordotonal organ, preferably pyridine azomethanes selected from pymetrozine and pyrifluquinazone, or pyropenes selected from aphidopyropene.

(10) CHS1-acting mite growth inhibitors selected from clofentezine, hexythiazox, diflavin and etoxazole.

(11) Microbial disruptors of insect gut membranes selected from Bacillus israelensis subspecies, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, plant Bt proteins selected from Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb and Cry34Ab1/35Ab1.

(12) Mitochondrial ATP synthase inhibitors, preferably ATP depleters selected from diafenthiuron, or organotin compounds selected from azocyclotin, cyhexatin and fenbutatin oxide, or propargite or tetradifone.

(13) Uncouplers of oxidative phosphorylation by disrupting the proton gradient, selected from chlorfenapyr, DNOC and sulfluramide.

(14) Nicotinic acetylcholine receptor channel blockers selected from bensultap, cartap hydrochloride, thiocylamide and thiosultap sodium.

(15) Chitin biosynthesis inhibitors affecting CHS1, preferably benzoylureas selected from bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and triflumuron.

(16) Chitin biosynthesis inhibitors type 1 selected from buprofezin.

(17) A moult disruptor (particularly for dipterans, i.e. two-winged insects) selected from cyromazine.

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

(19) Octopamine receptor agonists selected from amitraz.

(20) Mitochondrial complex III electron transfer inhibitors selected from hydramethylnon, acequinocil, fluacrypyrim and bifenazate.

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

(22) Voltage-gated sodium channel blockers, preferably oxadiazines selected from indoxacarb or semicarbazones selected from metaflumizone.

(23) Acetyl-CoA carboxylase inhibitors, preferably derivatives of tetronic and tetramic acids selected from spirodiclofen, spiromesifen, spiropidion and spirotetramate.

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

(25) Mitochondrial complex II electron transfer inhibitors, preferably beta-ketonitrile derivatives selected from cyanopyrafen and cyflumetofen, or carboxanilides selected from piflubamide.

(28) Ryanodine receptor modulators, preferably diamides selected from chlorantraniliprole, cyantraniliprole, cyclaniliprol, flubendiamide and tetraniliprol.

(29) Chordotonal organ modulators (with unspecified target site) selected from flonicamid.

(30) GABA-controlled allosteric modulators of chloride channels, preferably meta diamides selected from broflanilide or isoxazoles selected from fluxamethamide.

(31) Baculovisuses, preferably granuloviruses (GV) selected from Cydia pomonella GV and Thaumatotibia leucotreta (GV), or nucleopolyhedroviruses (NPV) selected from Anticarsia gemmatalis MNPV and Helicoverpa armigera NPV.

(32) Allosteric modulators of the nicotinic acetylcholine receptor (site II) selected from the GS-omega/kappa peptide HXTX-Hvla.

(33) other active compounds selected from acinonapyr, afoxolaner, azadirachtin, benclothiase, benzoximate, benzpyrimoxane, bromopropylate, quinomethionate, chlorprallethrin, cryolite, cyclobutrifluram, cycloxapride, cyetpyrafen, cyhalodiamide, cyproflanilide (CAS 2375110-88-4), dichloromesothiase, dicofol, dimpropyridase, epsilon-metofluthrin, epsilon-momfluthrin, flomethoquine, fluazaindolisine, flucipyriprole (CAS 1771741-86-6), fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, flupirimine, fluralaner, fufenozide, flupentiophenox, guadipir, heptafluthrin, imidaclotiza, iprodione, isocycloseram, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, nicofluprole (CAS 1771741-86-6), oxazosulfil, paichongding, pyridyl, riflukinazone, pyriminostrobin, saramatox Spirobudiclofen, Tetramethylfluthrin, Tetrachlorantraniliprole, Tigolaner, Thioxazafen, Thiofluoximate, Cyclopyrazoflor, Iodomethane; in addition, preparations based on Bacillus firmus (I-1582, Votivo) and azadirachtin (BioNeem), as well as 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 2010052161) (CAS 1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-dia Zaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP2647626) (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-trifluoropropan-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 (known from 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-oxido-3-thietanyl)benzamide, 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (known from WO 2013/050317 A1) (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 WO 2013/162715 A2, WO 2013/162716 A2, 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)thioxomethyl]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 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 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 CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(2)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]-hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenylcyclopropanecarboxylic acid ester (known from CN 103524422 A) (CAS 1542271-46-4); (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]indeno[1,2-e][1,3,4]oxadiazine-4a(3H)-methyl carboxylate (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl-, 1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US 2014/0275503 A1) (CAS 1 181213-14-8); 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-cmn)-8-(2-cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from WO 2007040280 A1, WO 2007040282 A1) (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 CN 103265527 A) (CAS 1452877-50-7), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014/187846 A1) (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 WO 2010/06 6780 A1, WO 2011151146 A1) (CAS 1229023-00-0), N-[1-(2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-(trifluoromethyl)benzamide (known from WO 2014/053450 A1) (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 (known from 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).

Fungicides

The active ingredients listed here under their generic name are known and described, for example, in the Pesticide Handbook (16th ed. British Crop Protection Council) or can be found on the Internet (e.g. www.alanwood.net/pesticides).

All named fungicidal mixing components of classes (1) to (15) may, if their functional groups so permit, optionally form salts with suitable bases or acids. All named mixing partners of classes (1) to (15) may include tautomeric forms where applicable.

1) Ergosterol biosynthesis inhibitors, for example, (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamide, (1.005) fenpropidine, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) conazole, (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) pyrizoxazole, (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, ( 1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol , (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) ( 8)-[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, (1.03 9) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2 ,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel.(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5- yl thiocyanate, (1.041) 1-{[rel.(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2, 4-triazol-5-ylthiocyanate, (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,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6 ,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2, 4-triazole-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1 ,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl) propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4 -chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2 -[4-(4-chlorophenoxy)-2 -(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazol-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-triazol-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-methylimidoformamide, (1.064) N'-(2,5-dimethyl- 4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2,5-dimethyl-4-{[3-( 2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{ 3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2 ,2,2-trifluoroethyl)sulfanyl)]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3 -tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl )-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.073) N '-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{ 4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl- N-methylimidoformamide, (1.076) N'-{5-bromo-6 -[(lR)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[( 1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5- bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3 ,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.081) ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6- (4-bromophenoxy)-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy )-2-(trifluoromethyl)-3-pyridyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3- (3-chloro-2-fluorophenyl)-2-hydroxypropyl]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-triazole- 1-yl)propyl]-3-pyridyl]oxy]benzonitrile.

2) Inhibitors of complex I or II of the respiratory chain, such as, for example, (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxide, (2.008) furametpyr, (2.009) isofetamide, (2.010) isopyram (anti-epimeral enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimeral enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimeral racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrase (syn-epimeric enantiomer 1R,4S,9R), (2.015) isopyrase (syn-epimeric enantiomer 1S,4R,9S), (2.016) isopyrase (syn- epimeric racemate 1RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pidiflumetofen, (2.020) pyraziflumide, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.028) inpirfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) 3-(difluoromethyl)-N-(7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide, (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-carboxamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoine.

3) Respiratory inhibitors acting on complex III of the respiratory chain, such as (3.001) amethoctradine, (3.002) amisulbrom, (3.003) azoxytrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyramethostrobin, (3.019) pyraoxystrobin, (3.020) tri-phloxystrobin (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,37)-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)phenpicoxamide, (3.026) 2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (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)-H,3-dimethylpent-3-enamide, (3.029) Methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) methyltetraprole, (3.031) florylpicoxamide.

4) inhibitor of mitosis and cell division, for example, (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-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- Sh-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine.

5) Compounds having multidirectional activity, for example, (5.001) Bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+)-sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) zinc metiram, (5.017) copper oxine, (5.018) propineb, (5.019) sulfur and sulfur preparations including calcium polysulfide, (5.020) thiram, (5.021) zinb, (5.022) ziram, (5.023) 6-Ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

6) Compounds that are capable of inducing host defense, such as (6.001) acibenzolar-8-methyl, (6.002) isothianyl, (6.003) probenazole, (6.004) tiadinil.

7) Inhibitors of amino acid and/or protein biosynthesis, such as, for example, (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hy-dart, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-Fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

(8) ATP production inhibitors, such as, for example, (8.001) silthiofam.

9) Cell wall synthesis inhibitors such as, for example, (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamide, (9.006) pyrimorph, (9.007) valiphenalate, (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.

10) Inhibitors of lipid and membrane synthesis, such as, for example, (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) toclofos-methyl.

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

12) Inhibitors of nucleic acid synthesis, such as, for example, (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) Metalaxyl, (12.004) Metalaxyl-M (mefenoxam).

13) Signal transduction inhibitors, such as, for example, (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

14) Compounds that can act as uncouplers, such as (14.001) fluazinam, (14.002) meptyldinocap.

15) other fungicides selected from the group consisting of the following: (15.001) abscisic acid, (15.002) benthiazole, (15.003) betoxazine, (15.004) capsimycin, (15.005) carvone, (15.006) quinomethionate, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) flctianil, (15.012) fosetyl aluminum, (15.013) fosetyl calcium, (15.014) fosetyl sodium, (15.015) Methyl isothiocyanate, (15.016) Metraphenone, (15.017) Mildiomycin, (15.018) Natamycin, (15.019) Nickel dimethyldithiocarbamate, (15.020) Nitrothal-isopropyl, (15.021) Oxamocarb, (15.022) Oxathiapiproline, (15.023) Oxyphenthiin, (15.024) Pentachlorophenol and salts, (15.025) Phosphonic acid and its salts, (15.026) Propamocarb-fosetylate, (15.027) Pyriophenone (Chlazafenone), (15.028) Tebufloquine, (15.029) Tecloftalam, (15.030) Tonilphanide, (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) -{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)quinazole in, (15.034) 2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetron, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2- in-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)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1, 2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) lorphenyl methanesulfonate, (15.041) 2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapyroline, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and its salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (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-sulfonhydrazide, (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) Ethyl (2Z)-3-amino-2-cyano-3-phenyl acrylate, (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) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-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}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1 ,2,4-oxadiazol-3-yl]benzamide, (15.077) N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl))-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methylcarbonimidoyl]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-methoxy-C-methylcarbomidoyl]-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-trifluoropropanamide, (15.090) 1-methoxy-1-methyl-3-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-diethyl-3-[[4-[5-(trifluoromethyl)}-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.093) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-dimethoxy-N-[[4-[5-(trifluoromethyl}-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102) 4,4-dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isooxazolidin-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, (15.10 8)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.

Biological pesticides as mixing components

Compounds of formula (I) can be combined with biological pesticides.

Biological pesticides include, but are not limited to, bacteria, fungi, yeasts, plant extracts and products formed by microorganisms, including proteins and secondary metabolites.

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

Examples of such bacteria that are used or can be used as biological pesticides are:

Bacillus amyloliquefaciens strain FZB42 (DSM 231179), or Bacillus cereus, in particular B. cereus strain CNCM 1-1562 or Bacillus firmus strain I-1582 (Accession No. CNCM I-1582) or Bacillus pumilus, in particular strain GB34 (Accession No. ATCC 700814) and strain QST2808 (Accession No. NRRL B-30087), or Bacillus subtilis, in particular strain GB03 (Accession No. SD-1397), or Bacillus subtilis strain QST713 (Accession No. NRRL B-21661) or Bacillus subtilis strain OST 30002 (Accession No. NRRL B-50421) Bacillus thuringiensis, in particular, B. thuringiensis subsp. israelensis (serotype H-14), strain AM65-52 (ATCC accession no. 1276), or B. thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), or B. thuringiensis subsp. kurstaki strain HD-1, or B. thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (ATCC accession no. SD-5834), Streptomyces microflavus strain AQ6121 (=QRD 31.013, NRRL B-50550), Streptomyces galbus strain AQ 6047 (NRRL accession no. 30232).

Examples of fungi and yeasts that are or can be used as biological pesticides:

Beauveria bassiana, in particular strain ATCC 74040, Coniothyrium minitans, in particular strain CON/M/91-8 (Accession No. DSM-9660), Lecanicillium spp., in particular strain HRO LEC 12, Lecanicillium lecanii, (formerly known as Verticillium lecanii), in particular strain KV01, Metarhizium anisopliae, in particular strain F52 (DSM3884/ATCC 90448), Metschnikowia fructicola, in particular strain NRRL Y-30752, Paecilomyces fumosoroseus (now: Isaria fumosorosea), in particular strain IFPC 200613, or strain Arorca 97 (Accession No. ATCC 20874), Paecilomyces lilacinus, in particular P. lilacinus strain 251 (AGAL 89/030550), Talaromyces flavus, in particular strain V117b, Trichoderma atroviride, in particular strain SC1 (Accession No. CBS 122089), Trichoderma harzianum, in particular T. harzianum rifai T39. (Accession No. CNCM 1-952).

Examples of viruses that are or could be used as biological pesticides:

Adoxophyes orana (yellow leaf roller) granulosis virus (GV), Cydia pomonella (copper moth) granulosis virus (GV), Helicoverpa armigera (cotton leaf roller) nuclear polyhedrosis virus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV, Spodoptera littoralis (African cotton leaf roller) NPV.

Also included are bacteria and fungi that are added as an "inoculant" to plants, plant parts or plant organs and that, through their special properties, promote plant growth and plant health. Examples that may be mentioned are:

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.

Examples of plant extracts and microbial products, including proteins and secondary metabolites, that are used or could be used as biological pesticides include:

Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), pyrethrum/pyrethrin, Quassia amara, Quercus, Quillaja, Regalia, "Requiem™ Insecticide", rotenone, ryania/ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extract, in particular oilseed rape powder or mustard powder, and bioinsecticidal/acaricidal active substances obtained from olive oil, in particular unsaturated fatty/carboxylic acids having a carbon chain length of C ₁₆ -C ₂₀ as active ingredients, such as, for example, contained in the product under the trade name FLiPPER®.

Protective agents as mixing components

The compounds of formula (I) can be combined with preservatives such as, for example, benoxacor, cloquintocet(-mexyl), cyometrinil, cipro-sulfamide, dichlormide, fenchlorazole(-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen(-ethyl), mefenpyr(-diethyl), naphthoic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

Plants and parts of plants

According to the invention, all plants and plant parts can be treated. Plants in the context of the present invention are all plants and plant populations, such as desirable and undesirable wild plants or cultivated plants (including natural cultivated plants), for example cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugar cane, tomatoes, red peppers and chili peppers, cucumbers, melons, carrots, watermelons, onions, lettuce, spinach, leeks, beans, Brassica oleracea (e.g. cabbage) and other types of vegetables, cotton, tobacco, oilseed rape, as well as fruit plants (apple trees, pears with fruits, citrus fruits and grapes). Cultivated plants may be plants obtainable by conventional plant breeding and optimization techniques or by biotechnology and genetic engineering techniques or by combinations of these techniques, including transgenic plants and including many plants that may or may not be protected by plant breeders' rights. Plants shall be understood to mean all stages of plant development, such as seeds, cuttings, and young (immature) plants to mature plants. Plant parts are all parts and organs of plants above and below the soil level, such as seedling, leaf, flower and root, with specific examples being leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include crops (harvested plants and plant parts) and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, lateral shoots and seeds.

The treatment according to the present invention of plants and plant parts with the compounds of formula (I) is carried out directly or by conventional treatment methods, for example by dipping, spraying, evaporating, fogging, scattering, coating or injection and, in the case of propagation material, in particular in the case of seeds, also by one or more coatings.

As already noted 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 varieties or those obtained by conventional breeding methods, such as crossing or fusion of protoplasm, and parts thereof are treated. In another preferred embodiment, transgenic plants and plant varieties obtained by genetic engineering methods, if possible in combination with conventional methods (genetically modified organisms), and parts thereof are treated. The terms "plants", "plant parts" and "plant parts" are explained above. More preferably, according to the present invention, plants and plant varieties are treated, which in each case are commercially available or grown. Plant varieties are plants having new characteristics ("traits"), which are imparted by conventional crossing, mutagenesis or a method using recombinant DNA. They can be cultivars, biotypes and genotypes.

Transgenic Plants, Seed Treatment and Integration Events According to the invention, the compounds of formula (I) can be advantageously used for treating transgenic plants, plant varieties or plant parts that have received genetic material that imparts useful and/or beneficial properties (traits) to these plants, plant varieties or plant parts. It is therefore envisaged that the present invention can be combined with one or more recombinant traits or transgenic event(s) or a combination thereof. For the purposes of the present application, a transgenic event is created by inserting a specific recombinant DNA molecule into a specific position (locus) in a chromosome of the plant genome. The insertion creates a new DNA sequence, called an "event", and is characterized by the inserted recombinant DNA molecule and a certain amount of genomic DNA immediately adjacent to or bordering both ends of the inserted DNA. Such traits or transgenic events include, but are not limited to, pest resistance, water use efficiency, yield, drought tolerance, seed quality, improved nutritional quality, hybrid seed production, and herbicide tolerance, where the trait is measured relative to a plant lacking such trait or transgenic event. Specific examples of such advantageous and/or beneficial properties (traits) are improved plant growth, vigor, stress tolerance, 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 to water or soil salinity levels, improved flowering characteristics, easier harvesting, accelerated ripening, higher yields, higher quality and/or higher nutritional value of harvested products, improved shelf life and/or processability of harvested products, and increased resistance to or tolerance against animal and microbial pests such as insects, arachnids, nematodes, mites, slugs and snails.

Among the DNA sequences encoding proteins that confer resistance or tolerance properties to such animal and microbial pests, in particular insects, special mention should be made of the genetic material from Bacillus thuringiensis encoding the Bt proteins, widely described in the literature and well known to those skilled in the art. Proteins extracted from bacteria such as Photorhabdus (WO 97/17432 and WO 98/08932) will also be mentioned. In particular, the Bt Cry or VIP proteins will be mentioned, which include the Cry1A, CryIAb, CryIAc, CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF proteins or toxic fragments thereof, as well as hybrids or combinations thereof, in particular Cry1F. protein or fusions derived from the Cry1F protein (e.g. Cry1A-Cry1F fusion proteins or toxic fragments thereof), Cry1A type proteins or toxic fragments thereof, preferably the Cry1Ac protein or fusions derived from the Cry1Ac protein (e.g. Cry1AbCry1Ac fusion proteins), or the Cry1Ab or Bt2 protein or toxic fragments thereof, the Cry2Ae, Cry2Af or Cry2Ag proteins or toxic fragments thereof, the Cry1A.105 protein or a toxic fragment thereof, the VIP3Aa19 protein, the VIP3Aa20 protein, the VIP3A proteins derived from the COT202 or COT203 event cotton, the VIP3Aa protein or a toxic fragment thereof, as described in Estruch et al. (1996), Proc Natl Acad Sci US A. 28; 93(11):5389-94, Cry proteins as described in WO 2001/47952, insecticidal proteins from Xenorhabdus (as described in WO 98/50427), Serratia (in particular from S. entomophila) or strains of Photorhabdus species, such as the Photorhabdus Tc proteins as described in WO 98/08932. Also included in the present description are any variants or mutants of any of these proteins which differ in some amino acids (1-10, preferably 1-5) from any of the above sequences, in particular the toxic fragment sequence thereof, or which are fused to a transit peptide such as a plastid transit peptide or another protein or peptide.

