Pyrazine compounds for invertebrate pest control.

Abstract

The present invention relates to a compound of formula I [Formula 1] TIFF2024532329000027.tif30170 (wherein the variables have the meanings defined herein), compositions containing same, combinations of active compounds containing same and their use for protecting growing plants and animals from attack or infestation by invertebrate pests, as well as seeds containing such compounds.

Description

[Technical field]

[0001] The present invention relates to a compound represented by formula (I) [ka] (In the formula, R 1 is H, OH, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C5-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-alkyl-C3-C6-cycloalkyl, C1-C4-alkyl-C3-C6-halocycloalkyl (these groups are unsubstituted or partially or completely replaced by R 11 ; or C(=NR 11 )R 12 , C(O)R 11a ) and R 11 CN, NO2, NR 12 R 13 , C(O)NH2, C(S)NH2, C(O)OH, OR 14 , Si(CH3)3; C1-C6-alkyl; C1-C6-haloalkyl; C2-C6-alkenyl; C2-C6-haloalkenyl; C2-C6-alkynyl; C2-C6-haloalkynyl; C3-C4-cycloalkyl-C1-C2-alkyl (the rings are unsubstituted or substituted by one or two halogens); 3- to 6-membered heterocyclyl (the rings are unsubstituted or substituted by R a 5- or 6-membered hetaryl, or phenyl (these rings are unsubstituted or substituted by R 3a ) and R a is halogen, CN, NO2, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O) m-C1-C4-Alkyl, S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3-C4-halocycloalkyl, and oxo; R 11a is NR 12 R 13 , C(O)NH2, C(S)NH2, C(O)OH, OR 14 , Si(CH3)3; C1-C6-haloalkyl; C2-C6-alkenyl; C2-C6-haloalkenyl; C2-C6-alkynyl; C2-C6-haloalkynyl; C3-C4-cycloalkyl-C1-C2-alkyl (the rings are unsubstituted or substituted by one or two halogens); 3- to 6-membered heterocyclyl (the rings are unsubstituted or substituted by R a ) and R 12 , R 13 are independently H, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-haloalkyl, C3-C6-cycloalkyl, C(O)-C1-C4-alkyl, C(O)-C1-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-C3-C4-halocycloalkyl, C(O)NR 121 R 131 , S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclyl (these rings are unsubstituted or a 5- or 6-membered hetaryl or phenyl (these rings are unsubstituted or substituted by R 3a is replaced by; or R 12 and R 13together with the nitrogen atom to which they are attached form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocycle which may further contain, as ring members, 1 or 2 heteroatoms or heteroatom groups selected from N, O and S(O)m, which heterocycle is unsubstituted or is a and is substituted by one or more substituents selected from: R 121 and R 131 are each independently H, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy; C1-C4-alkyl-phenyl, C1-C4-alkyl-3- to 6-membered hetaryl, phenyl, 3- to 6-membered heterocyclyl (these rings are unsubstituted or a or 5- or 6-membered hetaryl (these rings are unsubstituted or substituted by R 3a is replaced by; or R 121 and R 131 together with the nitrogen atom to which they are attached form a 3-6 membered saturated, partially or fully unsaturated heterocycle, which may further contain 1 or 2 heteroatom ring members selected from N, O and S, where S may be oxidized, and which may be unsubstituted or may be substituted with R a has been replaced by; m is 0, 1 or 2; R 14 is H, C1-C4-alkyl, C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C4-cycloalkyl-C1-C2-alkyl, C3-C4-halocycloalkyl-C1-C2-alkyl, C(O)-C1-C4-alkyl, C(O)-C1-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-C3-C4-halocycloalkyl, or unsubstituted or R 3a is phenyl partially or fully substituted by R 2is H, CN, C1-C3-alkyl, C1-C3-haloalkyl, C2-C3-alkenyl, C2-C3-alkynyl; X is CH, CR, or N; R 3 is halogen, CN, NO2, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, OR 14 , S(O) m -R 14 (These may be unsubstituted or R 3a ) and R 3a is halogen, CN, NO2, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O) m -C1-C4-Alkyl, S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3-C4-halocycloalkyl; n is 0, 1, 2 or 3; R 4 OR 14 , CN, C1-C6-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl (each of which is unsubstituted or 41 partially or completely replaced by); S(O) m -C1-C4-Alkyl, S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3~C4-Halocycloalkyl, NR 12 R 13 , C(O)NR 12 R 13 , C(O)OR 14, 3- to 6-membered heterocyclyl (these rings are unsubstituted or a 5- or 6-membered hetaryl, or phenyl (these rings are unsubstituted or substituted by R 3 (partially or completely replaced by); R 41 H, OR 15 , N.R. 12 R 13 , C1~C4-alkyl, C1~C4-haloalkyl, C3~C6-cycloalkyl, C(O)-C1~C4-alkyl, C(O)-C1~C4-haloalkyl, C(O)-C3~C4-cycloalkyl, C(O)-C3~C4-halocycloalkyl, C(O)NR 121 R 131 ; S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl; These non-aromatic cyclic R 41 The group is unsubstituted or partially or fully substituted by Ra; Aromatic R 41 The group may be unsubstituted or partially or completely R 3a has been replaced by; R 15 is H, C1-C4-alkyl, or C1-C4-haloalkyl, C3-C6-cycloalkyl, C1-C6-halocycloalkyl (these carbon chains are unsubstituted or 11 or 3- to 6-membered heterocyclyl (the rings are unsubstituted or partially or fully substituted by R a 5- or 6-membered hetaryl, or phenyl (these rings are unsubstituted or substituted by R 3a is partially or completely replaced by and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