Another and particularly emphasized example of such properties is tolerance to one or more herbicides, such as imidazolinones, sulfonylureas, glyphosate or phosphinothricin. Among the DNA sequences encoding proteins that confer to transformed plant cells and plants the properties of tolerance to certain herbicides, mention should be made in particular of the bar or PAT gene or the Streptomyces coelicolor gene described in WO 2009/152359, which confers resistance to glufosinate herbicides, the gene encoding a suitable EPSPS (5-enolpyruvylshikimate-3-phosphate synthase), which confers resistance to herbicides having EPSPS as a target, especially herbicides such as glyphosate and its salts, the gene encoding glyphosate p-acetyltransferase, or the gene encoding glyphosate oxidoreductase. Other suitable herbicide resistance traits include at least one ALS (acetolactate synthase) inhibitor (e.g., WO 2007/024782), a mutated Arabidopsis ALS/AHAS gene (e.g., U.S. Patent 6,855,533), genes encoding 2,4-D monooxygenases conferring resistance to 2,4-D (2,4-dichlorophenoxyacetic acid), and genes encoding dicamba monooxygenases conferring tolerance to dicamba (3,6-dichloro-2-methoxybenzoic acid).

Other and particularly emphasized examples of such properties are increased resistance to phytopathogenic fungi, bacteria and/or viruses, due to, for example, systemic acquired resistance (SAR), systemin, phytoalexins, elicitors, as well as resistance genes and correspondingly expressed proteins and toxins.

Particularly useful transgenic events in transgenic plants or plant varieties that can be advantageously treated according to the invention include Event 531/PV-GHBK04 (cotton, insect control, described in WO 2002/040677), Event 1143-14A (cotton, insect control, not deposited, described in WO 2006/128569); Event 1143-51B (cotton, insect control, not deposited, described in WO 2006/128570); Event 1445 (cotton, herbicide resistance, not deposited, described in US-A 2002-120964 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-A 2005-216969); Event 3006-210-23 (cotton, insect control - herbicide tolerance, deposited as PTA-6233, described in US-A 2007-143876 or WO 2005/103266); Event 3272 (corn, quality trait, deposited as PTA-9972, described in WO 2006/098952 or US-A 2006-230473); Event 33391 (wheat, herbicide tolerance, deposited as PTA-2347, described in WO 2002/027004), Event 40416 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-11508, described in WO 11/075593); Event 43A47 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-11509, described in WO 2011/075595); Event 5307 (corn, insect control, deposited as ATCC PTA-9561, described in WO 2010/077816); Event ASR-368 (bent grass, herbicide resistance, deposited as ATCC PTA-4816, described in US-A 2006-162007 or WO 2004/053062); Event B16 (corn, herbicide resistance, not deposited, described in US-A 2003-126634); Event BPS-CV127-9 (soybean, herbicide resistance, deposited under number NCIMB 41603, described in WO 2010/080829); Event BLR1 (oilseed rape, restoration of male sterility, deposited as NCIMB 41193, described in WO 2005/074671), Event CE43-67B (cotton, insect control, deposited as DSM ACC2724, described in US-A 2009-217423 or WO 2006/128573); Event CE44-69D (cotton, insect control, not deposited, described in US-A 2010-0024077); Event CE44-69D (cotton, insect control, not deposited, described in WO 2006/128571); Event CE46-02A (cotton, insect control, not deposited, described in WO 2006/128572); Event COT102 (cotton, insect control, not deposited, described in US-A 2006-130175 or WO 2004/039986); Event COT202 (cotton, insect control, not deposited, described in US-A 2007-067868 or WO 2005/054479); Event COT203 (cotton, insect control, not deposited, described in WO 2005/054480);); Event DAS21606-3/1606 (soybean, herbicide tolerance, deposited as PTA-11028, described in WO 2012/033794), Event DAS40278 (corn, herbicide tolerance, deposited as ATCC PTA-10244, described in WO 2011/022469); Event DAS-44406-6 / pDAB8264.44.06.1 (soybean, herbicide tolerance, deposited as PTA-11336, described in WO 2012/075426), Event DAS-14536-7 /pDAB8291.45.36.2 (soybean, herbicide tolerance, deposited as PTA-11335, described in WO 2012/075429), Event DAS-59122-7 (corn, insect control - herbicide tolerance, deposited as ATCC PTA 11384, described in US-A 2006-070139); Event DAS-59132 (corn, insect control - herbicide tolerance, not deposited, described in WO 2009/100188); Event DAS68416 (soybean, herbicide tolerance, deposited as ATCC PTA-10442, described in WO 2011/066384 or WO 2011/066360); Event DP-098140-6 (corn, herbicide tolerance, deposited as ATCC PTA-8296, described in US-A 2009-137395 or WO 08/112019); Event DP-305423-1 (soybean, quality trait, not deposited, described in US-A 2008-312082 or WO 2008/054747); Event DP-32138-1 (corn, hybridization system, deposited as ATCC PTA-9158, described in US-A 2009-0210970 or WO 2009/103049); Event DP-356043-5 (soybean, herbicide tolerance, deposited as ATCC PTA-8287, described in US-A 2010-0184079 or WO 2008/002872); Event EE-I (bacillus, insect control, not deposited, described in WO 07/091277); Event Fil 17 (corn, herbicide tolerance, deposited as ATCC 209031, described in US-A 2006-059581 or WO 98/044140); Event FG72 (soybean, herbicide tolerance, deposited as PTA-11041, described in WO 2011/063413), Event GA21 (corn, herbicide tolerance, deposited as ATCC 209033, described in US-A 2005-086719 or WO 98/044140); Event GG25 (corn, herbicide resistance, deposited as ATCC 209032, described in US-A 2005-188434 or WO 98/044140); Event GHB119 (cotton, insect control - herbicide resistance, deposited as ATCC PTA-8398, described in WO 2008/151780); Event GHB614 (cotton, herbicide resistance, deposited as ATCC PTA-6878, described in US-A 2010-050282 or W02007/017186); Event GJ11 (maize, herbicide resistance, deposited as ATCC 209030, described in US-A 2005-188434 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 resistance, deposited as NCIMB 41158 or NCIMB 41159, described in US-A 2004-172669 or WO 2004/074492); Event JOPLIN1 (wheat, disease resistance, not deposited, described in US-A 2008-064032); Event LL27 (soybean, herbicide tolerance, deposited as NCIMB41658, described in WO 2006/108674 or US-A 2008-320616); Event LL55 (soybean, herbicide tolerance, deposited as NCIMB 41660, described in WO 2006/108675 or US-A 2008-196127); Event LLcotton25 (cotton, herbicide tolerance, deposited as ATCC PTA-3343, described in WO 2003/013224 or US-A 2003-097687); Event LLRICE06 (rice, herbicide tolerance, deposited as ATCC 203353, described in US 6,468,747 or WO 2000/026345); Event LLRice62 (rice, herbicide tolerance, deposited as ATCC 203352, described in WO 2000/026345), Event LLRICE601 (rice, herbicide tolerance, deposited as ATCC PTA-2600, described in US-A 2008-2289060 or WO 2000/026356); Event LY038 (corn, quality trait, deposited as ATCC PTA-5623, described in US-A 2007-028322 or WO 2005/061720); Event MIR162 (corn, insect control, deposited as PTA-8166, described in US-A 2009-300784 or WO 2007/142840); Event MIR604 (corn, insect control, not deposited, described in US-A 2008-167456 or WO 2005/103301); Event MON15985 (cotton, insect control, deposited as ATCC PTA-2516, described in US-A 2004-250317 or WO 2002/100163); Event MON810 (corn, insect control, not deposited, described in US-A 2002-102582); Event MON863 (corn, insect control, deposited as ATCC PTA-2605, described in WO 2004/011601 or US-A 2006-095986); Event MON87427 (corn, pollination control, deposited as ATCC PTA-7899, described in WO 2011/062904); Event MON87460 (corn, stress tolerance, deposited as ATCC PTA-8910, described in WO 2009/111263 or US-A 2011-0138504); Event MON87701 (soybean, insect control, deposited as ATCC PTA-8194, described in US-A 2009-130071 or WO 2009/064652); Event MON87705 (soybean, quality trait - herbicide tolerance, deposited as ATCC PTA-9241, described in US-A 2010-0080887 or WO 2010/037016); Event MON87708 (soybean, herbicide tolerance, deposited as ATCC PTA-9670, described in WO 2011/034704); Event MON87712 (soybean, yield, deposited as PTA-10296, described in WO 2012/051199), Event MON87754 (soybean, quality trait, deposited as ATCC PTA-9385, described in WO 2010/024976); Event MON87769 (soybean, quality trait, deposited as ATCC PTA-8911, described in US-A 2011-0067141 or WO 2009/102873); Event MON88017 (corn, insect control - herbicide tolerance, deposited as ATCC PTA-5582, described in US-A 2008-028482 or WO 2005/059103); Event MON88913 (cotton, herbicide tolerance, deposited as ATCC PTA-4854, described in WO 2004/072235 or US-A 2006-059590); Event MON88302 (oilseed rape, herbicide tolerance, deposited as PTA-10955, described in WO 2011/153186), Event MON88701 (cotton, herbicide tolerance, deposited as PTA-11754, described in WO 2012/134808), Event MON89034 (corn, insect control, deposited as ATCC PTA-7455, described in WO 07/140256 or US-A 2008-260932); Event MON89788 (soybean, herbicide tolerance, deposited as ATCC PTA-6708, described in US-A 2006-282915 or WO 2006/130436); Event MSI 1 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-850 or PTA-2485, described in WO 2001/031042); Event MS8 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 2001/041558 or US-A 2003-188347); Event NK603 (maize, herbicide tolerance, deposited as ATCC PTA-2478, described in US-A 2007-292854); Event PE-7 (rice, insect control, not deposited, described in WO 2008/114282); Event RF3 (oilseed rape, pollination control - herbicide tolerance, deposited as ATCC PTA-730, described in WO 2001/041558 or US-A 2003-188347); Event RT73 (oilseed rape, herbicide tolerance, not deposited, described in WO 2002/036831 or US-A 2008-070260); Event SYHT0H2/SYN-000H2-5 (soybean, herbicide tolerance, deposited as PTA-11226, described in WO 2012/082548), Event T227-1 (sugar beet, herbicide tolerance, not deposited, described in WO 2002/44407 or US-A 2009-265817); Event T25 (corn, herbicide tolerance, not deposited, described in US-A 2001-029014 or WO 2001/051654); Event T304-40 (cotton, insect control - herbicide resistance, deposited as ATCC PTA-8171, described in US-A 2010-077501 or WO 2008/122406); Event T342-142 (cotton, insect control, not deposited, described in WO 2006/128568); Event TC 1507 (corn, insect control - herbicide resistance, not deposited, described in US-A 2005-039226 or WO 2004/099447); Event VIP1034 (corn, insect herbicide tolerance, deposited as ATCC PTA-3925, described in WO 2003/052073), Event 32316 (corn, insect herbicide tolerance, deposited as PTA-11507, described in WO 2011/084632), Event 4114 (corn, insect herbicide tolerance, deposited as PTA-11506, described in W02011/084621), Event EE-GM3/FG72 (soybean, herbicide tolerance, ATCC accession number PTA-11041), optionally combined with Event EE-GM1/LL27 or Event EE-GM2/LL55 (WO 2011/063413A2), Event DAS-68416-4 (soybean, herbicide resistance, ATCC accession number PTA-10442, WO 2011/066360 A1), Event DAS-68416-4 (soybean, herbicide resistance, ATCC accession number PTA-10442, WO2011/066384A1), Event DP-040416-8 (corn, insect control, ATCC accession number PTA-11508, WO2011/075 593A1), Event DP-043A47-3 (corn, insect control, ATCC accession number PTA-11509, WO2011/075595A1), Event DP-004114-3 (corn, insect control, ATCC Accession No. PTA-11506, WO 2011/084621 A1), event DP-032316-8 (corn, insect control, ATCC Session Accession No. PTA-11507, WO 2011/084632 A1), event MON-88302-9 (oilseed rape, herbicide tolerance, ATCC Accession No. PTA-10955, WO 2011/153186 A1), event DAS-21606-3 (soybean, herbicide tolerance, ATCC Accession No. PTA-11028, WO 2012/033794A2), event MON-87712-4 (soybean, quality trait, ATCC Accession No. PTA-10296, WO2012/051199A2), Event DAS-44406-6 (soybean, complex herbicide tolerance, ATCC Accession Number PTA-11336, WO 2012/075426 A1), Event DAS-14536-7 (soybean, complex herbicide tolerance, ATCC Accession Number PTA-11335, WO 2012/075429 A1), Event SYN-000H2-5 (soybean, herbicide tolerance, ATCC Accession Number PTA-11226, WO 2012/082548 A2), Event DP-061061-7 (rapeseed, herbicide tolerance, Deposit Number Not Available, WO 2012071039 A1), Event DP-073496-4 (oilseed rape, herbicide tolerance, no deposit number, US 2012131692), event 8264.44.06.1 (soybean, cumulative herbicide tolerance, accession number PTA-11336, WO 2012075426 A2), event 8291.45.36.2 (soybean, multilayered herbicide tolerance, accession number PTA-11335, WO 2012075429A2), event SYHT0H2 (soybean, ATCC accession number PTA-11226, WO 2012/082548 A2), event MON88,701 ATCC accession number PTA-11754, WO 2012/134808 A1), event KK179-2 (alfalfa, ATCC accession number PTA-11833, WO 2013/003558 A1), event pDAB8264.42.32.1 (soybean, tolerance to complex herbicides, ATCC accession number PTA-11993, WO 2013/010094 A1), event MZDT09Y (corn, ATCC accession number PTA-13025, WO 2013/012775 A1).

In addition, a list of such transgenic events is provided by the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) and can be found on their website at aphis.usda.gov. The status of such listing as of the filing date of this application is relevant to this application.

The genes/events that confer the desired traits in question may also be present in combination with each other in transgenic plants. Examples of transgenic plants that may be mentioned are important agricultural plants such as cereals (wheat, rice, triticale, barley, rye, oats), corn, soybeans, potatoes, sugar beets, sugar cane, tomatoes, peas and other types of vegetables, cotton, tobacco, oilseed rape, as well as fruit plants (with fruits of apples, pears, citrus and grapes), with particular attention to corn, soybeans, wheat, rice, potatoes, cotton, sugar cane, tobacco and oilseed rape. Particular emphasis is placed on such traits as increased plant resistance to insects, arachnids, nematodes, slugs and snails, as well as increased plant resistance to one or more herbicides.

Commercially available examples of such plants, plant parts or plant seeds that can be advantageously treated according to the invention include commercial products such as plant seeds sold or distributed under the trade names GENUITY®, DROUGHTGARD®, SMARTSTAX®, RIB COMPLETE®, ROUNDUP READY, VT DOUBLE PRO®, VT TRIPLE PRO®, BOLLGARD II®, ROUNDUP READY 2 YIELD®, YIELDGARD®, ROUNDUP READY® 2 XTEN ^D ™, INTACTA RR2 PRO®, VISTIVE GOLD®, and/or XTENDFLEX™.

Protection of cultivated plants - types of treatment

The treatment of plants and plant parts with the compounds of formula (I) is carried out directly or by acting on their environment, habitat or storage space by using conventional treatment methods, for example by dipping, spraying, atomizing, irrigation, evaporation, dusting, aerosol irrigation, scattering, foaming, painting, spreading, injection, watering (soaking), drip irrigation and, in the case of propagation material, in particular in the case of seed, also in the form of a powder for dry seed treatment, a solution for liquid seed treatment, a water-soluble powder for suspension treatment, by crust coating, by coating with one or more coatings, etc. It is also possible to apply the compounds of formula (I) by means of a microvolume method or to inject the application form or the compound of formula (I) itself into the soil.

The preferred direct treatment of plants is foliar application, i.e. the compounds of formula (I) are applied to the leaves, where the frequency of treatment and the application rate should be adjusted depending on the level of infestation by the pest in question.

In the case of systemic active compounds, the compounds of formula (I) also have access to the plants via the root system. The plants are then treated by the action of the compounds of formula (I) on the plant habitat. This can be done, for example, by flooding or by mixing into the soil or nutrient solution, i.e. the locus of the plant (e.g. soil or hydroponic systems) is impregnated with the liquid form of the compounds of formula (I), or by soil application, i.e. the compounds of formula (I) according to the present invention are introduced in solid form (e.g. in the form of granules) into the locus of the plants. In the case of paddy rice crops, this can be done by dosing the compound of formula (I) in the form of a soil application (e.g. in the form of granules) into the flooded rice field.

Digital technologies

The compounds of the present invention can be used in combination with models, such as those built into computer programs for site-specific crop management, satellite farming, precision farming, or precision agriculture. Such models support site-specific crop management with data from various sources, such as soils, 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., in order to optimize profitability, sustainability, and environmental protection. In particular, such models can help optimize agronomic decisions, monitor the accuracy of pesticide application, and record the work performed.

For example, the compounds of the present invention can be applied to crop plants in accordance with an appropriate dosing regimen if the model simulates the development of the pest and calculates that a threshold has been reached at which it is recommended to apply the compound of the present invention to the crop plants.

Commercially available systems that include agronomic models include, for example, FieldScriptsTM from The Climate Corporation, XarvioTM from BASF, AGLogicTM from John Deere, etc.

The compounds according to the present invention can also be used in combination with intelligent spraying equipment, such as, for example, spot spraying equipment or precision spraying equipment attached to or placed inside an agricultural vehicle, such as a tractor, robot, helicopter, aircraft, unmanned aerial vehicle (UAV), such as an unmanned aerial vehicle, etc. Such equipment typically includes input sensors (such as, for example, a camera) and a processing unit configured to analyze the input data and configured to issue a decision on the basis of the analysis of the input data on the application of the compound of the invention to crop plants (respectively weeds) in a specific and accurate manner. The use of such intelligent spraying equipment typically also requires location systems (such as GPS receivers) for localizing the recorded data and guiding or controlling the agricultural vehicles; geographic information systems (GIS) for presenting the information on understandable maps and the corresponding agricultural vehicles for performing the necessary agricultural actions, such as spraying.

For example, pests can be detected from images captured by a camera. For example, pests can be identified and/or classified based on these images. Such identification and/or classification can use image processing algorithms. Such image processing algorithms can use machine learning algorithms such as trained neutral networks, decision trees, and artificial intelligence algorithms. Thus, the connections described here can be applied only where necessary.

Seed processing

The control of animal pests by treating plant seeds has been known for a long time and is the subject of continuous improvement. However, seed treatment is associated with a number of problems that cannot always be solved in a satisfactory manner. It is therefore desirable to develop methods for protecting the seed and the germinating plant that do not involve or at least significantly reduce the additional application of pesticides during storage, after sowing or after germination of the plants. In addition, it is desirable to optimize the amount of active compound applied in such a way as to ensure optimal protection for the seed and the germinating plant against the action of animal pests, but without damaging the plant itself by the active compound applied. In particular, seed treatment methods should also take into account the intrinsic insecticidal or nematicidal properties of the pest-resistant or tolerant transgenic plants in order to achieve optimal protection of the seed as well as the germinating plant with a minimum of pesticide application.

The present invention therefore also relates in particular to a method for protecting seed and germinating plants from the action of pests by treating the seed with one of the compounds of formula (I). The method according to the present invention for protecting seed and germinating plants from the action of pests furthermore encompasses a method in which the seed is treated simultaneously in one operation or successively with a compound of formula (I) and a mixing component. A method in which the seed is treated at different points in time with a compound of formula (I) and a mixing component is also encompassed.

The present invention similarly relates to the use of compounds of formula (I) for treating seed to protect the seed and the resulting plant from animal pests.

The present invention further relates to a seed which has been treated with a compound of formula (I) according to the present invention, so that protection against animal pests is achieved. The present invention also relates to a seed which has been treated simultaneously with a compound of formula (I) and a mixing component. The present invention further relates to a seed which has been treated at different times with a compound of formula (I) and a mixing component. In the case of a seed which has been treated at different times with a compound of formula (I) and a mixing component, the individual substances may be present on the seed in different layers. According to the present invention, the layers containing the compound of formula (I) and the mixing components may, if necessary, be separated by intermediate layers. The present invention also relates to a seed to which the compound of formula (I) and the mixing component are applied as a component of a coating or as an additional layer or additional layers, in addition to the coating.

Furthermore, the present invention relates to a seed which, after treatment with a compound of formula (I), is subjected to a film coating process to prevent the abrasive action of dust on the seed.

One of the advantages provided by the systemic action of the compound of formula (I) is the fact that by treating the seed, not only the seed itself, but also the plants obtained from it, are protected from animal pests after germination. Thus, immediate treatment of the crop at the time of sowing or immediately after can be avoided.

Another advantage considered is that by treating the seed with a compound of formula (I), the development and germination of the treated seed can be enhanced.

Similarly, the advantage that the compounds of formula (I) can be used, in particular, also for transgenic seed is considered.

Furthermore, the compounds of formula (I) can be used in combination with signal transduction process compositions or compounds, resulting in improved colonization by symbiotic organisms such as, for example, nodule bacteria, mycorrhiza and/or endophytic bacteria or fungi, and/or in optimization of nitrogen fixation.

The compounds of formula (I) are suitable for protecting the seed of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture. In particular, it takes the form of seed of cereals (such as wheat, barley, rye, millet and oats), corn, cotton, soybeans, rice, potatoes, sunflowers, coffee, tobacco, canola, oilseed rape, beets (such as sugar beets and fodder beets), peanuts, vegetables (such as tomatoes, cucumbers, beans, cruciferous vegetables, onions and lettuce), fruit plants, lawn grasses and ornamental plants. The treatment of seed of cereals (such as wheat, barley, rye and oats), corn, soybeans, cotton, canola, oilseed rape, vegetables and rice is of particular importance.

As already mentioned above, the treatment of transgenic seed with a compound of formula (I) is also of particular importance. It is carried out with respect to a form of plant seed which, as a rule, contains at least one heterologous gene which controls the expression of a polypeptide with in particular insecticidal and/or nematicidal properties, the heterologous genes in the transgenic seed can originate from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly suitable for the treatment of transgenic seed which contains at least one heterologous gene originating from Bacillus sp. Particularly preferably, the heterologous gene originates from Bacillus thuringiensis.

In the context of the present invention, the compound of formula (I) is applied to the seed. Preferably, the seed is treated in a state in which it is sufficiently stable to avoid damage during the treatment. In general, the seed can be treated at any time by harvesting and sowing. The seed is usually used, separated from the plant and freed from cobs, skins, stalks, coverings, hairs or fruit pulp. For example, it is possible to use seed that has been harvested, cleaned and dried to a moisture content that ensures storage. Alternatively, it is also possible to use seed that, after drying, has been treated, for example, with water and then dried again, for example by absorption. In the case of rice seeds, it is also possible to use seed material that has been previously soaked in water, for example up to a certain stage (the "chicken breast" stage), which leads to both improved germination and more uniform growth.

When treating the seed, care must generally be taken to ensure that the amount of compound of formula (I) applied to the seed and/or the amount of other additives is selected in such a way that the germination of the seed is not adversely affected or that the resulting plant is not damaged. This must be ensured in particular in the case of active compounds that may exhibit phytotoxic effects at certain application rates.

In general, the compounds of formula (I) are applied to the seed in the form of a suitable composition. Suitable compositions and methods for treating seeds are known to those skilled in the art.

The compounds of formula (I) can be converted into standard seed dressing compositions such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV compositions.

These compositions are prepared in a known manner by mixing compounds of formula (I) with standard additives such as, for example, standard fillers, as well as solvents or diluents, colorants, wetting agents, dispersing agents, emulsifiers, antifoams, preservatives, secondary thickeners, adhesives, gibberellins, and also water.

The dyes that may be present in the seed dressing compositions that can be used according to the present invention are all dyes that are standard for such purposes. It is possible to use either pigments that are slightly soluble in water or dyes that are soluble in water. Examples include the dyes known under the names Rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1.

Useful wetting agents that may be present in the seed dressing compositions used according to the present invention are all substances that provide wetting and that are commonly used for the formulation of agriculturally active compounds. Alkyl naphthalene sulphonates, as well as diisopropyl or diisobutyl naphthalene sulphonates are preferred.

Useful dispersants and/or emulsifiers which may be present in the seed dressing compositions used according to the present invention are all nonionic, anionic and cationic dispersants conventionally used for the formulation of active agricultural ingredients. The use of nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants is preferred. Suitable nonionic dispersants include in particular ethylene oxide/propylene oxide block polymers, alkylphenol polyglycol ethers and tristyrylphenol polyglycol ethers, and phosphated or sulfated derivatives thereof. Suitable anionic dispersants include in particular lignosulfonates, polyacrylic acid salts and arylsulfonate/formaldehyde condensates.

Antifoams that may be present in the seed dressing compositions used according to the present invention are all foam inhibiting substances commonly used for the composition of active agricultural ingredients. Preferably, antifoams based on silicon and magnesium stearate are used.

The concertants that may be present in the seed dressing compositions used according to the present invention are all substances used for such purposes in agricultural compositions. Examples include dichlorophen and benzyl alcohol hemiacetal.

Secondary thickeners that may be present in the seed dressing compositions used according to the present invention are all substances that can be used for such purposes in agricultural compositions. Preferred are cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely ground silicic acid.

The adhesives that may be present in the seed dressing compositions used according to the present invention are all standard binders used in seed dressing products. As preferred, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and tylose may be mentioned.

The gibberellins which may be present in the compositions used according to the present invention may preferably be the gibberellins A1, A3 (= gibberellic acid), A4 and A7; the use of gibberellic acid is particularly preferred. Gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- and Schädlingsbekämpfungsmittel", Vol. 2, Springer Verlag, 1970, pp. 401-412).

The seed dressing compositions used according to the present invention can be used to treat a wide variety of different types of seeds, either directly or after preliminary dilution with water. For example, concentrates or preparations obtained from them by dilution with water can be used to treat the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, oilseed rape, peas, beans, cotton, sunflower, soybeans and beets, or a wide variety of different vegetable seeds. The seed dressing compositions used according to the present invention, or diluted forms of application thereof, can also be used to treat the seeds of transgenic plants.

For treating the seed with the seed dressing compositions used according to the present invention or the application forms obtained from them by adding water, all mixing components commonly used for seed dressing are useful. In particular, the seed dressing technique consists of placing the seed in a mixer operating periodically or continuously, adding a specific desired amount of the seed dressing composition, either as such or after preliminary dilution with water, and mixing all the components until the desired homogeneity of the composition on the seed is achieved. If necessary, this is accompanied by a drying operation.

The application rate of the seed dressing compositions used according to the present invention may vary over a relatively wide range. In this case, the specific content of the compounds of formula (I) in the compositions and the seed is guided. The application rates of the compound of formula (I) are generally from 0.001 to 50 g per kilogram of seed, preferably from 0.01 to 15 g per kilogram of seed.

Animal Health

In the field of animal health, i.e. in the field of veterinary medicine, the compounds of formula (I) are active against animal pests, in particular ectoparasites or endoparasites. The term endoparasites includes in particular helminths and protozoa such as coccidia. Ectoparasites are generally and preferably arthropods, in particular insects and acarids.

In the field of animal health, the compounds of formula (I) are suitable, with favourable homeothermic toxicity, for the control of parasites that occur in animal husbandry and livestock farming in farm animals, breeding animals, zoo animals, laboratory animals, experimental animals and pets. They are active against all or specific stages of parasite development.

Farm animals include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffalo, rabbits, reindeer, fallow deer and in particular cattle and pigs; or poultry such as turkeys, ducks, geese and in particular chickens; fish and crustaceans, for example in aquaculture; and insects such as bees.

Pets include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets, and especially dogs, cats, caged birds, reptiles, amphibians and aquarium fish.

According to a preferred embodiment of the present invention, the compounds of formula (I) are administered to mammals.

According to another preferred embodiment of the present invention, the compounds of formula (I) are administered to birds, in particular caged birds and in particular poultry.

By using the compounds of formula (I) to combat parasites in animals, it is intended to reduce or prevent illnesses, deaths and bring characteristics to standard conditions (in the case of meat, milk, wool, skins, eggs, honey and the like), so that more economical and easier maintenance of animals becomes possible and better welfare of animals is achieved.

The term "control" or "control" as used in this application, in relation to the field of animal health, means that the compounds of formula (I) are effective to reduce the infestation of the relevant parasite in an animal infected with such parasites to safe levels. More specifically, the term "control" as used in this application means that the compound of formula (I) is effective to kill the relevant parasite, inhibit its growth or inhibit its reproduction.

Arthropods include, for example, but are not limited to

from the order Lice, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.;

from the order Poucheda and the suborders Amblycerina and Ischnocerina, for example, Bovicola spp., Damalina spp., Felicola spp.; Lepikentron spp., Menopon spp., Trichodectes spp., Trimenopon spp., Trinoton spp., Werneckiella spp;

from the order Diptera and suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Atylotus spp., Braula spp., Calliphora spp., Chrysomyia spp., Chrysops spp., Culex spp., Culicoides spp., Eusimulium spp. , Fannia spp., Gasterophilus spp., Glossina spp., Haematobia spp., Haematopota spp., Hippobosca spp., Hybomitra spp., Hydrotaea spp., Hypoderma spp., Lipoptena spp., Lucilia spp., Lutzomyia spp., Melophagus spp., Morellia spp., Musca spp., Odagmia spp., Oestrus spp., Philipomyia spp., Phlebotomus spp., Rhinoestrus spp., Sarcophaga spp., Simulium spp., Stomoxis spp., Tabanus spp., Tipula spp., Wilhelmia spp., Wohlfahrtia spp.;

from the order Fleas, for example, Ceratophyllus spp., Ctenocephalides spp., Pulex spp., Tunga spp., Xenopsylla spp.;

from the order Klopata, for example, Cimex spp., Panstrongylus spp., Rhodnius spp., Triatoma spp.; as well as nuisance and hygienic pests from the order Blattarida.

In addition, as arthropods, by way of example and not limitation, the following mites may be mentioned:

From the subclass Acarina and the order Metastigmata, such as from the family Acarinae, such as Argas spp., Ornithodorus spp., Otobius spp., from the family Ixodid ticks, such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp., Rhipicephalus spp. (the original genus of ticks with multiple hosts); from the order Mesostigmata, such as Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Tropilaelaps spp., Varroa spp.; from the order Actinedida (Prostigmata), for example, Acarapis spp., Cheyletiella spp., Demodex spp., Listrophorus spp., Myobia spp., Neotrombicula spp., Ornithocheyletia spp., Psorergates spp., Trombicula spp.; and from the order Acaridida (Astigmata), for example, Acarus spp., Caloglyphus spp., Chorioptes spp., Cytodites spp., Hypodectes spp., Knemidocoptes spp., Laminosioptes spp., Notoedres spp., Otodectes spp., Psoroptes spp., Pterolichus spp., Sarcoptes spp., us spp., Tyrophagus spp.

Examples of parasitic protozoa include, but are not limited to:

Flagellates (Flagellata), such as:

Metamonads: from the order Diplomonads, e.g. Giardia spp., Spironucleus spp.

Parabasalia: from the order Trichomonas, for example, Histomonas spp., Pentatrichomonas spp., Tetratrichomonas spp., Trichomonas spp., Tritrichomonas spp.

Euglenozoans: from the order Trypanosomatida, for example, Leishmania spp., Trypanosoma spp.

Sarcomastigophora (Rhizopoda), e.g. Entamoebidae, e.g. Entamoeba spp., Centramoebidae, e.g. Acanthamoeba sp., Euamoebidae, e.g. Hartmanella sp.

such as Apicomplexa (Sporozoa): such as Cryptosporidium spp.; from the order Eimeriida such as Besnoitia spp., Cystoisospora spp., Eimeria spp., Hammondia spp., Isospora spp., Neospora spp., Sarcocystis spp., Toxoplasma spp.; from the order Adeleida such as Hepatozoon spp., Klossiella spp.; from the order Haemosporida such as Leucocytozoon spp., Plasmodium spp.; from the order Piroplasmida such as Babesia spp., Ciliophora spp., Echinozoon spp., Theileria spp.; from the order Vesibuliferida such as Balantidium spp., Buxtonella spp.

Microsporidia, such as Encephalitozoon spp., Enterocytozoon spp., Globidium spp., Nosema spp., and also, for example, Myxozoa spp.

Helminths pathogenic to humans and animals include, for example, flatworms, nematodes, acanthocephalans and pentastocephalans (e.g., monogeneans, cestodes and trematodes).

Examples of helminths include, but are not limited to:

Monogenea: for example: Dactylogyrus spp., Gyrodactylus spp., Microbothrium spp., Polystoma spp., Troglecephalus spp.;

Cestodes: from the order Pseudophyllidea, for example: Bothridium spp., Diphyllobothrium spp., Diplogonoporus spp. Ichthyobothrium spp., Ligula spp., Schistocephalus spp., Spirometra spp.

From the order Cyclophyllidae, for example: Andyra spp., Anoplocephala spp., Avitellina spp., Bertiella spp., Cittotaenia spp., Davainea spp., Diorchis spp., Diplopylidium spp., Dipylidium spp., Echinococcus spp., Echinocotyle spp., Echinolepis spp., Hydatigera spp., Hymenolepis spp., Joyeuxiella spp., Mesocestoides spp., Moniezia spp., Paranoplocephala spp., Raillietina spp., Stilesia spp., Taenia spp., Thysaniezia spp., Thysanosoma spp.

Trematodes: from the class of digenetic flukes, for example: Austrobilharzia spp., Brachylaima spp., Calicophoron spp., Catatropis spp., Clonorchis spp. Collyriclum spp., Cotylophoron spp., Cyclocoelum spp., Dicrocoelium spp., Diplostomum spp., Echinochasmus spp. ., Echinoparyphium spp., 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: from the order Trichinella, for example: Capillaria spp., Trichinella spp., Trichomosoides spp., Trichuris spp.

From the order Tylenchida, for example: Micronema spp., Parastrangyloides spp., Strongyloides spp.

From the order Rhabditidae, for example: Aelurostrongylus spp., amidostomum spp., Ancylostoma spp., Angiostrongylus spp., Bronchonema spp., Bunostomum spp., Chabertia spp., Cooperia spp., Cooperioides spp., Crenosoma spp., Cyathostomum spp., cycling spp., Heligmosomoides spp., Hyostrongylus spp., Marshallagia spp., Metastrongylus spp., Muellerius spp., Necator spp., Nematodirus spp., Neostrongylus spp., Nippostrongylus spp., Obeliscoides spp., Oesophagodontus spp., Oesophagostomum spp. , Ollulanus spp.; Ornithostrongylus spp., Oslerus spp., Ostertagia spp., Paracooperia spp., Paracrenosoma spp., Parafilaroides spp., Parelaphostrongylus spp., Pneumocaulus spp., Pneumostrongylus spp., Poteriostomum spp., Protostrongylus spp., Spicocaulus spp., Stagehanurus spp. ., Strongylus spp., Syngamus spp., Teladorsagia spp., Trichonema spp., Trichostrongylus spp., Triodontophorus spp., Troglostrongylus spp., Uncinaria spp.

From the order Spiruridae, for example: Acanthocheilonema spp., Anisakis spp., Ascaridia spp.; Ascaris spp., Ascarops spp., Aspiculuris spp., Baylisascaris spp., Brugia spp., Cercopithifilaria spp., Crassicauda spp., Dipetalonema spp., Dirofilaria spp., Dracunculus spp.; Draschia spp., Enterobius spp., Filaria spp., Gnathostoma spp., Gongylonema spp., Habronema spp., Heterakis spp.; Litomosoides spp., Loa spp., Onchocerca spp., Oxiuris spp., Parabronema spp., Parafilaria spp., Parascaris spp., Passalurus spp., Physaloptera spp., Probstmayria spp., Pseudofilaria spp., Setaria spp., Skjrabinema spp. ., Spirocerca spp., Stagehanofilaria spp., Strongyluris spp., Syphacia spp., Thelazia spp., Toxascaris spp., Toxocara spp., Wuchereria spp.

Acanthocephala: from the order Oligacanthorhynchida, for example: Macracanthorhynchus spp., Prosthenorchis spp.; from the order Moniliformida, for example: Moniliformis spp.,

From the order Polymorphida, for example: Filicollis spp.; from the order Echinorhynchida, for example, Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp.

Pentastoma: from the order Porocephalida, e.g. Linguatula spp.

In the field of veterinary medicine and in the field of animal health, the administration of the compounds of formula (I) is carried out in ways generally known in the art, such as enterally, parenterally, dermally or nasally, in the form of suitable preparations. The administration can be carried out prophylactically or therapeutically.

Thus, one embodiment of the present invention relates to the use of a compound of formula (I) as a medicine.

Another object is the use of a compound of formula (I) as an anti-endoparasitic agent.

Another particular object of the present invention is the use of compounds of formula (I) as an anthelmintic, in particular for use as a nematicide, an antiflatworm, an antiacanthic or an antipentacular agent.

Another object is the use of a compound of formula (I) as an antiprotozoan agent.

Another object is the use of a compound of formula (I) as an anti-ectoparasitic agent, in particular an arthropodicide such as an insecticide or acaricide.

Another object of the present agent is veterinary compositions containing an effective amount of at least one compound of formula (I) and at least one of the following: a pharmaceutically acceptable excipient (for example, solid or liquid diluents), a pharmaceutically acceptable adjuvant (for example, surfactants), in particular a pharmaceutically acceptable excipient commonly used in veterinary drugs, and/or a pharmaceutically acceptable adjuvant traditionally used in veterinary drugs.

Another object of the present invention is a method for producing a veterinary composition as described in the present application, which comprises the step of mixing at least one compound of formula (I) with pharmaceutically acceptable excipients and adjuvants, especially with pharmaceutically acceptable excipients conventionally used in veterinary compositions and/or adjuvants conventionally used in veterinary compositions.

Another specific object of the present invention are veterinary compositions selected from the group of ectoparasitic and endoparasitic compositions, in particular selected from the group of compositions against flatworms, compositions against protozoa and arthropodicidal compositions, most preferably selected from the group of nematicidal compositions, compositions against flatworms, compositions against acanthocephalans, compositions against pentas, insecticidal and acaricidal compositions, according to the said objects, as well as a method for producing them.

Another object of the present invention is a method for treating a parasitic infection, in particular an infection caused by a parasite selected from the group of ectoparasites and endoparasites mentioned in the present application, using an effective amount of a compound of formula (I) in an animal, in particular a non-human animal, in need thereof.

Another object of the present invention is a method for treating a parasitic infection, in particular an infection caused by a parasite selected from the group of ectoparasites and endoparasites mentioned in the present application, using a veterinary composition as defined in the present application, in an animal, in particular a non-human animal, in need thereof.

Another object of the present invention is the use of compounds of formula (I) for the treatment of a parasitic infection, in particular an infection caused by a parasite selected from the group of ectoparasites and endoparasites mentioned in the present application, in an animal, in particular a non-human animal.

In the context of veterinary medicine or animal health protection, the term "treatment" includes prophylactic, metaphylactic and therapeutic treatment.

In a particular embodiment of the present invention for the veterinary field, mixtures of at least one compound of formula (I) with other active ingredients, in particular with endo- and ectoparasitic agents, are provided.

In the field of animal health, "mixing" not only means that two (or more) different active substances are formulated in one formulation and used together, but also refers to products containing separate formulations for each active substance. Accordingly, if more than two active substances are to be used, all active substances may be in one formulation, or all active substances may be in different formulations; mixed forms are also possible, in which some of the active substances are formulated together and some of the active substances are formulated separately. Separate formulations allow the separate and sequential use of the respective active substances.