[0002] The present invention also provides agricultural compositions comprising at least one compound of formula I, its stereoisomers and / or its agriculturally acceptable salts, and at least one liquid and / or solid carrier, in particular at least one inert liquid and / or solid agriculturally acceptable carrier.

[0003] The present invention also provides veterinary compositions comprising at least one compound of formula I, its stereoisomers and / or its veterinarily acceptable salts, and at least one liquid and / or solid carrier, in particular at least one inert veterinary liquid and / or solid acceptable carrier.

[0004] The present invention also provides a method for controlling invertebrate pests which comprises treating the pest, its food source, its habitat or its breeding ground or the cultivated plants, plant propagation material (such as seeds), soil, area, material or environment in which the pest is growing or may grow or the material, cultivated plants, plant propagation material (such as seeds), soil, surface or space to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I as defined herein or a salt thereof.

[0005] The present invention also relates to plant propagation material, particularly seeds, which comprise at least one compound of formula I and / or an agriculturally acceptable salt thereof.

[0006] The present invention further relates to a method for treating or protecting an animal against infestation or infection by a parasite, comprising contacting the animal with a parasiticidally effective amount of a compound of formula I or a veterinarily acceptable salt thereof. Contacting an animal with compound I, its salt or the veterinary composition of the present invention means applying or administering it to the animal. [Background technology]

[0007] WO 2017 / 192385, WO 2020 / 070049, WO 2021 / 037614, WO 2021 / 122645, WO 2021 / 068179, and WO 2021 / 069575 describe structurally closely related active compounds that are said to be useful for controlling invertebrate pests. Summary of the Invention [Problem to be solved by the invention]

[0008] Nevertheless, there remains a need for highly effective and versatile agents for combating invertebrate pests. It is therefore an object of the present invention to provide compounds that have good pesticidal activity and exhibit a broad spectrum of activity against many different invertebrate pests, particularly pests such as insects that are difficult to control. [Means for solving the problem]

[0009] It has now been found that these objects can be achieved by compounds of formula I as shown and defined below, as well as their stereoisomers, salts, tautomers and N-oxides, particularly the agriculturally acceptable salts thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Compound I can be obtained by alkylating compound II with a suitable alkylating agent III (e.g., an alkyl halide). 1 has the meaning as in formula I and Y is a nucleophilic leaving group such as a halide, preferably Br or Cl. The alkylation can be carried out under standard conditions known from the literature. [ka]

[0011] This transformation is usually carried out in an inert solvent in the presence of a base at a temperature between −10° C. and +110° C., preferably between 0° C. and 25° C. [see WO 2002100846].

[0012] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of III based on II.