The active ingredients listed under their "common name" are known and described, for example, in the "Pesticide Manual" (see above) or can be found on the Internet (for example, http://www.alanwood.net/pesticides).

Exemplary active substances from the group of ectoparasites as a mixing partner include, but are not limited to, the insecticides and acaricides described above, other useful agents are listed below according to the above classification based on the current IRAC classification system: (1) Acetylcholinesterase (AChE) inhibitors; (2) GABA-dependent chloride channel blockers; (3) Sodium channel modulators; (4) Nicotinic acetylcholine receptor (nAChR) agonists; (5) Allosteric nicotinic acetylcholine receptor (nAChR) modulators; (6) Allosteric glutamate-dependent chloride channel (GluCl) modulators; (7) Juvenile hormone mimetics; (8) Miscellaneous non-specific (multi-site) inhibitors; (9) Insect auditory modulators; (10) Mite growth inhibitors; (12) Mitochondrial ATP synthesis inhibitors such as ATP disruptors; (13) Agents that uncouple oxidative phosphorylation by disrupting the proton gradient; (14) Nicotinergic acetylcholine receptor blockers; (15) Chitin biosynthesis inhibitors type 0; (16) Chitin biosynthesis inhibitors type 1; (17) Molting inhibitors (particularly for Diptera, i.e. flies); (18) Ecdysone receptor agonists; (19) Octopaminergic agonists; (21) Mitochondrial complex I electron transport inhibitors; (25) Mitochondrial complex II electron transport inhibitors, (20) Mitochondrial complex III electron transport inhibitors; (22) Voltage-gated sodium channel blockers; (23) Acetyl-CoA carboxylase inhibitors; (28) Ryanodine receptor modulators; (30) GABA-gated allosteric chloride channel modulators.

Active ingredients with unknown or non-specific mechanisms of action, such as fentrifanil, fenoxacrim, cycloprene, chlorobenzilate, chlordimeform, flubenzimine, dicyclanil, amidoflumet, quinomethionate, triaraten, clothiazoben, tetrazul, potassium oleate, kerosene, metoxadiazone, gossiplur, flutensin, bromopropylate, cryolite;

Compounds from other classes, such as butacarb, dimethylan, cloetocarb, fosfocarb, pirimiphos(-ethyl), parathion(-ethyl), methacryphos, isopropyl-o-salicylate, trichlorfon, sulprofos, propafos, sebufos, pyridathion, protoate, dichlorfenthion, demeton-S-methylsulfone, isazophos, cyanofenphos, dialifos, carbofenotion, autathiophos, aromfenvinphos(-methyl), azinphos(-ethyl), chlorpyrifos(-ethyl), phosmethylan, iodofenphos, dioxabenzophos, formothion, fonophos, flupyrazophos, fensulfothion, etrimphos;

Organochlorines, such as camphechlor, lindane, heptachlor; or Phenylpyrazoles, such as acetoprole, pyrafluprole, pyriprole, vaniliprole, sisapronil; or Isoxazoline, such as sarolaner, afoxolaner, lotilaner, fluralaner;

Pyrethroids, such as (cis-, trans-)metofluthrin, profluthrin, flufenprox, flubrocitrinate, flubfenprox, fenfluthrin, protrifenbut, pyresmethrin, RU 15525, terallethrin, cis-resmethrin, heptafluthrin, bioethanomethrin, biopermethrin, fenpyritrin, cis-cypermethrin, cis-permethrin, clocitrin, cyhalothrin (lambda), chlovaportrin, or halogenated hydrocarbon compounds (HCH),

neonicotinoids, such as nitiazine

dichloromesothiasis, triflumesopyrim

macrocyclic lactones, such as nemadectin, ivermectin, latidectin, moxidectin, selamectin, eprinomectin, doramectin, emamectin benzoate; milbemycin oxime

Triphen, Epophenonan, diophenolan;

Biological substances, hormones, pheromones, for example natural products such as thuringiensin, codlemon or neem components Codlemon or Neem

dinitrophenols, such as dinocap, dinobuton, binapacryl;

benzoylureas, for example fluazuron, penfluron,

Amidine derivatives, such as Chlormebuform, Simiazole, Demiditraz

Acaricides to protect bees from Varroa mites, such as organic acids, such as formic acid, oxalic acid.

Examples of active substances from the endoparasiticide group as mixing partners include, but are not limited to, anthelmintics and antiprotozoal agents.

Anthelmintic agents include, for example, the following active substances against nematodes, trematodes and/or cestodes:

from the class of macrocyclic lactones, for example: eprinomectin, abamectin, nemadectin, moxidectin, doramectin, selamectin, lepimectin, latidectin, milbemectin, emamectin, milbemycin;

from the class of benzimidazoles and probenzimidazoles, for example: oxibendazole, mebendazole, triclabendazole, thiophanate, parbendazole, oxfendazole, netobimin, fenbendazole, febantel, thiabendazole, cyclobendazole, cambendazole, albendazole sulfoxide, albendazole, flubendazole;

from the class of depsipeptides, preferably cyclic depsipeptides, especially 24-membered cyclic depsipeptides, for example: emodepside, PF1022A;

from the class of tetrahydropyrimidines, for example: morantel, pyrantel, oxantel;

from the class of imidazothiazoles, for example: butamisole, levamisole, tetramisole;

from the class of aminophenylamidines, for example: amidantel, diacylated amidantel (dAMD), tribendimidine;

from the class of aminoacetonitriles, for example: monepantel;

from the class of paraherquiamides, for example: paraherquiamide, derquiantel;

from the class of salicylanilides, for example: tribromsalan, bromxanide, brotianide, clioxanide, closantel, niclosamide, oxyclozanide, rafoxanide;

from the class of substituted phenols, for example: nitroxynil, bithionol, disophenol, hexachlorophene, niclofolan, meniclofolan;

from the class of organophosphates, for example: trichlorfon, naphthalophos, dichlorvos/DDVP, crufomate, koumaphos, haloxone;

from the piperazine/quinoline class, for example: praziquantel, epsiprantel;

from the piperazine class, for example: piperazine, hydroxyzine;

from the class of tetracyclines, for example: tetracycline, chlortetracycline, doxycycline, oxytetracycline, rolitetracycline;

from various other classes, such as: bunamidine, niridazole, resorantel, omphalotin, oltipraz, nitroscanate, nitroxynil, oxamniquine, mirazan, miracil, lucanton, hycanton, getolin, emetine, diethylcarbamazine, dichlorphen, diamphenetide, clonazepam, befenium, amoscanate, clorsulon;

Examples of active compounds against protozoa as mixing or combination partners are, for example:

from the class of triazines, for example: diclazuril, ponazuril, letrazuril, toltrazuril;

from the class of polyether ionophores, for example: monensin, salinomycin, maduramicin, narasin;

from the class of macrocyclic lactones, for example: milbemycin, erythromycin;

from the class of quinolones, for example: enrofloxacin, pradofloxacin;

from the class of quinolones, for example: enrofloxacin, pradofloxacin;

from the quinine class, for example: chloroquine;

from the class of pyrimidines, for example: pyrimethamine;

from the class of sulfonamides, for example: sulfaquinoxaline, trimethoprim, sulfaclosine;

from the thiamine class, for example: amprolium;

from the lincosamide class, for example: clindamycin;

from the class of carbanilides, for example: imidocarb;

from the nitrofuran class, for example: nifurtimox;

from the class of quinazolinone alkaloids, for example: halofuginone;

from other classes, for example: oxamniquine, paromomycin,

from the class of vaccines or antigens of microorganisms, for example: Babesia canis rossi, Eimeria tenella, Eimeria praecox, Eimeria necatrix, Eimeria mitis, Eimeria maxima, Eimeria brunetti, Eimeria acervulina, Babesia canis vogeli, Leishmania infantum, Babesia canis canis, Dictyocaulus viviparus.

All the above mentioned mixing partners can, if they are capable on the basis of their functional groups, optionally form salts with suitable bases or acids.

Control of infection vectors

The compounds of formula (I) can also be used to combat infection vectors. For the purposes of the present invention, an infection vector is an arthropod, in particular an insect or arachnid, capable of transmitting pathogens such as, for example, viruses, worms, protozoa and bacteria from a reservoir (plant, animal, human, etc.) to a host. Pathogens can be transmitted either mechanically (e.g. trachoma by non-stinging flies) to the host, or by injection (e.g. malarial plasmodium by mosquitoes) into the host.

Examples of carriers of infections and diseases and pathogens that they may disguise include:

1) Mosquitoes

- Malarial mosquito: malaria, filariasis;

- Culex: Japanese encephalitis, filariasis, other viral diseases, transmission of worms;

- Biting: tropical fever, dengue fever, filariasis, other viral diseases, filariasis;

- Midges: transmission of worms, in particular Onchocerca volvulus;

- Butterfly flies: transmission of leishmaniasis;

2) Lice: skin infections, hospital fever;

3) Fleas: plague, hospital fever, tapeworms;

4) Flies: African trypanosomiasis (Trypanosomiasis); cholera, other bacterial diseases;

5) Ticks: acarodermatitis, hospital fever, vesicular rickettsiosis, tularemia, St. Louis encephalitis, tick-borne encephalitis (TBE), Crimean-Congo hemorrhagic fever, borrelio

6) Scabies: borreliosis such as Borrelia duttoni, tick-borne encephalitis, Australian Q fever (Coxiella burnetii), babesiosis (Babesia canis canis), ehrlichiosis.

Examples of infection vectors in the context of the present invention are insects, such as aphids, flies, grasshoppers or thrips, which are capable of transmitting plant viruses to plants, other infection vectors capable of transmitting plant viruses are spider mites, lice, beetles and nematodes.

Other examples of vectors of infections in the context of the present invention are insects and arachnids, such as mosquitoes, in particular of the genus Kusaka, Anopheles, for example A. gambiae, A. arabiensis, A. funestus, A. dims (malaria) and Culex, lice, fleas, flies, ticks and mites, capable of transmitting pathogens to animals and/or humans.

Control of infection vectors is also possible if the compounds of formula (I) are resistance-overcoming.

The compounds of formula (I) are suitable for use in the prevention of diseases and/or pathogens transmitted by vectors. Thus, another object of the present invention is the use of compounds of formula (I) for the control of vectors, for example in agriculture, horticulture, parks and recreation areas, and for the protection of materials and products in storage.

Protection of industrial materials

The compounds of formula (I) are suitable for protecting industrial materials from attack or destruction by insects, for example from the orders Coleoptera, Hymenoptera, Termites, Lepidoptera, Booklice and Bristletails.

Industrial materials in the context of the present invention are understood to mean inanimate materials, such as preferably plastics, soils, stones, paper and cardboard, leather, wood, processed wood products and coating compositions. The use of the present invention for the protection of wood is particularly preferred.

In another embodiment of the present invention, the compounds of formula (I) are used together with at least one other insecticide and/or at least one fungicide.

In another embodiment of the present invention, the compounds of formula (I) are present in the form of a pesticide ready for use, i.e. they can be applied to the material in question without further modification. Suitable other insecticides or fungicides are in particular those mentioned above.

It has been surprisingly found that compounds of formula (I) can be used to protect objects that come into contact with salt water or hard water, in particular clothing, fences, nets, buildings, anchors and signal systems, from biofouling. Likewise, compounds of formula (I), alone or in combination with other active compounds, can be used as antifouling agents.

Animal pest control in the hygiene sector

The compounds of formula (I) are suitable for controlling animal pests in the hygiene sector. In particular, the present invention can be used in the household sector, in the hygiene sector and for protecting products during storage, especially for controlling insects, arachnids and mites found in closed spaces such as living quarters, factory premises, offices, vehicle cabins, for controlling animal pests, the compounds of formula (I) are used alone or in combination with other active compounds and/or auxiliary substances. They are preferably used in household insecticidal products. The compounds of formula (I) are effective against sensitive and resistant species and against all development stages.

These pests include, for example, pests from the class Arachnida, from the orders Scorpions, Spiders and Harvestmen, from the classes Labiopoda and Diplopoda, from the class Insecta from the order Cockroaches, from the orders Coleoptera, Dermatoptera, Diptera, Bugs, Hymenoptera, Termites, Lepidoptera, Lice and Chewing Louses, Orthoptera or Orthoptera, Fleas and Bristletails and from the class Higher Crustacea from the order Isopoda.

They are used, for example, in the form of aerosols, pressure-free spray products such as atomizers and atomized sprays, automatic mist irrigation systems, aerosol sprayers, foams, gels, evaporator-based products with evaporator tablets made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, screw evaporators, energy-free or passive evaporation systems, moth paper, moth bags and in the form of gels, in the form of granules or dust, as baits for distribution or as traps.

Abbreviations and symbols

AcOH: acetic acid

aq.: aquatic

br.: wide

Boc: tert-butyloxycarbonyl

d: doublet

DAST: diethylaminosulfur trifluoride

DCC: N,N'-dicyclohexylcarbodiimide

DCM: dichloromethane

DIPEA: N,N-diisopropylethylamine

DMF: N,N- dimethylformamide

DMSO: dimethyl sulfoxide

ee: enantiomeric excess

equiv.: 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: binding constant

M: molarity

m: multiplet

MeCN: acetonitrile

MeOH: methanol

NMR: Nuclear Magnetic Resonance

q: quartet

r.t: room temperature

s: singlet

us.: saturated

T: temperature

t: triplet

T3P ^® : propylphosphonic acid anhydride

TLC: thin layer chromatography

THF: tetrahydrofuran (THF)

δ: chemical shift

Description of methods and intermediate products

Compounds of formula I and the compounds shown in Table 3 can be prepared as shown in the following scheme 1, where R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the meanings given above or denote the corresponding fragments of the compounds shown in Table 3. X is OH or Cl.

Scheme 1

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

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

Carboxylic acids of formula (b) (X=OH) and carboxylic acid chlorides of formula (b) (X=Cl) are commercially available or can be synthesized by methods known to those skilled in the art. The desired triazole compounds of formula (a) can be prepared as shown in the following scheme 2, wherein R and ^R4 are as previously described, ^R1 is _C1 - _C6 alkyl and ^R5 is _C1 - _C3 alkyl, or ^R1 , ^R3 , ^R4 and ^R5 are the corresponding moieties of the compounds shown in Table 3. LG is a suitable leaving group (see also WO2017192385).

Scheme 2

An amine of formula (c) is reacted with a substituted triazole of formula (d) to form compounds of formula (a). For example, a mixture of a triazole of formula (d), an amine of formula (c), a suitable base such as _K2CO3 , _NaH or DIPEA, in a suitable solvent such as acetonitrile or DMF, is mixed at a temperature in the range of about 20 to 120°C to form compounds of formula (a), which can then be isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

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

Amines of formula (c) and compounds of formula (f) are commercially available or can be synthesized by methods known to those skilled in the art.

The desired triazole compounds of formula (d) can be prepared as shown in the following scheme 3, wherein R ³ and R ⁴ are as previously described and R ⁵ is C ₁ -C ₃ alkyl; or R ³ , R ⁴ and R ⁵ are the corresponding moieties of the compounds shown in Table 3, LG is a suitable leaving group (see also WO 2017192385).

Scheme 3

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

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

For example:

For 5-bromo-2-hydrazinopyridine see WO 2013/038362

For 2-hydrazino-1,3-thiazole, see US 2008/0234327, WO 2018/064119, WO 2008/144767, WO 2008\121861, WO 2004046120.

Compounds of formula I and the compounds shown in Table 3 can be prepared as shown in the following scheme 4, wherein R ¹ , R ² , R ³ and R ⁴ have the meanings indicated above, and R ⁵ is C ₁ -C ₃ alkyl; or R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the corresponding moieties of the compounds shown in Table 3.

Scheme 4

An amide of formula (n) is reacted with an N,N-dimethylamide dimethyl acetal of formula (g) to form compounds of formula (o), which are then reacted with substituted hydrazines of formula (j) under acidic conditions to form compounds of formula I. For example, a compound of formula (n) and an N,N-dimethylamide dimethyl acetal of formula (g) are reacted in a suitable solvent such as CH ₂ Cl ₂ under reflux to form compounds of formula (o). After removal of the solvent, the compounds of formula (o) are 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 temperatures in the range of from about 20 to 100°C. The resulting compounds of formula I can then be isolated and, if necessary and desirably, purified using techniques well known in the art such as chromatography.

The required amides of formula (n) can be prepared as shown in the following scheme 5, where R ² and R ³ are as described previously and R ¹ is C ₁ -C ₆ alkyl or H (see also WO 2017192385); or R ¹ , R ² and R ³ are the corresponding moieties of the compounds shown in Table 3.

Scheme 5

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

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

Compounds of formulae (b) and (q) are commercially available. The required aminoamide compounds of formula (p) are commercially available or can be prepared as shown in the following scheme 6, where R ¹ and R ³ are as previously described or represent the corresponding moieties of the compounds shown in Table 3, and LG is a suitable leaving group (see also WO 2017192385).

Compounds of formulas (c) and (h) are commercially available.

The required amines of formula (p) can be prepared as shown in the following scheme 6, where R ¹ and R ³ are as described previously (see also WO 2017192385) or represent the corresponding moieties of the compounds shown in Table 3.

Scheme 6

An amine of formula (c) is reacted with an amide of formula (h) to form compounds of formula (p). For example, a mixture of an amine of formula (c), an amide _of formula (h), a suitable base such as _K2CO3 or DIPEA, in a suitable solvent such as acetonitrile or DIPEA, is mixed at 25-80°C to form compounds of formula (p), which can then be isolated and, if necessary and desirably, purified using techniques well known in the art such as chromatography.

In an alternative approach, compounds of formula I can be prepared as shown in the following scheme 7, wherein R ¹ , R ² , R ³ , R ⁴ have the meanings indicated above, and R ⁵ is ethyl, isopropyl, tert-butyl, difluoromethyl or cyclopropyl; or R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the corresponding moieties of the compounds shown in Table 3.

Scheme 7

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

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

Compounds of formula (j) can be prepared as shown in the following scheme 8, wherein E is trifluoromethoxy, difluoromethoxy or trifluoromethylsulfanyl, LG is chloro, fluoro, methylthio, methylsulfinyl or methylsulfonyl, and A is N or CH.

Scheme 3

A compound of formula (x) containing a leaving group (LG) (WO 2016/001266 for LG = methylsulfonyl) is reacted with hydrazine hydrate to form hydrazines of formula (j'). For example, a mixture of compound (x) containing a leaving group and hydrazine hydrate in a suitable solvent such as methanol or ethanol is reacted at 0-80°C to form compounds of formula (j') or their hydrochloride, hydrobromide or methanesulfonate salts, which can then be isolated and, if necessary and desirably, purified using methods well known in the art.

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

Compounds of formula (zb) can be prepared as shown in the following scheme 9, wherein R ¹ , R ² , R ³ and R ⁵ have the meanings indicated above; or R ¹ , R ² , R ³ and R ⁵ are the corresponding moieties of the compounds shown in Table 3. T is a pyridine or pyrimidine ring which is substituted with an -NH ₂ -group, -NH ₂ -group or -NH-A-group, respectively. LG is a suitable leaving group and A is CO-C ₁ -C ₆ alkyl, CO-cyclopropyl, CO-(4-fluorophenyl).

Scheme 9

The nitro compound of formula (y) is converted into the corresponding amino compound of formula under reducing conditions similar to hydrogen and palladium on carbon in a suitable solvent such as THF or ethanol (European Journal of Medicinal Chemistry, 158, 322-333; 2018), with tin(II) chloride and HCl in a suitable solvent such as ethanol (WO 2018085247), with iron powder and HCl in a suitable solvent such as ethanol (WO 2017216293), or with iron powder in a mixture of acetic acid and ethanol. The resulting amino compound (z) is reacted in the presence of a suitable base such as DIPEA or potassium carbonate with A-LG acylation or benzoylating reagents of formula (za). The resulting compounds of formula (zb) are then, if necessary and desirable, purified using techniques well known in the art, such as chromatography.

Carboxylic acid chlorides of formula (za) are commercially available or can be synthesized by methods known to those skilled in the art. The desired compounds of formula (y) can be prepared as described in Scheme 4.

Compounds of formula (ze) can be prepared as shown in the following scheme 10, wherein R ¹ , R ² , R ³ and R ⁵ are as previously defined; or R ¹ , R ² , R ³ and R ⁵ are the corresponding moieties of the compounds shown in Table 3. T is pyridine or pyrimidine substituted with an alkyl group -CO ₂ , -COOH or -CON(E ¹ )E ² , respectively. E ¹ and E ² are independently selected from the group consisting of H, C ₁ -C ₆ alkyl and cyclopropyl.

Scheme 10

The ester compound of formula (zc) is saponified to give the corresponding carboxylic acid compound of formula (zd), followed by a step of coupling the amide with amines of formula (zx) to give amides of formula (ze) by methods known to those skilled in the art.

For example, a mixture of an amine of formula (zx), a carboxylic acid (zd), a suitable coupling reagent such as T3P®, HATU, or DCC/HOBt, a suitable base such as triethylamine or DIPEA, in a suitable solvent such as ethyl acetate or DMF, are mixed at temperatures ranging from about 0 to 100°C to provide compounds of formula (ze), which can then be isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

Amines of formula (zx) are commercially available or can be synthesized by methods known to those skilled in the art. The desired compounds of formula (zc) can be prepared as described in Scheme 4.

Compounds of formula (e) can also be prepared as shown in the following scheme 11, wherein R ¹ , R ³ and R ⁴ have the meanings indicated above, and R ⁵ is C ₁ -C ₃ alkyl, or R ¹ , R ³ , R ⁴ and R ⁵ are the corresponding moieties of the compounds shown in Table 3.

Scheme 11

An amide of formula (zf) is reacted with an N,N-dimethylamide dimethyl acetal of formula (g) to form compounds of formula (zg), which are then reacted with substituted hydrazines of formula (j) under acidic conditions to form compounds of formula (zh). For example, a compound of formula (zf) and an N,N-dimethylamide dimethyl acetal of formula (g) are reacted in a suitable solvent such as CH ₂ Cl ₂ at reflux temperature to form compounds of formula (zg). After removal of the solvent, the compounds of formula (zg) are 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 from about 20 to 80 °C. The resulting compounds of formula (zh) can then be isolated and, if necessary and desirable, purified using techniques well known in the art, such as chromatography.

The carbamate of formula (zh) is treated with an acid to form amines of formula (a). For example, the carbamate of formula (zh) and a suitable acid such as hydrochloric acid 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 of from 0 to 80 °C. The resulting amines of formula (a) can then be isolated as their acid salts after treatment with a base as free amines and, if necessary and desired, purified using methods well known in the art such as chromatography.

The required amides of formula (zf) and hydrazines of formula (j) are commercially available or can be synthesized by the methods described in this application or by methods known to those skilled in the art.

Compounds of formula (zj) can be prepared as shown in the following scheme 12, where R ¹ , R ² , R ³ and R ⁵ are as previously defined; or R ¹ , R ² , R ³ and R ⁵ are the corresponding moieties of the compounds shown in Table 3. LG is a suitable leaving group such as chlorine, bromine or iodine, Rz is optionally substituted 5-6 membered heteroaryl or methylsulfonyl.

Scheme 12

The desired compounds of formula (zi) can be prepared as described in Scheme 4.

For example, LG may be bromine, which may be replaced by an appropriate nucleophile, for example in a transition metal catalyzed reaction with a substituted pyrazole or triazole or sulfinate, according to well-known methods. For example, in the case of replacing bromine with pyrazoles, see: WO 2013/062981 A1 p. 37, example 6, step 1.

Compounds of formula (zl) can be prepared as shown in the following scheme 13, where R ¹ , R ² , R ³ and R ⁵ are as defined previously. Hal is chlorine, bromine or iodine.

Scheme 13

Compounds of formula (zk) can be further derivatized by halogenation of the thiazole. The required methods are known to those skilled in the art. For example, chlorination is carried out using a halogenating agent such as N-chlorosuccinimide in a suitable solvent such as DMF (the synthesis of example II-15 is described in this application).

Compounds of formula (zk) can be prepared as shown in Schemes 1-7 and 11.

Scheme 14 illustrates the preparation of 3-haloalkyltriazole containing amines (e'), which is used for the synthesis of, for example, Example I-9. R ⁵ is difluoromethyl and E' is CN.

Scheme 14

In the first step, the hydrazone amide (zn) is formed as described in EP 1 099 695. In the second step, (α,S)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride, prepared from (α,S)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) and oxalyl chloride according to Tetrahedron: Asymmetry, 21(8), 936-942, 2010, is reacted with the hydrazone amide in the presence of a base such as pyridine, as described in EP 1 099 695, to form a triazole of formula (zo); partial or complete racemization is possible. In the third step, the phthalimide protecting group is removed by reaction with hydrazine hydrate in a suitable solvent such as ethanol, as described in WO 2018086605. In the final step, the resulting amine (e') is reacted with a carboxylic acid to form exemplary compounds, such as I-9, as described in Scheme 1.

Scheme 15 illustrates the preparation of alkyltriazole-containing amines (e') that are used to synthesize, for example, Example 1-6. R ⁵ is ethyl, isopropyl, or cyclopropyl, and E' is CN. Z is NH ₂ or OC ₁ -C ₆ alkyl.

Scheme 15

N-(tert-butoxycarbonyl)-L-alanine reacts with an alkylamine (for Z=NH ₂ ) or an alkyl imidate (for Z=OC ₁ -C ₆ alkyl) to form intermediates of formula (zq), which are then reacted with substituted hydrazines of formula (j'') to form alkyltriazoles of formula (zr). For example, in the case of Z= _NH2 (cf. J. Org. Chem. 2011, 76, 1177-1179), N-(tert-butoxycarbonyl)-L-alanine and an alkyl amidine of formula (zp) are reacted in the presence of a suitable coupling reagent such as HATU, a suitable base such as triethylamine or DIPEA, in a suitable solvent such as DMF, at a temperature in the range of from 0 to 50 °C to form an acylamidine intermediate of formula (zq). After removal of the solvent, the intermediates of formula (zq) are reacted with a substituted hydrazine of formula (j") in a suitable solvent such as acetic acid, at a temperature in the range of from about 20 to 80 °C. The resulting alkyl triazoles of formula (zr) can then be isolated and, if necessary and desirably, purified using techniques well known in the art, such as chromatography.

In the case of Z= _OC1 - _C6, the alkyl N-(tert-butoxycarbonyl)-L-alanine and the alkyl imidate of formula (zp) or a suitable salt thereof are reacted in the presence of a suitable coupling reagent such as HATU, a suitable base such as triethylamine or DIPEA, in a suitable solvent such as THF, at a temperature of from 0 to 25°C to form acyl imidate intermediates of formula (zq). Upon addition of a substituted hydrazine of formula (j"), the intermediate of formula (zq) is reacted at a temperature of from 20 to 80°C to form alkyl triazoles of formula (zr), which can then be isolated and, if necessary and desired, purified using techniques well known in the art such as chromatography.

Carbamates of formula (zr) are treated with acid (e.g. 4N HCl in dioxane) to form amines of formula (e') as shown in Scheme 11.

The required alkyl amidines and alkyl imidates or their suitable salts and hydrazines of formula (j'') are commercially available or can be synthesized by the methods described in this application or by methods known to those skilled in the art.

Scheme 16 illustrates the preparation of alkoxytriazole-containing amines (e1), which are used for the synthesis of, for example, Example 1-10. Alkyl is methyl, ethyl, or isopropyl, and E' is CN.

Scheme 16

The synthesis begins with the reaction of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl chloride with potassium thiocyanate (KSCN) in acetone to afford the corresponding isocyanate intermediate (zs), which is treated in the next step with the appropriate alcohol to afford O-alkyl [(2S)-2-(l,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioates (zt). The reaction between the intermediate (zt) and hydrazine of formula (j'') in ethanol affords cyclized products of formula (zu), as described in Bioorganic & Medicinal Chemistry 26 (2018) 3321–3344. Deprotection of the amino group with hydrazine hydrate affords primary amines of formula (e1). In the final step, the resulting amine is reacted with a carboxylic acid to form example compounds, for example, 1-10, as described in Scheme 1.

Compounds of formula (zw) can be prepared as shown in the following scheme 17, wherein Alk is C ₁ -C ₆ alkyl, R ⁴ is 5-cyanopyridin-2-yl and R ⁵ is ethyl, n-propyl, isopropyl, cyclopropyl or t-butyl.

Scheme 17

(α,S)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride is reacted with an imidate (zq) or a suitable salt thereof to form an intermediate acyl imidate of formula (zv), which is then reacted with a hydrazine of formula (j) to give triazoles of formula (zw). For example, a mixture of the acid chloride and imidate of formula (zv) is reacted in a suitable solvent such as THF at a temperature of from 20 to 25 °C. The resulting intermediates of formula (zv) are then reacted with hydrazines of formula (j) in a suitable solvent such as THF at a temperature of from 0 °C to 80 °C. The resulting triazoles of formula (zw) are then, if necessary and desired, purified 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 give the corresponding free amines.

The required acid chloride can be prepared as described in Scheme 14, and the imidates of formula (zq) or their salts are commercially available or can be synthesized by methods known to those skilled in the art.

Scheme 18 illustrates the preparation of 3-halotriazole-containing amines (e') used to synthesize, for example, Example 1-39, where R ⁵ is halogen and E' is CN.

Scheme 18

In the first step, (α,S)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) reacts with 1-N-Boc-2-methyl-isothiourea (purchased from ABCR) in the presence of a base and the coupling reagent HATU to form N-acylated 1-N-Boc-2-methyl-isothiourea of formula (ya); partial or complete racemization is possible. In the second step, cyclization occurs with hydrazines (j'') (e.g. E' is CN) and in the presence of a base such as pyridine, as described in WO 2014009425 A1, to form 1,2,4-triazoles of formula (yb) containing an NH-Boc group. After deprotection of N-Boc in the third step under acidic conditions (e.g. 4N HCl in dioxane) 3-amino-1,2,4-triazole hydrochlorides of formula (yc) are formed, which can be treated in the fourth step with tert-butyl nitrite and then copper halides as salts like CuCl ₂ (R ⁵ = Cl) described in N. Desroy et al., J. Med. Chem. 2013, 56, 1418–1430, CuBR ² (R ⁵ = Br) as described in JP-Pat. 2010070503 A, CuI/I ₂ mixtures (R ⁵ = I) as described in K. Pchalek and M. P. Hay J. Org. Chem. 2006, 71, 6530-6535, or with diiodomethane (R ⁵ =I), as described in NR Norcross et al. J. Med. Chem., 2016, 59(13), 6101-6120, forming 3-halosubstituted 1,2,4-triazoles (yd). Alternatively, fluorine (R ⁵ =F) can be introduced, for example, using HF instead of copper halides, as described, for example, by V. Krchnak and Z. Arnold Coll. Czech. Chem. Common., 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 WO 2018086605. In the last step, the resulting amines (e') are reacted with carboxylic acids to form example compounds, such as 1-39 or 1-48, as described in Scheme 1.

Examples of receipt

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 1-9)

Stage 1

2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoroethaneimidic acid

To 2.33 g (17.4 mmol) of 5-hydrazinyl-2-pyridinecarbonitrile in methanol (30 ml) was added 3.15 g (24.3 mmol) of ethyl 2,2-difluoroethanecarboximidate (purchased from Enamine Building Blocks) and the reaction mixture was stirred 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 give 3.38 g (purity: 90.4%; yield: 83.0%) of 2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoroethanimidine acid.

ESI mass [m/z]: 211.1 [M+H] ⁺

Stage 2

2-[1-[3-(difluoromethyl)-1-(6-cyano-3-pyridinyl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione

To 3.28 g (14.0 mmol) of 2-[6-cyano-3-pyridinyl]hydrazide-2,2-difluoroethanimidine acid in pyridine (20 mL) was added 3.32 g (14.0 mmol) of (α)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetyl chloride (see preparation from (α,S)-1,3-dihydro-α-methyl-1,3-dioxo-2H-isoindole-2-acetic acid (Pht-Ala-OH, purchased from ABCR) and oxalyl chloride: DA Gruzdev et al., Tetrahedron: Asymmetry, 21(8), 936–942, 2010), and the reaction mixture was stirred at room temperature overnight. Water (200 ml) was then added and the mixture was extracted with dichloromethane (200 ml). The organic phase was extracted twice with saturated aqueous NaHCO3 (100 ml), dried over _Na2SO4 and evaporated under reduced pressure. The remaining solid residue was chromatographed with a cyclohexane/ _acetone gradient on silica gel to afford 1.09 g (purity: 95.7%, yield: 18.8%) of the racemic title compound as a colourless solid.

ESI mass [m/z]: 395.2 [M+H] ⁺

Stage 3

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

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) was added 577 mg (6.34 mmol) of hydrazine hydrate and the reaction mixture was heated under reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated under reflux for another hour, acetone (15 mL) was added and heating was continued for another 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give 663 mg of 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.

ESI mass [m/z]: 265.2 [M+H] ⁺

¹ H-NMR peak list see Table 2 (INT-4).

Stage 4

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

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

ESI mass [m/z]: 471.1 [M+H] ⁺

¹ H-NMR peak list see Table 1.

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

Stage 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

A solution of 5.00 g (95% pure, 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 of absolute _CH2Cl2 was treated with 3.78 mL (43.3 mmol) of oxalyl chloride at 0 °C. The reaction mixture was stirred for 2 days at ambient temperature. All volatiles were removed under reduced pressure, and the residue was used for the next step without further purification.

To a solution of 3.13 g (95% purity, 21.6 mmol) of methyl 2-methylpropanimidate hydrochloride (1:1) in 40 ml of absolute THF were added 15.1 ml (86.4 mmol) of absolute DIPEA at 0°C. The acid chloride obtained in the first step was dissolved in 20 ml of absolute THF and added dropwise to the imidate solution over 25 min. After stirring for 30 min at 0°C, 3.19 g (23.7 mmol) of 6-hydrazinonicotinonitrile and 10 ml of absolute THF were added. The reaction mixture was stirred for 30 min at 0°C and overnight at ambient temperature. All volatiles were removed under reduced pressure. To the residue were added 200 ml of water 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 . The solvent was removed under reduced pressure and the residue was purified by chromatography on silica (cyclohexane/ethyl acetate) to yield 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.

ESI mass [m/z]: 387.5 [M+H] ⁺

Stage 2

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

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 for 2 h at 80 °C. The resulting suspension was stirred overnight at ambient temperature and then cooled to 10 °C. The mixture was filtered and the residue was washed with ice-cold ethanol. The filtrate was concentrated under reduced pressure to give 1.57 g (70% purity) of 6-{5-[(1S)-1-aminoethyl]-3-isopropyl-1H-1,2,4-triazol-1-yl}nicotinonitrile.

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)

Stage 1

tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}carbamate

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 h. 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 h and then at room temperature overnight. The reaction mixture was cooled to room temperature, saturated aqueous _Na2CO3 solution was added and then the mixture was extracted with EtOAc. The combined organic layers were washed with water, aqueous 5% _NaH2PO4 solution, _brine and finally dried over _Na2SO4 . After filtration and evaporation of the solvent in vacuo _, 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%).

ESI mass [m/z]: 355.3 [M+N] ⁺

¹ H-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)

Stage 2

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

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 at room temperature overnight. The resulting precipitate was collected by filtration and air-dried to give the title compound (0.71, 100%).

ESI mass [m/z]: 255.1 [M+H-HCl] ⁺

Stage 3

3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-cyclopropyl-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide

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) were added 0.01 mL (0.48 mmol) of N,N-diisopropylethylamine, followed by 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 at room temperature overnight. The reaction mixture was quenched with an aqueous solution of 5% NaH ₂ PO ₄ and then extracted with dichloromethane. The organic phase was dried over _{Na2SO4 ,} filtered and after evaporation of the solvent in vacuo 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%).

ESI mass [m/z]: 461.2 [M+N] ⁺

¹ H NMR peak list see Table 1.

Synthesis of 3-chloro-N-{(1S)-1-[l-(5-cyanopyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethyl}-5- (trifluoromethyl)benzamide (Example I-10)

Stage 1:

O-methyl[(2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoyl]carbamothioate

To a solution of 1.0 g (4.6 mmol) of (2S)-2-(1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)propanoic acid in toluene (15 ml) were added 0.80 ml (9.12 mmol) of oxalyl chloride and one drop of N,N-dimethylformamide. The reaction mixture was stirred for 3 h at room temperature, 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 h and finally evaporated. The crude residue was dissolved in acetone (15 ml), then 0.44 g (4.56 mmol) of KSCN as a solution in acetone (5 ml) were added and the mixture was stirred at 60 °C for 2 h. Then 0.46 ml (11.4 mmol) of methanol was added and the mixture was stirred at 60 °C overnight, cooled to room temperature and evaporated under reduced pressure. The resulting residue was dissolved in EtOAc, washed with water and _brine respectively, and finally the organic layer was dried over anhydrous _Na2SO4 and then concentrated under reduced pressure. The crude product was purified by silica gel chromatography to give the title compound (0.82 g, 59%).

ESI mass [m/z]: 293.1 [M+H] ⁺

Stage 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

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

ESI mass [m/z]: 375.1 [M+H] ⁺

Stage 3:

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

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

ESI mass [m/z]: 245.1 [M+H] ⁺

Stage 4:

3-chloro-N-{(1S)-1-[1-(5-cyanopyridin-2-yl)-3-methoxy-1H-1,2,4-triazol-5-yl]ethyl}-5-(trifluoromethyl)benzamide

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) were added 0.74 ml (1.15 mmol) of N,N-diisopropylethylamine, followed by 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% aqueous NaH ₂ PO ₄ and then extracted with dichloromethane. The organic phase was dried over Na ₂ SO ₄ , filtered and evaporated under reduced pressure. The crude material was purified by preparative HPLC (water/acetonitrile, 0.1% formic acid). The combined product fractions were evaporated and the residue was purified by silica gel chromatography to give the title compound (75 mg, 20%).

ESI mass [m/z]: 451.2 [M+N] ⁺

¹ H NMR peak list see Table 1.

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

Stage 1:

tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate

To a solution of 2.00 g (10.6 mmol) of N2-(tert-butoxycarbonyl)-L-alanine amide in 40 mL of CH ₂ Cl ₂ was added 2.1 mL (16 mmol) of N,N-dimethylformamide dimethyl acetal. The solution was heated under reflux for 2 h, after which the solvent was removed under reduced pressure. The residue was dissolved in a mixture of 20 mL of 1,4-dioxane and 20 mL of glacial acetic acid. 1.7 g (13 mmol) of 6-hydrazinocotinonitrile was added and the mixture was stirred at 50 °C for 60 min. The solvents were removed under reduced pressure, saturated aqueous NaHCO ₃ solution was added and the mixture was re-extracted with ethyl acetate. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure. The residue was purified by reverse phase chromatography ( _H2O /acetonitrile) to give 3.0 g of tert-butyl {(1S)-1-[1-(5-cyanopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}carbamate. (c=1.0; ethanol)

^1H NMR (DMSO- _d6 , 400 MHz): 9.10 (s, 1H), 8.57 (dd, 1H), 8.21 (s, 1H), 8.05 (d, 1H), 7.52 (d, 1H), 5.63 (m, 1 N), 1.43 (d, 3 N), 1.31 (s, 9 N).