[0013] Compounds II can be obtained by reaction of amino compounds IV with carboxylic acids V. [ka]

[0014] This transformation is usually carried out in an inert solvent in the presence of a base at temperatures between −20° C. and 50° C., preferably between 0° C. and 25° C. [see A. El-Faham, Chem. Rev. 2011, 6557], or alternatively in two steps by preparing an intermediate acyl chloride from V under conditions known from the literature, for example by reaction with thionyl chloride or oxalyl chloride in dimethylformamide (see Schaefer et al., Organic Syntheses 1929, 32), followed by reaction with IV in the presence of a base, optionally under Schotten-Baumann conditions (Baumann, Chem. Ber. 1886, 3218). Suitable peptide coupling reagents are, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride, or chloro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate, which are generally used together with catalytic, stoichiometric, excess amounts of additives, such as 1-hydroxybenzotriazole, 1-hydroxy-7-aza-benzotriazole, 4-(dimethylamino)pyridine, and / or 1-methylimidazole.

[0015] Suitable solvents are halogenated hydrocarbons, such as dichloromethane (DCM) or 1,2-dichloroethane, ethers, such as diethyl ether, tetrahydrofuran (THF) or 1,4-dioxane, or high boiling solvents, such as dimethylformamide (DMF), preferably DCM or DMF, or aqueous media.

[0016] Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides, e.g., LiOH, NaOH, KOH, or Ca(OH)2, alkali metal and alkaline earth metal carbonates, e.g., Na2CO3, K2CO3, or Cs2CO3, alkali metal bicarbonates, e.g., NaHCO3, or organic bases, e.g., tertiary amines, e.g., triethylamine, diisopropylethylamine, N-methylpiperidine, or basic aromatic rings, e.g., pyridine, 2,4,6-collidine, 2,6-lutidine, or 4-(dimethylamino)pyridine, or bicyclic amines, e.g., 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), or 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0017] Particularly preferred are triethylamine, diisopropylethylamine and NaOH.

[0018] The base is generally used in a stoichiometric amount or in excess, but can also be used in a catalytic amount or, where appropriate, as a solvent.

[0019] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of IV based on V.

[0020] Compound IV can be obtained by reductive amination of compound VI. [ka]

[0021] This transformation is usually carried out in an alcoholic and / or aqueous medium and in the presence of a reagent and a reducing agent at a temperature between 0°C and 130°C, preferably between 20°C and 70°C [see WO2021037614]. Suitable solvents are alcohols, such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, or water, preferably methanol. It is also possible to use mixtures of the above solvents. Suitable reagents are ammonium acetate (NH4Ac), ammonium formate, NH4OH, NH4Cl, or ammonia. Suitable reducing agents are NaBH3CN, sodium triacetoxyborohydride, or NaBH4.

[0022] Ammonium acetate and NaBH3CN are each preferred.

[0023] Compounds VI can be obtained from compounds VII in a two-step sequence consisting of Stille coupling of VII with an alkoxyalkenylstannane such as VIII, followed by hydrolysis of the resulting enol ether moiety to ketone VI. [ka]

[0024] The Stille coupling reaction is usually carried out at temperatures between 50°C and 150°C, preferably between 70°C and 120°C, in an inert solvent, in the presence of one or more catalysts, and optionally in the presence of one or more additives and a base [see H.Lin et al., Bioorg Med Chem Lett 2010, 679]. Suitable solvents are aromatic hydrocarbons, such as toluene, o-, m-, p-xylene and mesitylene, or ethers, such as THF and 1,4-dioxane, preferably toluene or 1,4-dioxane. It is also possible to use mixtures of the above solvents.

[0025] Suitable catalysts are palladium complexes, such as tetrakis(triphenylphosphine)palladium, tris(dibenzylideneacetone)dipalladium, palladium diacetate, dichloro-bis(triphenylphosphine)palladium, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium, preferably dichlorobis(triphenylphosphine)palladium. Further suitable optional catalysts are common ligands such as dicyclohexyl[2',4',6'-tris(propan-2-yl)[1,1'-biphenyl]-2-yl]phosphine or triphenylphosphine. Suitable additives are generally inorganic compounds, such as cesium fluoride and cuprous iodide. The starting materials are generally reacted with each other in equimolar amounts. In terms of yield, it may be advantageous to use an excess of VIII based on VII.