ESI mass [m/z]: 259.2 [M-S ₄ N ₈ + N] ⁺

Stage 2:

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

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 were added 23 ml of 4 M HCl solution in 1,4-dioxane. The mixture was stirred for 4 h at 50 °C and overnight at room temperature. The solvent was removed under reduced pressure to give 2.81 g of a residue containing 6-{5-[(1S)-1-aminoethyl]-1H-1,2,4-triazol-1-yl}nicotinonitrile hydrochloride. It was used without further purification.

^1H NMR (DMSO- _d6 , 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

To a solution of 500 mg (2.60 mmol) of 5-(difluoromethoxy)-2-(methylsulfanyl)pyrimidine in 2 ml of ethanol was added 0.52 ml (11 mmol) of hydrazine hydrate. The mixture was refluxed overnight. The reaction mixture was then cooled to 5°C, during which a white precipitate formed. The suspension was filtered and the precipitate was washed with ethanol. The residue was dried under reduced pressure, yielding 125 mg of 5-(difluoromethoxy)-2-hydrazinopyrimidine.

¹ H NMR (DMSO-d6, 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)

Stage 1:

3-chloro-5-(difluoromethyl)benzonitrile

A solution of 5.00 g (30.1 mmol) of 3-chloro-5-formylbenzonitrile in 150 mL _{of CH2Cl2} was treated with 5.84 g (36.2 mmol) of diethylaminosulfur trifluoride (DAST) and stirred for 2 h at room temperature. The reaction was quenched by careful addition of saturated _NaHCO3 solution and the mixture was re-extracted _{with CH2Cl2} . The combined organic layers were washed with brine and dried over _Na2SO4 . The solvent was removed under reduced pressure to yield 5.31 g of 3-chloro-5-(difluoromethyl)benzonitrile, which was used without further _purification .

EI mass [m/z]: 187 [M] ⁺

Stage 2:

3-chloro-5-(difluoromethyl)benzoic acid (INT-10)

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 for 45 min at this temperature. Then all the volatiles were removed under reduced pressure. Water was added and the pH was adjusted to 1 using concentrated hydrochloric acid. The mixture was re-extracted with EtOAc. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ and the solvent was removed under reduced pressure to yield 278 mg of 3-chloro-5-(difluoromethyl)benzoic acid, which was used without further purification in the synthesis of Example II-12.

¹ H 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+N] ⁺

Synthesis of 3-chloro-5-(difluoromethyl)benzoic acid (INT-09)

Stage 1:

O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate

38.9 mL (279 mmol) of triethylamine, 1.14 g (9.3 mmol) of N,N-dimethylpyridin-4-aminomethyl (DMAP), and 13.8 g (112 mmol) of dimethylcarbamothioyl chloride were 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 resulting precipitate was filtered off, washed with 150 ml of a mixture of diethyl ether and n-hexane, 1:1, dried in vacuum at 60°C (1 torr, 3 h) to obtain 9.3 g (86%) of O-(3-chloro-5-cyanophenyl)dimethylcarbamothioate as colorless crystals.

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

Stage 2:

3-chloro-5-sulfanylbenzoic acid

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

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

Stage 3:

3-chloro-5-sulfanylbenzoic acid

A hot (ca. 70°C) solution of 68.5 g (1.71 mol) NaOH in 300 ml water was added to a suspension of 27.5 g (114 mmol) S-(3-chloro-5-cyanophenyl)dimethylcarbamothioate in 700 ml warm (ca. 40°C) methanol. The reaction mixture was stirred under reflux (20 h). Methanol was removed in vacuo and the aqueous solution was washed with 2×200 ml diethyl ether. The aqueous layer was separated and added dropwise to a suspension of 300 g ice in concentrated aqueous HCl (under argon, cooling with an ice bath). The resulting solution was filtered, washed with 2×50 ml water, 50 ml n-hexane and dried in vacuo at 60°C (1 Torr, 3 h). 21.2 g (98%) of 3-chloro-5-sulfanylbenzoic acid were obtained as a white powder.

¹ H 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 instrument).

Stage 4:

3-chloro-5-[(difluoromethyl)sulfanyl]benzoic acid (INT-09)

12.44 g (90 mmol) of K ₂ CO ₃ and 18.3 g (120 mmol) of sodium chloro(difluoro)acetate were successively added to 11.32 g (60 mmol) of 3-chloro-5-sulfanylbenzoic acid in anhydrous DMF under argon atmosphere. The reaction mixture was stirred at 95-100°C for 3 h. Caution: At 90-95°C CO ₂ is evolved intensively. The volatiles 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 h, the precipitate was filtered off, washed with water 2×50 ml and a mixture of n-hexane and diethyl ether, 1/1. Vacuum drying at 60 °C (1 Torr, 3 h) gave 11 g of 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.

¹ H NMR (400 MHz, CDCl ₃ ) δ: 6.90 (t, 1H, J=74.4 Hz), 7.83 (t, 1H, J=2 Hz), 8.14 (t, 1H, J=2 Hz), 8.20 ( s, 1H), 10.50 (brs, 1H). (measured on Varian Gemini 2000).

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

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 dimethyl acetal in 40 mL of dichloromethane was heated to reflux. After 1 h, 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 for 1 h at 100 °C. The solvent was removed under reduced pressure. Water was added to the residue and the mixture was re-extracted with EtOAc. The combined organic layers were washed with _brine , dried over _Na2SO4 and filtered. The filtrate was concentrated under reduced pressure to give 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.

ESI mass [m/z]: 474.2 [M+H] ⁺

Stage 2:

6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]ethyl}-1H-1,2,4-triazol-1-yl)-N-cyclopropyl-N-methylnicotinamide (example II-38)

To a solution of 250 mg (0.52 mmol) of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]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% solution of T3P (cyclic propanephosphonic anhydride) 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 give 113 mg of 6-(5-{(1S)-1-[3,5-bis(trifluoromethyl)benzamido]ethyl}-1H-1,2,4-triazol-1-yl)-N-cyclopropyl-N-methylnicotinamide.

ESI mass [m/z]: 527.2 [M+H] ⁺

¹ H NMR peak list see table 3

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)

Stage 1:

N-{(1S)-1-[1-(5-aminopyridin-2-yl)-1H-1,2,4-triazol-5-yl]ethyl}-3-chloro-5-(trifluoromethyl)benzamide

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 volatiles 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 , dried over _Na2SO4 , 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.

ESI mass [m/z]: 411.2 [M+N] ⁺

Stage 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)

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 2-methylpropanoyl chloride and 30 μl (0.21 mmol) of triethylamine. The reaction mixture was stirred overnight at room temperature. All volatiles 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.

ESI mass [m/z]: 481.2 [M+H] ⁺

¹ H NMR peak list see table 3

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)

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 overnight at room temperature. Conversion of the starting material was incomplete, so an additional 0.73 g (4.1 mmol) of N-bromosuccinimide was added and stirring was continued for 5 h. Aqueous sodium bisulfite was added and the mixture was re-extracted with EtOAc. The combined organic layers were washed with water, aq. saturated NaHCO ₃ solution and brine. All volatiles were removed under reduced pressure and the residue was purified by silica chromatography (cyclohexane/EtOAc) to give 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.

ESI mass [m/z]: 497.9 [M+H] ⁺

¹ H NMR peak list see table 3

Synthesis of 3,5-di(trifluoromethyl)-N-{1-[3-chloro-1-(3-cyano-pyridin-6-yl)-1H-l,2,4-triazol-5-yl]ethyl} -benzamide (example I-39)

Stage 1

tert-butyl N-[(E)-N-[2-(1,3-dioxoisoindolin-2-yl)propanoyl]-C-methylsulfanylcarbonimidoyl]carbamate

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-methylisothiourea (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 for 2 hours at 80 °C. Then, water was added, and the mixture was extracted with sodium hydrogen carbonate solution and dichloromethane. The organic phase was separated, dried over _Na2SO4 , filtered and the solvent _was evaporated. The remaining solid residue was purified by chromatography with a cyclohexane/acetone gradient on silica gel to give 1.40 g (purity: 97.0%, yield: 69.6%) of the racemic title compound.

ESI mass [m/z]: 392.2 [M+H] ⁺

¹ H-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)

Stage 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

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

ESI mass [m/z]: 404.3 [M-H ₂ C=(CH ₃ ) ₂ ] ⁺

¹ H-NMR peak list (400 MHz, DMSO-d6, 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)

Stage 3

2-[1-[3-amino-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione hydrochloride

1.9 g (4.14 mmol) of 2-[1-[3-(N-Boc-amino)-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione was treated with 4 N HCl in dioxane (50 mL) and the reaction mixture was stirred for 18 h at room temperature. The reaction mixture was then concentrated and the racemic solid residue was used for halogen introduction (step 4) without purification.

ESI mass [m/z]: 360.3 [M-HCl] ⁺

¹ H-NMR peak list (400 MHz, DMSO-d6, 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)

Stage 4

2-[1-[3-chloro-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione

To 1.14 g (3.17 mmol) of 2-[1-[3-amino-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione hydrochloride in acetonitrile (91.2 ml) were added 725.1 mg (5.39 mmol) of Cu(II) chloride and then 458.0 mg (4.44 mmol) of tert-butyl nitrite were added dropwise to the reaction mixture at room temperature. The reaction mixture was then stirred for 1 h at 70°C, 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 cyclohexane/acetone gradient chromatography on silica gel to give 670 mg (purity: 100%, yield: 55.7%) of the racemic title compound.

ESI mass [m/z]: 379.1 [M+H] ⁺

Stage 5

6-[5-(1-aminoethyl)-3-chloro-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-11)

To 650.0 mg (1.71 mmol) of 2-[1-[3-chloro-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl)ethyl]-1H-isoindole-1,3(2H)-dione in ethanol (36.1 mL) was added 390.5 mg (4.29 mmol) of hydrazine hydrate and the reaction mixture was heated under reflux. After 30 min, a colorless precipitate formed. The reaction mixture was stirred and heated under reflux for another two hours, acetone (10 mL) was added and heating was continued for another 30 min. The reaction mixture was concentrated and the solid residue was treated with ethanol. After filtration, the filtrate was evaporated under reduced pressure to give racemic 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.

ESI mass [m/z]: 249.2 [M+H] ⁺

Stage 6

3,5-di(trifluoromethyl)-N-{1-[3-chloro-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}-benzamide (Example I-39)

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) were added 146.6 mg (0.55 mmol) of 3,5-bis(trifluoromethyl)benzoic acid, 100 mg (0.77 mmol) of N,N-diisopropylethylamine (Hunig's base) in acetonitrile (6.25 mL), 258.3 mg (0.67 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N/N',N'-tetramethyluronium hexafluorophosphate] (HATU), and the reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure and the solid residue was treated with _{dichloromethane} and then extracted with saturated aqueous _NaHCO3 and water. The organic phase was separated, dried over _Na2SO4 and the solvent was evaporated under reduced pressure. The remaining brown oily substance was purified by preparative HPLC with a neutral gradient of water/acetonitrile to give 106.0 mg (purity: 100%, yield: 39.3%) of the racemic title compound.

ESI mass [m/z]: 489.1 [M+H] ⁺

¹ H NMR peak list see table 1

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

Stage 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

To 250.0 mg (0.69 mmol) of 2-[1-[3-amino-1-(3-cyanopyridin-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 Cu(II) bromide, and then the reaction mixture was treated dropwise at room temperature with 110.0 mg (1.06 mmol) of tert-butyl nitrite. Then the reaction mixture was stirred for 1 h at 70 °C, followed by treatment with ethyl acetate and extraction 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 chromatographed with a cyclohexane/acetone gradient on silica gel to give 300 mg (purity: 96.2%) of the racemic title compound.

ESI mass [m/z]: 423.3 [M+N] ⁺

Stage 2

6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile (INT-12)

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

ESI mass [m/z]: 293.0 [M+H] ⁺

Stage 3

3,5-di(trifluoromethyl)-N-{1-[3-bromo-1-(3-cyanopyridin-6-yl)-1H-1,2,4-triazol-5-yl]ethyl}benzamide (Example I-48)

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) were added 170.0 mg (0.63 mmol) of 3,5-bis(trifluoromethyl)benzoic acid, 115.9 mg (0.89 mmol) of N,N-diisopropylethylamine (Hunig's base) in acetonitrile (6.25 mL), 299.4 mg (0.78 mmol) of [O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate] (HATU), and the reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under reduced pressure and the solid residue was treated with _{dichloromethane} and then extracted with saturated aqueous _NaHCO3 and water. The organic phase was separated, dried over _Na2SO4 and the solvent was evaporated under reduced pressure. The remaining brown oily substance was purified by preparative HPLC with a water/acetonitrile gradient to give 81.0 mg (purity: 94.8%, yield: 22.5%) of the racemic title compound.

ESI mass [m/z]: 535.0 [M+N] ⁺

¹ H NMR peak list see table 1

Synthesis of 3-chloro-5-[(trifluoromethyl)sulfanyl|benzoic acid

Stage 1:

[3-chloro-5-(methoxycarbonyl)phenyl]boronic acid

To a suspension of 12 g (40 mmol) of methyl 3-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate in 30 ml of acetone and 30 ml of H ₂ O were added 17.3 g (80.9 mmol) of sodium periodate and 6.24 g (80.9 mmol) of ammonium acetate. The mixture was stirred at 25 °C for 2 h and then filtered through celite. The filtrate was evaporated. The residue was diluted with 200 ml of ethyl acetate and washed with 100 ml of H ₂ O. The organic phase was washed with brine, 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 min. 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.

¹ H-NMR (400 MHz, CDCl ₃ ): δ=8.72 (s, 1H), 8.35 (s, 1H), 8.27 (s, 1H), 4.02 (s, 3H). Associated with trace signal of CHCl ₃ at 7.25 ppm. Measured on a Varian 400MR NMR instrument.

Stage 2:

Methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate

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 sieves in 500 mL of DMF were stirred at 25 °C for 16 h under N ₂ . The mixture was filtered through celite. The filtrate was diluted with 1.5 L of methyl tert-butyl ether and washed with 2×500 mL of _H2O . The organic phase was washed with brine, dried over _{anhydrous Na2SO4} , filtered and concentrated in vacuo. The crude product was purified by silica gel MELC (petroleum ether:ethyl acetate = 1:0-20:1) to give 5.5 g of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate as a light yellow oil.

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). Associated with trace signal of CHCl ₃ at 7.25 ppm. Measured on a Varian 400MR NMR system.

Stage 3:

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

5.5 g (20 mmol) of methyl 3-chloro-5-[(trifluoromethyl)sulfanyl]benzoate were dissolved in a mixture of 12 ml of tetrahydrofuran and 12 ml of _H2O . To the mixture was added 1.63 g (40.6 mmol) of NaOH, then stirred at 25°C for 2 h. The mixture was adjusted to pH 5 by adding 40 ml of 1 M HCl and extracted with 150 ml of ethyl acetate. The organic phase was washed with brine, dried over _{anhydrous Na2SO4} , filtered and concentrated in vacuo. The crude product was triturated with 50 ml of petroleum ether at 25°C for 15 min. The mixture was filtered and the residue was dried under reduced pressure to give 3.0 g of 3-chloro-5-(trifluoromethylsulfanyl)benzoic acid as a yellow solid.

¹ H-NMR (400 MHz, CDCl ₃ ): δ=11.28 (br s, 1H), 8.29 (s, 1H), 8.20-8.25 (m, 1H), 7.91 (s, 1H). Associated with trace signal of CHCl ₃ at 7.25 ppm. Measured on a Varian 400MR NMR instrument.

ESI mass [m/z]: 254.8 [M-N] ^-

LC-MS analysis was performed using acetonitrile and 10 mM aqueous ammonium bicarbonate as mobile phase; linear gradient from 15% acetonitrile to 90% acetonitrile, flow rate 0.80 ml/min; instruments: Agilent 1200 and Agilent 6120. Chromatography was performed using an Xbridge Shield RPC18 2.1*50 mm column (5 μm particles). Detection methods were diode array detection (DAD), evaporative light scattering detection (ELSD), and electrospray negative ionization.

Synthesis of 3-chloro-5-(pentafluoroethyl)benzoic acid (intermediate INT-13)

Stage 1:

methyl 3-chloro-5-(pentafluoroethyl)benzoate

To methyl 3-chloro-5-iodobenzoate (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, monitoring by TLC. Water (200 mL) and EtOAc (300 mL) were added to the reaction mixture, 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%).

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 on a Bruker 400 MHz NMR instrument.

Stage 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). To the above solution was added LiOH (1.66 g, 69.3 mmol) in _H2O (50 mL), and the mixture was stirred at 25 °C for 5 h, monitoring 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 1 N HCl to pH = 5-6, 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, 84.0% yield).

¹ H-NMR (400 MHz, MeOD): δ=8.24 (s, 1H), 8.14 (s, 1H), 7.88 (s, 1H). Measured on a Bruker 400 MHz NMR device.

ESI mass [m/z]: 272.9 [M] ⁺

Synthesis of 3-(difluoromethyl)-5-(trifluoromethoxy)benzoic acid (intermediate INT-14)

Stage 1:

1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene

To a solution of 5.00 g (18.5 mmol) of 3-bromo-5-(trifluoromethoxy)benzaldehyde in 100 mL _{of CH2Cl2} was added 3.0 mL (23 mmol) of diethylaminosulfur trifluoride. The reaction mixture was stirred for 2 h at room temperature. After this time, the reaction mixture was quenched with saturated aqueous _NaHCO3 and extracted with _CH2Cl2 . The combined organic layers _were dried over _{Na2SO4 ,} filtered, and concentrated under reduced pressure. NMR analysis of the crude product revealed incomplete conversion of the starting material. Therefore, the residue was redissolved in 100 mL _{of CH2Cl2} 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 _CH2Cl2 . The combined organic layers _{were dried over Na2SO4 , filtered} and concentrated under reduced pressure to give 4.87 g of a residue containing 1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene. A portion of this crude material was purified by silica chromatography (cyclohexane/EtOAc) to give 1.78 g of pure 1-bromo-3-(difluoromethyl)-5-(trifluoromethoxy)benzene. This was used for the next carbonylation reaction.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ=7.92 (s, 1H), 7.88 (s, 1H), 7.65 (s, 1H), 7.10 (t, J=55 Hz, 1H).

EI mass [m/z]: 290, 292 [M] ⁺

Stage 2:

Methyl 3-(difluoromethyl)-5-(trifluoromethoxy)benzoate

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 the adduct of dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) and acetone. The solution was then stirred for 16 h at 80°C in an autoclave under carbon monoxide (5 bar). 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.

EI mass [m/z]: 270 [M] ⁺

Stage 3:

3-(difluoromethyl)-5-(trifluoromethoxy)benzoic acid

To the solution from the first stage were added 70 ml of THF and 5.3 ml of 45% aqueous sodium hydroxide solution. The mixture was heated under reflux for 45 min, then acidified to pH 1-2 with conc. hydrochloric acid. The resulting precipitate was removed by filtration. The filtrate was evaporated to dryness. Water was added to the residue and the mixture was extracted several times with diethyl ether. The combined organic layers were washed with brine, dried over Na ₂ SO ₄ , filtered and concentrated under reduced pressure to give 1.44 g of methyl 3-(difluoromethyl)-5-(trifluoromethoxy)benzoate.