[0026] The hydrolysis is usually carried out in an aqueous acidic medium containing aqueous HCl at a concentration of 0.5M to 3M, and optionally containing an organic solvent such as acetonitrile, acetone, THF or methanol, at a temperature between -20°C and 40°C, preferably 0°C to 25°C (see H. Lin et al., Bioorg Med Chem Lett 2010, 679).

[0027] Compounds VII can be obtained from triazoles IX: In formula X, group Z is a leaving group, for example, a halide such as I, Br and Cl, or a sulfonate such as triflate or mesylate. [ka]

[0028] This transformation is usually carried out in an inert solvent, in the presence of a base, at temperatures between 0° C. and 100° C., preferably between 10° C. and 60° C. [see J. Bradshaw et al., J. Heterocycl. Chem. 1986, 361]. Suitable solvents are halogenated hydrocarbons, such as DCM, 1,2-dichloroethane or chloroform, ethers, such as diethyl ether, tert-butyl methyl ether, dioxane or THF, nitriles, such as acetonitrile or propionitrile, alcohols, such as methanol or ethanol, and polar aprotic solvents, such as dimethylsulfoxide (DMSO), DMF or dimethylacetamide (DMA), preferably acetonitrile. It is also possible to use mixtures of the above solvents.

[0029] Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydrides, for example NaH, KH, alkali metal and alkaline earth metal carbonates, for example Na2CO3, K2CO3 or Cs2CO3, alkali metal bicarbonates, for example NaHCO3, or organic bases, for example tertiary amines, for example triethylamine or diisopropylethylamine. K2CO3 is preferred. The base is generally used in equimolar amounts, but can also be used in excess or as a solvent if appropriate.

[0030] The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to use an excess of X based on IX.

[0031] It is known from the literature that triazole IX can be obtained from compound XI by reaction with 1 to 1.5 equivalents of hydrazine hydrate XII in acetic acid (AcOH) as solvent, optionally with alcohols such as methanol, ethanol, 2-propanol, or ethers such as 1,4-dioxane as cosolvents, at temperatures between 25° C. and 110° C. (see Lin et al, J. Org. Chem. 1979, 4160; Wrobleski et al, J. Med. Chem. 2019, 8973). Alternatively, compound VII can be obtained by the reaction of R4 It can be obtained directly from compound XI by reaction with substituted hydrazines of the NH-NH2 type. [ka]

[0032] Compound XI can be obtained from commercially available 3-chloropyrazine-2-carboxamide (XII) by reaction with N,N-dimethylformamide dimethyl acetal (DMFDMA). [ka]

[0033] This transformation is typically carried out in an inert solvent at temperatures between 0° C. and 100° C., preferably between 25° C. and 90° C., using 1.5 to 3 equivalents of DMFDMA [see Lin et al., J. Org. Chem. 1979, 4160; Wrobleski et al., J. Med. Chem. 2019, 8973]. Suitable solvents are halogenated hydrocarbons such as DCM and 1,2-dichloroethane, ethers such as THF, aromatic solvents such as toluene, and polar aprotic solvents such as DMSO, preferably DCM.

[0034] The starting materials are generally reacted with each other in equimolar amounts. In terms of yield, it may be advantageous to use an excess of DMFDMA based on XII.

[0035] Additionally, compound I may be a 4-methoxybenzyl-(PMB-) substituted compound I (R 4=PMB) or such a positional isomer of compound I in which the PMB group is attached to any one of the three nitrogen atoms of the triazole ring, can be obtained, for example, in a two-step sequence comprising removal of the PMB group by treatment with an acid such as TFA, followed by reaction of intermediate (Int) with reagents and reaction conditions as described above for the synthesis of compound VII from compound IX, as described in WO2011076725. Intermediate compound (Int) is novel. The variables in formula (Int) are as defined for formula I. [ka]

[0036] The reaction mixture is worked up in the usual way, for example by mixing with water, extracting with a suitable organic solvent, separating the phases and, if appropriate, chromatographically purifying the crude product. Some of the intermediates and final products are obtained in the form of a colorless or slightly brownish viscous oil, which is purified or stripped of volatile components under reduced pressure and at moderately elevated temperatures. If the intermediates and final products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0037] If the individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.