¹ H-NMR (DMSO-d ₆ , 400 MHz): δ=13.8 (brs, 1H), 8.15 (s, 1H), 7.98 (s, 1H), 7.89 (s, 1H), 7.20 (t, J=55 Hz, 1H).

ESI mass [m/z]: 254.8 [M-N] ^-

Synthesis of 3-(difluoromethoxy)-5-(difluoromethyl)benzoic acid (intermediate INT-15)

Stage 1:

Methyl 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate

3-(Difluoromethoxy)-5-(methoxycarbonyl)benzoic acid (known from WO 2012019428 (7.38 g, 30 mmol) was suspended in dry toluene (30 ml). Oxalyl chloride (5.71 g, 45 mmol) was added in one portion, followed by 1 drop of DMF at room temperature. The reaction mixture was stirred at room temperature for 12 h and then at 60-70 °C for 2 h. The reaction mixture was evaporated to give 7.9 g of crude methyl 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate, which should be used without further purification.

Stage 2:

methyl 3-(difluoromethoxy)-5-formyl benzoate

2,6-lutidine (3.38 g, 3.68 mL, 31.5 mmol) and 3-(chlorocarbonyl)-5-(difluoromethoxy)benzoate from step 1 (7.94 g, 30 mmol) were dissolved in absolute THF (100 mL), Pd/C (Alfa, dry, 10%, 430 mg) was added and the mixture was hydrogenated for 48 h (H ₂ balloon). The formed precipitate was filtered off, washed with diethyl ether (200 mL), saturated aqueous NaHCO ₃ solution (30 mL) was added to the filtrate and stirred for 12 h at room temperature. The solution was further diluted with diethyl ether (300 mL) and water (300 mL). The organic layer was separated, washed with water (2 x 300 mL), aqueous citric acid (5%, 200 mL), water (300 mL), and brine (300 mL). Volatiles were removed in vacuo to give crude methyl 3-(difluoromethoxy)-5-formyl benzoate (4.1 g, 59% yield).

¹ H-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 on a Varian Gemini 2000 device.

Stage 3:

Methyl 3-(difluoromethoxy)-5-(difluoromethyl)benzoate

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. 5.60 g (34.8 mmol) of DAST was added in one portion and the reaction mixture was stirred for 12 h (slowly warming to room temperature). The reaction mixture was poured into saturated aqueous NaHCO ₃ (200 mL) and DCM (100 mL) was added, followed by separation of the organic layer, washing with water (100 mL) and drying 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.

¹ *H-NMR (400 MHz, CDCl ₃ ): 5=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 on a Varian Gemini 2000 device.

Stage 4:

3-(difluoromethoxy)-5-(difluoromethyl)benzoic acid

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 from step 3 (4.3 g, 17 mmol) in a mixture of THF (35 mL) and MeOH (35 mL). The reaction mixture was stirred at room temperature for 2 h. The 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, washed with water, dried at 100°C for 2 h and finally sublimed at 105°C (0.1 torr) to give the title compound (3.2 g, 79% yield).

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 on a Varian Gemini 2000 device.

Analytical data of compounds

Determination of [M+H] ⁺ or [M-H] ^- by LC-MS under acid chromatographic conditions was performed using 1 ml formic acid per liter of acetonitrile and 0.9 ml formic acid per liter of Millipore water as eluents. A Zorbax Eclipse Plus C18 50 mm * 2.1 mm column was used. The column oven temperature was 55°C.

Devices:

LC-MS3: Waters UPLC with SQD2 mass spectrometer and SampleManager autosampler. Linear gradient from 0.0 to 1.70 minutes from 10% acetonitrile to 95% acetonitrile, 1.70 to 2.40 minutes, constant 95% acetonitrile, flow 0.85 mL/min.

LC-MS6 and LC-MS7: Agilent 1290 LC, Agilent MSD, HTS PAL autosampler. Linear gradient from 0.0 to 1.80 minutes from 10% acetonitrile to 95% acetonitrile, from 1.80 to 2.50 minutes, constant 95% acetonitrile, flow 1.0 mL/min.

[M+H] ⁺ determination by LC-MS under neutral chromatographic conditions was performed using acetonitrile and Millipore water containing 79 mg/L ammonium carbonate as eluents.

[M+H] ⁺ determination by LC-MS under neutral chromatographic conditions was performed using acetonitrile and Millipore water containing 79 mg/L ammonium carbonate as eluents.

Devices:

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

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

1H-NMR data were determined using a Bruker AVIII 400 MHz spectrometer equipped with a 1.7 mm TCI cryoprobe, a Bruker Avance III 600 MHz equipped with a 5 mm multi-needle cryoprobe, or a Bruker Avance NEO 600 MHz equipped with a 5 mm TCI cryoprobe, with tetramethylsilane as a control (0.0) and CD3CN, CDCl3, or D6-DMSO solvents.

The NMR data of selected examples are listed either in the usual form (values, multiplet splitting, number of hydrogen atoms) or as lists of NMR peaks.

List of NMR peaks

1H-NMR data of selected examples are presented in the form of a list of 1H-NMR peaks. For each signal peak, the chemical shift value δ in ppm and the signal intensity in parentheses are given. Semicolons are used as separators between the δ value - signal intensity pairs.

The list of example peaks has the form:

δ1 (intensity 1); δ2 (intensity 2);…; δi (intensity i);…; δn (intensity n).

The intensity of sharp signals correlates with the height of the signals in the printed example NMR spectrum in cm and shows the real ratios of signal intensities. From broad signals, several peaks or the average signal and its relative intensity compared to the most intense signal in the spectrum can be shown.

For chemical shift calibration of the 1H NMR spectrum, tetramethylsilane and/or the chemical shift of the solvent used were used, especially in the case of the spectrum measured in DMSO. Therefore, the tetramethylsilane peak may appear in NMR peak lists, but is not required.

1H-NMR peak lists are similar to classical 1H-NMR fingerprints and therefore typically contain all peaks that are listed in classical NMR interpretation.

Additionally, they can show, like classical 1H-NMR fingerprints, signals of solvents, stereoisomers of target compounds, which is also covered by the present invention, and/or impurity peaks.

To show the delta range signals of the compound in solvents and/or water, common solvent peaks, such as the DMSO peaks in DMSO-D6, and the water peak are shown in our 1H-NMR peak lists and generally have a medium intensity height.

Stereoisomer peaks of target compounds and/or impurity peaks tend to have lower intensity on average than peaks of target compounds (e.g., with a purity of >90%).

Such stereoisomers and/or impurities may be typical for a particular production method. Therefore, their peaks may help to recognize the reproduction of the production method according to the present invention "fingerprint by-products".

An expert who calculates peaks of target compounds by known methods (MestreC, ACD-simulation, but also with empirically estimated expected values) can extract peaks of target compounds, optionally applying additional intensity filters if necessary. This extraction will be similar to the relevant peak extracted in the classical interpretation of 1H-NMR.

A more detailed description of the NMR data with peak lists can be found in Research Disclosure Database Number 564025.

The compounds of the present invention described in Table 1 below are also preferred compounds of formula (I) according to the invention, which are prepared according to or analogously to the preparation examples described above.

Additionally, the present invention relates to the following compounds:

Biological examples

Rhipicephalus (Boophilus) microplus - injection test (BOOPMI Inj)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is dissolved in 0.5 ml of solvent and the concentrate is diluted with the solvent to the desired concentration.

Five adult engorged female ticks (Rhipicephalus microplus) are injected with 1 μl of the compound solution into the abdominal cavity. The ticks are transferred to replica cups and incubated in a climate chamber.

After 7 days, the eggs are observed to lay fertile eggs. Eggs that are not fertile are stored in a climate chamber until hatching, approximately 42 days later. An efficiency of 100% means that all eggs are sterile; 0% means that all eggs are fertile.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 20 μg/mite: 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, 4, 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-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.

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

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 4 μg/mite: 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-30, II-31, II-ZZ, 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, 7, II-98, II-99, II-100, II-101, II-102, II-104, II-105, II-106, II-107, II-109, II-Ш, II-112, II-113, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 4 μg/mite: 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.

Rhipicephalus (Boophihis) microplus - in vitro contact testing of cattle tick larvae (Parkhurst strain, resistant to synthetic pyrethroids) (BOOPMI Conf)

9 mg of the compound are dissolved in 1 ml of acetone and diluted with acetone to the desired concentration. 250 μl of the test solution are poured into 25 ml glass test tubes and evenly distributed over the inner walls by rotating and tilting on a shaking device (2 h at 30 rpm). At a compound concentration of 900 parts per million, an internal surface of 44.7 cm2 and uniform distribution, a dose of 5 μg/cm2 is achieved.

After the solvent has evaporated, 20-50 cattle tick larvae (Rhipicephalus microplus) are placed in each tube, closed with a perforated lid and incubated horizontally at a relative humidity of 85% and a temperature of 27°C in an incubator. After 48 hours, the effectiveness is determined. The bottom of the tubes with larvae is slapped and negative geotactic behavior is recorded. Larvae that rise back to the top of the vial in a manner comparable to untreated control larvae are marked as alive, larvae that do not rise back like untreated control larvae but move uncoordinatedly or only twitch their legs are marked as dying, tick larvae remain at the bottom and do not move at all are considered dead.

The compound shows good efficacy against Rhipicephalus microplus if at a compound concentration of 5 μg/ ^cm2 an efficacy of at least 80% is observed. An efficacy of 100% means that all larvae are dead or dying; 0% means that there are no dead or dying larvae.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 5 μg/ ^cm2 (= 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-25,I-26,I-28,I-30, I-31, I-32, I-33, 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-49, I-50, I-52, I-53, I-54, I-56, I-57, I-58, I-59, I-60, I-61, I-63, I-64, I-65, II-2, II-5, II-8, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-18, II-19, -21, II-23, II-24, II-25, II-26, II-27, 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-52, II-53, II-54, II-55, II-57, 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, II-79, II-80, 1, II-82, II-85, II-86, II-88, II-90, II-91, 1I-92, 1I-93, 1I-94, 1I-96, 1I-97, II-98, II-99, II-100, II-101, II-104, II-105, II-106, II-107, II-109, II-111, II-112, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 5 μg/ ^cm2 (=500 g/ha): I-18, I-27, I-34, I-62, II-1, II-17, II-28, II-42, II-51, II-77, II-83, II-95, II-102, II-108.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 5 μg/ ^cm2 (=500 g/ha): I-8, I-51, I-55, II-9, II-22, II-56, II-87, II-89.

Rhipicephalus (Boophilus) microplus - BOOPMI Dip Test

Experimental animal: cattle ticks (Rhipicephalus microplus) strain ParkTiurst, SP-resistant

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound is dissolved in 0.5 ml of solvent and the concentrate is diluted with water to the desired concentration.

This compound solution is pipetted into test tubes. 8-10 swollen adult female cattle (Rhipicephalus microplus) are placed in perforated test tubes. These test tubes are immersed in an aqueous solution of the preparation until the ticks are completely moistened. After the liquid has drained, the ticks are transferred to filter paper in a plastic tray and stored in a climate chamber.

After 7 days, the eggs are observed to lay fertile eggs. Eggs that are not fertile are stored in a climate chamber until hatching, approximately 42 days later. An efficiency of 100% means that all eggs are sterile; 0% means that all eggs are fertile.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 100 ppm: I-1, I-2, I-7, I-8, II-5, II-43, II-50, II-53, II-63, II-73, II-96, II-97.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 100 ppm: II-38, II-47, II-54.

Ctenocephalides felis - in-vitro contact tests with adult feline fleas (CTECFE Conf)

9 mg of the compound were dissolved in 1 ml of acetone and then diluted to the desired concentration with acetone. 250 μl of the test solution were filled into 25 ml glass test tubes and homogeneously distributed on the inner walls by rotating and rocking on a shaking device (2 h at 30 rpm). At a compound concentration of 900 ppm, an internal surface area of 44.7 cm ² and homogeneous distribution, a dose of 5 μg/cm ² was achieved.

After evaporation of the solvent, each test tube was populated with 5-10 adult cat fleas (Ctenocephalides felis), sealed with a perforated plastic lid and incubated horizontally in the dark at room temperature and relative humidity. After 48 hours, the effectiveness was determined. For this, the jars are placed vertically, and the fleas end up at the bottom of the jar. Fleas that remain motionless at the bottom and move in an uncoordinated manner are considered dead or affected.

A compound shows good efficacy against Ctenocephalides felis if at least 80% efficacy is achieved in this test at an application rate of 5 μg/cm2. An efficacy of 100% means that all fleas are killed or dying. An efficacy of 0% means that no fleas are killed or dying.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 5 μg/ ^cm2 (= 500 g/ha): I-2, I-3, II-5, II-11, II-12, II-13, II-14, II-16, II-17, II-18, II-19, II-22,1I-26,1I-21, II-28, II-29, II-30, II-31, II-32, II-37, II-38, II-40, II-43, II-47, II-50, II-52, II-53, II-54, II-57, II-61,1I-62,1I-63,1I-65, II-70, II-71, II-72, II-73, II-74, II-77, II-79, II-80, II-81, II-83, II-85, II-86, II-88, II-91, II-92, II-94,1I-96,1I-91,1I-99, II-100, II-101, II-104, II-105, II-107, II-109, II-111, II-113, II-114, -116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 5 μg/cm2 (= 500 g/ha): I-1, I-64, II-1, II-2, II-7, II-8, II-33, II-69, II-75, II-93, II-106, II-115.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 5 μg/ ^cm2 (=500 g/ha): I-8, I-15, I-20, I-24, I-30, I-61, II-15, II-21, II-23, II-36, II-90, II-102, II-112.

Ctenocephalides felis - oral test (CTECFE oral)

Solvent: dimethyl sulfoxide

To obtain a suitable preparation of the active compound, 10 mg of the active compound was dissolved in 0.5 ml of solvent, and the concentrate was diluted with bovine blood to the desired concentration.

Approximately 20 adult hungry cat fleas (Ctenocephalides felis) are placed in flea chambers. The blood chamber, sealed at the bottom with parafilm, is filled with cattle blood laced with the compound solution and placed on the gauze-lined top of the flea chamber to allow the fleas to suck the blood. The blood chamber is heated to 37°C, while the flea chamber is maintained at room temperature.

After 2 days, the mortality rate was determined in %. 100% means that all fleas died; 0% means that not a single flea died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 100 ppm: I-3, I-5, I-7, I-9, I-10, I-11, I-13, I-15, I-19, I-21, I-24, I-25, I-27, I-28, I-30, I-31, I-32, I-34, I-35, I-41, I-42, I-43, I-44,I-46,I-48, II-1, II-2, II-7, II-8, II-10, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-19, II-20, II-21, II-22, II-28, II-29, II-30, II-46, II-47, II-49, II-50, II-52, II-53, II-57, II-60, II-61, II-62, II-63, II-64, II-65, II-69, II-75, II-77, II-79, II-80, II-81, II-82, II-83, II-86, II-91, 5, II-96, II-97, II-98, II-102, II-104, II-105, II-106, II-107, II-112, II-113.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 100 ppm: I-1, I-2, I-12, I-36, I-47, II-5, II-9, II-18, II-48, II-51, II-54, II-59, II-93, II-94.

Rhipicephalus sanguineus - in-vitro contact tests with adult brown dog ticks (RHIPSA Cont)

9 mg of the compound were dissolved in 1 ml of acetone and diluted to the desired concentration with acetone. 250 μl of the test solution were filled into 25 ml glass test tubes and homogeneously distributed on the inner walls by rotating and rocking on a shaking device (2 h at 30 rpm). At a compound concentration of 900 ppm, an internal surface of 44.7 cm ² and homogeneous distribution, a dose of 5 μg/cm ² was achieved.

After evaporation of the solvent, each test tube was populated with 5-10 adult dog ticks (Rhipicephalus sanguineus), sealed with a perforated plastic cap and incubated horizontally in the dark at room temperature and relative humidity. After 48 hours, the efficacy was determined. The ticks were dropped onto the bottom of the tubes and incubated on a hotplate at 45-50°C for a maximum of 5 min. Ticks that remained motionless on the bottom, or moved so uncoordinatedly that they could not purposefully fly upward to escape the heat, were considered killed or moribund.

A compound shows good efficacy against Rhipicephalus sanguineus if at least 80% efficacy is achieved in this test at an application rate of 5 μg/ ^cm2 . An efficacy of 100% means that all ticks are killed or dying. An efficacy of 0% means that no ticks are killed or dying.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 5 μg/ ^cm2 (= 500 g/ha): I-1, I-2, I-19, I-21, I-24, I-26, I-27, I-28, I-32, I-37, I-40, I-61, II-4, II-5, II-8, II-10, II-12, II-16, II-17, II-18, II-19, II-27, II-28, II-29, II-30, II-31, II-32, II-34, II-38, II-39, 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-57, II-61, II-62, II-63, II-65, II-68, II-69, II-70, II-71, II-72, II-73, II-74, II-75, II-77, II-83, II-85, II-91, II-92, II-93, II-94, II-96, II-97, II-98, 9, II-100, II-101, II-104, II-105, II-106, II-107, II-109, II-Ш, II-112, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 5 μg/ ^cm2 (= 500 g/ha): I-7, I-15, I-23, I-25, I-31, I-38, I-47, I-64, I-65, II-1, II-9, II-11, II-13, II-14, II-25, 1I-26, II-33, II-37, II-59, 1I-64, II-79, II-82, II-86.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 1 μg/cm2 (= 100 g/ha): I-2, I-7, I-19, I-21, I-24, I-25, I-27, I-28, I-36, I-37, I-38, I-47, I-61, II-4, II-5, II-8, II-12, II-13, II-16, II-18, II-19, II-26, II-27,1I-28, II-29, II-30, II-31, II-32, II-34, II-38, II-39, II-41, II-43, II-44, II-46, II-47, II-48, II-50, II-51, II-52, II-54, II-57, II-61, II-62, II-63, II-65, II-69, II-70, II-72, II-73, II-74, II-75, II-83, II-85, II-86, II-91, II-92, II-93, II-94, II-95, II-96, II-97, II-98, II-99, II-100, 101, II-104, II-105, II-106, II-107, II-109, II-111, II-112, II-114, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 1 μg/ ^cm2 (=100 g/ha): I-1, I-26, I-30, I-32, II-10, II-13, II-14, II-17, II-24, II-33, II-40, II-53, II-59, II-79, II-82, II-108, II-113.

Diabrotica balteata - spray test

Solvent: 78.0 parts by weight of acetone

1.5 wt. dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with the specified amount of solvent, and the concentrate was diluted with water at a concentration of 1000 parts per million emulsifier to the desired concentration. Further test concentrations were obtained by dilution with an emulsifier containing water.

Soaked wheat seeds (Triticum aestivum) were placed in a multi-well plate filled with agar and a little water and incubated for 1 day for germination (5 seeds per well). The germinated wheat seeds were sprayed with the test solution containing the desired concentration of the active ingredient. After that, each unit was infested with 10-20 larvae of the bordered flea beetle (Diabrotica balteata).

After 7 days, the efficiency is determined in %. 100% means that all seedlings grew as in the untreated, uninfected control; 0% means that none of the seedlings grew.

In this test, for example, the following compounds of the production examples showed good activity of 100% at an application rate of 500 g/ha (=160 μg/well): 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, 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-21, II-22, II-23, II-27, II-28, II-29, II-30, II-31, II-32, II-ЗЗ, II-34, II-37, II-38, II-39, II-40, II-41, II-42, II-43, II-44, II-46, II-66, II-67, II-68, II-70, II-71, II-72, II-73, II-74.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 500 g/ha (=160 μg/well): II-24, II-25.