[0038] However, if the synthesis gives rise to a mixture of isomers, separation is generally not always necessary since in some cases the individual isomers may interconvert during further processing or application for use (e.g. under the action of light, acid or base). Such conversions may also occur after use, for example in the treatment of plants, in treated plants or in pests to be controlled.

[0039] The groups of organic moieties referred to in the definitions of the variables above, as well as the term halogen, are generic names for the individual members of the group listed individually. n ~Cm indicates in each case the possible number of carbon atoms in the group.

[0040] The term "partially or fully substituted" by a group generally means that the group is substituted with the same or different groups.

[0041] The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine.

[0042] The term "alkyl" as used herein and in the alkyl portion of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group usually having 1 to 10 carbon atoms, frequently 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and more preferably 1 to 3 carbon atoms. Examples of alkyl groups are methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl, n-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 2 methylbutyl, 3 methylbutyl, 2,2-dimethylpropyl, 1 ethylpropyl, n-hexyl, 1,1-dimethyl-propyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methyl-propyl and 1-ethyl-2-methylpropyl.

[0043] The term "haloalkyl" as used herein and in the haloalkyl moiety of haloalkylcarbonyl, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl denotes a linear or branched alkyl group, usually having 1 to 10 carbon atoms, frequently 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in each case of which the hydrogen atoms of this group are partially or fully replaced by halogen atoms. Preferred haloalkyl moieties are selected from C1 to C4 haloalkyl, more preferably from C1 to C3 haloalkyl or C1 to C2 haloalkyl, in particular from C1 to C2 fluoroalkyl, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2 difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, etc.

[0044] The term "alkoxy" as used herein denotes a straight-chain or branched alkyl group, usually having 1 to 10 carbon atoms, frequently 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in each case bonded via an oxygen atom. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, etc.

[0045] The term "alkoxyalkyl" as used herein denotes an alkyl group, usually containing 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, with one carbon atom being as defined above, and usually containing 1 to 4, preferably 1 or 2 carbon atoms. Examples are CHOCH, CH-OCH, 2-(methoxy)ethyl and 2-(ethoxy)ethyl.

[0046] The term "haloalkoxy" as used herein denotes a linear or branched alkoxy group having 1 to 10 carbon atoms, frequently 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, in each case in which the hydrogen atoms of this group are partially or completely replaced by halogen atoms, especially fluorine atoms. Preferred haloalkoxy moieties include C1-C4 haloalkoxy, especially C1-C2 fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 fluoroethoxy, 2-fluoroethoxy, 2,2 difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2 dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, etc.

[0047] The term "alkylthio" (alkylsulfanyl: S-alkyl) as used herein refers to a straight or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-alkylthio), more preferably 1 to 3 carbon atoms attached via a sulfur atom.

[0048] The term "haloalkylthio" as used herein refers to an alkylthio group as defined above, wherein the hydrogen atoms are partially or fully replaced by fluorine, chlorine, bromine and / or iodine.

[0049] The term "alkylsulfinyl" (alkylsulfoxyl: S(=O)-alkyl) refers to a linear or branched saturated alkyl group (as described above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded at any position of the alkyl group via the sulfur atom of the sulfinyl group.

[0050] The term "haloalkylsulfinyl" as used herein refers to an alkylsulfinyl group as defined above, wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and / or iodine.

[0051] The term "alkylsulfonyl" (S(=O)2-alkyl) as used herein denotes a linear or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-alkylsulfonyl), preferably 1 to 3 carbon atoms, bonded at any position of the alkyl group via the sulfur atom of the sulfonyl group.

[0052] The term "haloalkylsulfonyl" as used herein refers to an alkylsulfonyl group as defined above, wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and / or iodine.

[0053] The term "alkylcarbonyl" refers to an alkyl group, as defined above, attached to the remainder of the molecule through the carbon atom of a carbonyl group (C=O).

[0054] The term "haloalkylcarbonyl" denotes an alkylcarbonyl group as defined above, wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and / or iodine.