In this test, for example, the following compounds of the production examples showed good activity of 100% at an application rate of 100 g/ha (=32 μg/well): 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-17, I-19, I-22, I-24, I-25, I-26, 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-42, I-43, I-44, I-45, I-46, I-48, I-49, I-52, I-53, I-55, I-56, I-57, I-60, I-61, I-62, I-63, I-64, I-65, II-2, 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, 1, II-23, II-28, II-29, II-30, II-31, II-32, II-33, II-34, II-37, II-38, II-39, II-40, II-41, II-42, II-43, II-44, II-46, II-47, II-48, II-49, II-50, II-52, II-53, II-61, II-62, II-63, II-64, II-66, II-68, II-70, II-71, II-72, II-73, II-74, II-75, II-77, II-79, II-83, II-85, II-86, II-87, II-88, II-89, II-91, II-93, II-94, II-96, 7, II-99, II-101, II-105, II-106, II-107, II-108, II-109, II-111, II-112, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 80% at an application rate of 100 g/ha (=32 μg/well): I-21, I-47, II-4, II-65, II-69, II-81, II-82.

Meloidogyne incognita - test

Solvent: 125.0 parts by weight of acetone

To obtain a suitable composition of the active substance, 1 part by weight of the active substance was mixed with a specified amount of solvent, and the concentrate was diluted with water to the desired concentration.

The vessels were filled with sand, a solution of the active substance, a suspension of eggs/larvae of southern root knot nematodes (Meloidogyne incognita) and lettuce seeds. The lettuce seeds germinated and the plants developed. Galls developed on the roots.

After 14 days, the nematicidal efficiency in % was determined by the formation of galls. In this case, 100% means that no galls were detected; 0% means that the number of galls on the treated plants corresponds to the untreated control.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 20 ppm: I-14, II-24.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 20 parts per million: I-12, I-13, I-19, I-23, II-3, II-25.

Myzus persicae - oral test

Solvent: 100 parts by weight of acetone

To prepare a suitable preparation of the active compound, 1 part by weight was dissolved using the established parts by weight of the solvent and diluted with water to achieve the desired concentration.

50 μl of the active compound preparation was transferred to a microtiter plate and filled with 150 μl of IPL41 insect medium (33%+15% sugar) to a final volume of 200 μl. The plate was then sealed with paraffin film through which the mixed population of green peach aphid (Myzus persicae), which is in a second microtiter plate, can consume the solution.

After 5 days, the effectiveness was determined as a percentage. 100% means that all aphids died; 0% means that no aphids died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 4 ppm: I-1, I-7, I-9, I-10, I-11, I-15, I-31, I-32, I-50, I-61, I-63, I-64, I-65, II-5, II-7, II-11, II-12, II-14, II-18, II-19, II-25, II-27, II-30, II-31, II-32, II-33, II-37, II-38, II-41, II-44, II-47, II-50, II-52, II-53, II-54, II-61, II-62, II-63, II-65, II-69, II-72, II-73, II-74, II-75, II-77, II-81, II-83, II-85, II-86, II-87, II-88, II-89, II-90, II-91, II-92, II-93, II-94, II-96, II-97, II-98, II-99, II-100, II-101, II-104, II-105, II-106, 07, II-109, II-111, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 4 parts per million: I-3, I-28, I-30, I-48, II-13, II-28, II-71, II-95.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 0.8 ppm: I-64, II-19, II-32, II-37, II-47, II-50, II-52, II-53, II-54, II-79, II-80, II-81, II-86, II-89, II-91, II-99, II-100, II-101, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at a loading rate of 0.8 ppm: I-44, II-77, II-109, II-111.

Myzus persicae - spray test

Solvent: 78 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with a specified amount of solvents and diluted with water containing an emulsifier concentration of 1000 parts per million to the desired concentration. Other test concentrations were obtained by dilution with water containing emulsifier.

The leaf discs of Chinese cabbage (Brassica pekinensis), which were parasitized by the green peach aphid (Myzus persicae) at all stages, were sprayed with the active compound preparation at the desired concentration.

After 5 days, the effectiveness was determined as a percentage. 100% means that all aphids died; 0% means that no aphids died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 500 g/ha: I-2, II-7, II-26, II-31, II-37, II-38, II-39, II-40, II-73.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 500 g/ha: I-3, II-2, II-5, II-8, II-12, II-27, II-32, II-36, II-71, I-74.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 100 g/ha: I-2, II-2, II-31, II-32, II-38, II-47, II-50, II-53, II-62, II-63, II-73, II-79, II-91, II-97, II-100, II-104, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 100 g/ha: I-3, I-37, I-64, I-65, II-12, II-16, II-32, II-47, II-52, II-54, II-57, II-61, II-65, II-71, II-77, II-80, II-81, II-83, II-92, II-93, II-94, II-96, II-98, II-99, II-101, II-105, II-106, II-109, II-113, II-114, II-115, II-116.

Nezara viridula - spray test

Solvent: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with a specified amount of solvents and the concentrate was diluted with water containing an emulsifier concentration of 1000 parts per million to the desired concentration. Other test concentrations were diluted with water containing an emulsifier.

Barley plants (Hordeum vulgare) infested with green vegetable bug (Nezara viridula) larvae were sprayed with the desired concentration of the active compound.

After 4 days, mortality was determined as a percentage. 100% means that all vegetable bugs died; 0% means that none of the vegetable bugs died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 500 g/ha: I-6, I-7, I-64, I-65, II-5, II-8, II-9, II-11, II-12, II-14, II-16, II-27, II-30, II-32, II-37, II-38, II-40, II-44, II-46, II-47, II-71, II-72, II-73, II-74.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 500 g/ha: I-2, I-4, I-11, II-2, II-7, II-13, II-15, II-21, II-28, II-31, II-36, II-39, II-70.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 100 g/ha: I-37, I-38, I-42, I-46, I-47, II-8, II-11, II-12, II-14, II-30, II-32, II-38, II-40, II-47, II-57, II-61, II-62, II-63, II-65, II-73, II-77, II-79, II-81, II-91, II-93, II-94, II-95, II-97, II-99, II-100, II-101, II-105, II-109, II-111, II-113, II-114, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 100 g/ha: I-28, I-64, II-5, II-16, II-32, II-37, II-41, II-53, II-92.

Nilaparvata lugens - spray test

Solvent: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with a specified amount of solvents and diluted with water containing an emulsifier concentration of 1000 parts per million to the desired concentration. To obtain other test concentrations, dilutions were made with water containing an emulsifier.

Rice (Oryza sativa) plants were sprayed with the active compound preparation at the desired concentration and then infested with rice cicada (Nilaparvata lugens) larvae.

After 4 days, mortality was determined as a percentage. 100% means that all rice cicadas died; 0% means that no rice cicadas died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 500 g/ha: II-8, II-73.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 500 g/ha: II-43, II-44, II-74.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 100 g/ha: I-26, I-43, II-95, II-96, II-99, II-104.

Spodoptera frugiperda - spray test

Solvent: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with a specified amount of solvents and diluted with water containing an emulsifier concentration of 1000 parts per million to the desired concentration. Other test concentrations were obtained by dilution with water containing emulsifier.

Corn leaf sections (Zea mays) were sprayed with the active substance composition at the desired concentration. Immediately after drying, the leaf sections were populated with cutworm larvae (Spodoptera frugiperda).

After 7 days, the effectiveness was determined as a percentage. 100% means that all caterpillars died; 0% means that none of the caterpillars died.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 500 g/ha: I-1, I-2, I-3, I-4, I-5, I-6, I-8, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, II-1, 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-17, II-18, II-19, II-20, II-21, II-23, II-24, II-25, II-26, 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-42, II-43, II-44, II-46, II-66, II-67, II-69, II-70, II-71, II-72, II-73, II-74.

In this test, for example, the following compounds of the preparation examples showed good activity of 83% at an application rate of 500 g/ha: I-7, I-18, II-22, II-27, II-68.

In this test, for example, the following compounds of the preparation examples showed good activity of 100% at an application rate of 100 g/ha: 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-15, I-17, I-19, I-21, I-24, I-25, I-26, I-28, I-30, I-32, I-34, I-36, I-37,I-39,I-40, I-41, I-42, I-43,I-44, I-45, I-46,I-47, I-48, I-49,I-51,I-52, I-53, I-54,I-55, I-56, I-57, I-59, I-61, I-63, I-64, I-65, II-1, II-4, II-5, II-10, II-11, II-12, II-13, II-14, II-16, II-18, II-19, II-23, II-25, II-30, II-31, II-32, II-33, II-34, II-36, -37, II-38, II-39, II-40, II-41, II-42, II-43, II-44, II-46, II-47, II-50, II-52, II-53, II-54, II-57, II-61, II-62, II-64, II-65, II-70, II-72, II-73, II-74, II-75, II-77, II-79, II-81, II-82, II-83, II-86, II-87, II-88, II-91, II-92, II-93, II-96, II-97, II-100, II-101, II-104, II-105, II-106, II-107, II-108, II-111, II-112, 3, II-115, II-116, II-117.

In this test, for example, the following compounds of the preparation examples showed good activity of 83% at an application rate of 100 g/ha: G14, I-38, I-58, I-60, II-9, II-26, II-27, II-29, II-69, II-85, II-90, II-98, II-114.

Tetranvchus urticae - spray test (OR resistance)

Solvent: 78.0 parts by weight of acetone

1.5 parts by weight of dimethylformamide

Emulsifier: alkyl aryl polyglycol ether

To obtain a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with a specified amount of solvents and diluted with water containing an emulsifier concentration of 1000 parts per million to the desired concentration. Other test concentrations were obtained by dilution with water containing emulsifier.

Leaf discs of bean (Phaseolus vulgaris) infested at all stages with two greenhouse red spider mites (TeTpanychus urticae) were sprayed with the desired concentration of the active compound.

After 6 days, the effectiveness was determined as a percentage. 100% means that all spider mites died; 0% means that no spider mites died.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 500 g/ha: II-80.

In this test, for example, the following compounds of the preparation examples showed good activity of 90% at an application rate of 100 g/ha: II-12, II-38, II-99.

Aedes (biter) test (AEDSAE surface treatment and contact analysis)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To obtain a suitable active substance composition, the active substance was dissolved in a solvent (2 mg/ml). The active substance composition was transferred to a glazed roofing tile using a pipette and, after drying, adult mosquitoes of the species Aedes aegypti strain MONHEIM were placed on the treated roofing tile. The exposure time was 30 minutes.

Mortality is determined as a percentage 24 hours after contact with the treated surface. 100% means that all mosquitoes have died; 0% means that none of the mosquitoes have died.

The following examples have shown 80-100% efficiency in this test at a surface concentration of 20 mg/m2: I-1, I-3, I-8, I-9, I-19, I-26, I-27, I-30, I-35, I-37, I-42, I-44, II-1, II-3, II-4, II-5, II-7, II-8, II-11, II-12, II-13, II-14, II-16, II-17, II-19, II-22, II-23, 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-46, II-47, II-48, II-50, II-52, II-53, II-54, II-57, II-61, II-62, II-63, II-64, II-65, II-77, II-79, II-80, II-81, II-82, II-83, II-96, II-97, II-99, II-101, II-111, II-117.

The following examples have shown 80-100% efficiency in this test at a surface concentration of 4 mg/m2: I-1, I-3, I-9, I-15, I-30, I-42, I-44, I-47, II-1, II-3, II-5, II-8, II-11, II-12, II-13, II-14, II-17, II-19, II-22, II-25, II-27, II-29, II-30, II-32, II-33, II-34, II-36, II-37, II-38, II-40, II-41, II-43, II-46, II-47, II-48, II-49, II-50, II-52, II-53, II-54, II-57, II-61, II-62, II-63, II-65, II-77, II-79, II-80, II-81, II-82, II-83, II-96, II-101, II-111, II-116, II-117.

Culex quinquefasciatus test (CULXFA surface treatment and contact analysis)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To obtain a sufficient solution containing the active ingredient, it is necessary to dissolve the test compound in a solvent mixture (acetone at 2 mg/ml / RME 2000 ppm). This solution is pipetted onto a glazed tile and after evaporation of the acetone, adult mosquitoes of the species Culex quinquefasciatus, strain P00, are placed on the dried surface. The exposure time is 30 minutes. After 24 hours of contact with the treated surface, the mortality is determined in percentage. In this case, 100% means that all insects died; 0% means that no insects died.

The following examples showed 80-100% efficiency in this test at a surface concentration of 20 mg/m2: II-1, II-2, II-3, II-4, II-5, II-7, II-8, II-9, II-11, II-12, II-13, II-16, II-17, II-18, II-19, II-22, II-27, II-28, II-30, II-31, II-36, II-37, II-38, II-40, II-41, II-42, II-57, II-62, II-63.

The following examples showed 80-100% efficiency in this test at a surface concentration of 4 mg/m2: II-8, II-11, II-12, II-22, II-28, II-30, II-36, II-40, II-41, II-43, II-50, II-52, II-57.

Anopheles mosquito test (ANPHFU surface treatment and contact assay)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To obtain a suitable active substance formulation, the active substance was dissolved in a solvent (2 mg/ml). The active substance formulation was transferred to a glazed roofing tile using a pipette and, after drying, adult mosquitoes of the species Anopheles funestus strain FUMOZ-R (Hunt et al., Med Vet Entomol. 2005 Sep; 19(3):27I-5) were placed on the treated roofing tile. The exposure time was 30 minutes. Mortality was determined in percentage 24 hours after contact with the treated surface. 100% means that all mosquitoes died; 0% means that none of the mosquitoes died.

The following examples showed 80-100% efficiency in this test at a surface concentration of 20 mg/m2: II-3, II-4, II-5, II-8, II-9, II-10, II-12, II-16, II-17, II-22, II-23, II-26, II-27, II-31, II-36, II-38, II-40, II-42, II-43, II-47, II-48, II-52, II-77, II-79, II-80, II-81, II-83, II-101, II-116.

The following examples showed 80-100% efficiency in this test at a surface concentration of 4 mg/m2: II-3, II-4, II-5, II-8, II-9, II-10, II-12, II-14, II-17, II-22, II-31, II-36, II-48, II-50, II-52, II-77, II-79, II-81, II-83, II-101.

Musca domestica test (MUSCDO surface treatment and contact analysis)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

To obtain a sufficient solution containing the active ingredient, it is necessary to dissolve the test compound in a solvent mixture (acetone at 2 mg/ml / RME 2000 ppm). This solution is pipetted onto a glazed tile and after evaporation of the acetone, adult flies of the species Musca domestica, strain WHO-N, are placed on the dried surface. The exposure time is 30 minutes. After 24 hours of contact with the treated surface, the mortality is determined in percentage. 100% means that all insects died; 0% means that no insects died.

The following examples have shown 80-100% efficiency in this test at a surface concentration of 20 mg/m3: I-1, I-3, I-4, I-6, I-9, I-10, I-11, I-28, I-30, I-31, I-34, I-35, I-37, I-38, I-42,I-44, I-46, I-47, II-4, II-5, II-7, II-8, II-9, II-11, II-12, II-13, II-14, II-15, II-16, II-17, II-18, II-19, II-21, II-22, II-23, II-25, II-28, II-30, II-31, II-32, II-33, II-36, II-39, II-40, II-41, II-43, II-46, II-47, II-50, II-52, II-53, II-54, II-57, II-61, II-62, II-63, II-65, II-77, II-81, II-83, II-96, II-97, II-99, II-101, II-111, II-116, II-117.

The following examples showed 80-100% efficiency in this test at a surface concentration of 4 mg/m2: I-2, I-3, I-33, I-37, I-44, I-47, II-5, II-8, II-11, II-12, II-13, II-14, II-17, II-18, II-21, II-22, II-30, II-32, II-33, II-39, II-41, II-46, II-47, II-50, II-52, II-53, II-54, II-57, II-61, II-62, II-65, II-77, II-83, II-96, II-97, II-99, II-101, II-111, II-116, II-117.

Blattella germanica test (BLTTGE surface treatment and contact analysis)

Solvent: Acetone + 2000 ppm Rapeseed Oil Methyl Ester (RME)

In order to obtain a sufficient solution containing the active ingredient, it is necessary to dissolve the test compound in a solvent mixture (acetone at 2 mg/ml / RME 2000 ppm). This solution was pipetted onto the glazed tile and after evaporation of the acetone, adult animals of the species Blattella germanica, strain PAULINIA, were placed on the dried surface. The exposure time was 30 minutes. After 24 hours of contact with the treated surface, the mortality was determined in percentage. 100% means that all insects died; 0% means that no insects died.

The following examples showed 80-100% efficiency in this test at a surface concentration of 20 mg/ ^m2 : II-77, II-80, II-83, II-101, II-111, II-116.

The following examples showed 80-100% efficiency in this test at a surface concentration of 4 mg/m3: II-111, II-116.

Claims (30)

1. Compound of formula (I) , in which R ¹ represents hydrogen; ^R2 is phenyl or pyridine, wherein the phenyl or pyridine is optionally substituted with one or two substituents, provided that the substituent(s) is(are) not on any of the carbon atoms adjacent to the carbon atom bonded to the C=O group, each independently selected from the group consisting of fluoro, chlorine, bromine, -CN, methyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, methoxy, difluoromethoxy, trifluoromethoxy, difluoromethylthio, trifluoromethylthio, difluoroethylthio and trifluoroethylthio; R ³ is C ₁ -C ₃ alkyl; R ⁴ is pyridine or pyrimidine, wherein the pyridine or pyrimidine is substituted with CN; R ⁵ is ethyl, isopropyl, tert-butyl, difluoromethyl, cyclopropyl, methoxy, ethoxy, isopropoxy or halogen. 2. The compound according to item 1, in which R ¹ represents 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, 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. 3. Compound of formula (e) , in which the structural elements R ³ , R ⁴ and R ⁵ have the meanings given in paragraph 1 or 2. 4. The compound according to claim 3, selected from the group consisting of 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 and 6-[5-(1-aminoethyl)-3-bromo-1,2,4-triazol-1-yl]pyridine-3-carbonitrile and their hydrochlorides. 5. Connections 6. A composition for combating unwanted animal pests, comprising at least one compound of formula (I) according to claim 1 or 2. 7. The composition according to claim 6, additionally containing at least one filler and/or at least one surfactant. 8. The composition according to claim 6 or 7, characterized in that the compound of formula (I) is in a mixture with at least one additional active compound. 9. A method for combating pests, characterized in that any compound of formula (I) according to claim 1 or 2 or a composition according to any of claims 6-8 acts on pests and/or their habitat, wherein methods of surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body are excluded. 10. The method according to paragraph 9, characterized in that the pest is an animal pest and includes an insect, arachnid or nematode, or that the pest is an insect, arachnid or nematode, wherein methods of surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body are excluded. 11. The use of a compound of formula (I) according to claim 1 or 2 or a composition according to any of claims 6 to 8 for combating animal pests, wherein the use of methods for surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body is excluded. 12. The use according to paragraph 11, characterized in that the pest is an animal pest and includes an insect, arachnid or nematode, or that the pest is an insect, arachnid or nematode, and the use of methods of surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body is excluded. 13. Use according to paragraph 11 or 12 for plant protection, whereby the use of methods of surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body is excluded. 14. Use according to paragraph 11 or 12 in the field of animal health, whereby the use of methods of surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body is excluded. 15. A method for protecting seeds or germinating plants from pests, comprising a method step in which the seeds are brought into contact with a compound of formula (I) according to claim 1 or 2 or with a composition according to any of claims 6 to 8, wherein methods for surgical and therapeutic treatment of the human or animal body and diagnostic methods carried out on the human or animal body are excluded.