[0055] The term "alkoxycarbonyl" denotes an alkylcarbonyl group, as defined above, attached to the remainder of the molecule through an oxygen atom.

[0056] The term "haloalkoxycarbonyl" denotes an alkoxycarbonyl group as defined above, wherein the hydrogen atoms are partially or fully substituted with fluorine, chlorine, bromine and / or iodine.

[0057] The term "alkenyl" as used herein denotes in each case a monounsaturated hydrocarbon group usually having 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, such as vinyl, allyl (2-propen-1-yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl, 3-buten-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en-1-yl, and the like.

[0058] The term "haloalkenyl" as used herein refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or fully replaced with halogen atoms.

[0059] The term "alkynyl" as used herein denotes in each case a monounsaturated hydrocarbon group, usually having 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, such as ethynyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1-yl), 2-butyn-1-yl, 3-butyn-1-yl, 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl, 1-ethylprop-2-yn-1-yl, and the like.

[0060] The term "haloalkynyl" as used herein refers to an alkynyl group as defined above wherein the hydrogen atoms have been partially or fully replaced with halogen atoms.

[0061] The term "cycloalkyl" as used herein and in the cycloalkyl portion of cycloalkoxy and cycloalkylthio means, in each case, a monocyclic alicyclic group usually having 3 to 10 or 3 to 6 carbon atoms, such as cyclopropyl (cC3H5), cyclobutyl (cC4H7), cyclopentyl (cC5H9), cyclohexyl (cC6H7), cyclopropyl (cC6H8), cyclobutyl (cC4H9), cyclopentyl (cC5H9), cyclohexyl (cC6H8), cyclopropyl (cC6H8), cyclohexyl (cC6H8), cyclobutyl (cC4H8), cyclopentyl (cC5H8), cyclohexyl (cC6 ... 11), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0062] The term "halocycloalkyl" as used herein and in the halocycloalkyl moiety of halocycloalkoxy and halocycloalkylthio denotes a monocyclic alicyclic group, usually having 3 to 10 C atoms or 3 to 6 C atoms, in each case in which at least one, for example 1, 2, 3, 4 or 5, of the hydrogen atoms is replaced by a halogen, in particular fluorine or chlorine. Examples are 1- and 2-fluorocyclopropyl, 1,2-, 2,2- and 2,3-difluorocyclopropyl, 1,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclopropyl, 1- and 2-chlorocyclopropyl, 1,2-, 2,2- and 2,3-dichlorocyclopropyl, 1,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclopropyl, 1-, 2- and 3-fluorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-, 2- and 3-chlorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl, and the like.

[0063] The term "cycloalkenyl" as used herein and in the cycloalkenyl moiety of cycloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic or bicyclic, preferably a monocyclic monounsaturated non-aromatic group, usually having 3 to 10, for example 3 or 4 or 5 to 10, carbon atoms, preferably 3 to 8 carbon atoms. Examples are cyclopenten-1-yl and cyclohexen-1-yl.

[0064] The term "halocycloalkenyl" as used herein and in the halocycloalkenyl moiety of halocycloalkenyloxy and halocycloalkenylthio denotes a monocyclic monounsaturated non-aromatic group, usually having 3 to 10, for example 3 or 4 or 5 to 10 carbon atoms, preferably 3 to 8 carbon atoms, in each case in which at least one, for example 1, 2, 3, 4 or 5 of the hydrogen atoms is replaced by a halogen, in particular fluorine or chlorine. Examples are 3,3-difluorocyclopropen-1-yl and 3,3-dichlorocyclopropen-1-yl.

[0065] The term "cycloalkenylalkyl" denotes a cycloalkenyl group as defined above, which is bonded to the remainder of the molecule via an alkyl group, such as a C1-C5 alkyl group or a C1-C4 alkyl group, in particular a methyl group (=cycloalkenylmethyl).

[0066] The term "carbocycle" or "carbocyclyl" includes a monocyclic non-aromatic ring, generally 3 to 12 members, preferably 3 to 8 members or 5 to 8 members, more preferably 5 or 6 members, containing 3 to 12, preferably 3 to 8 or 5 to 8 members, more preferably 5 or 6 carbon atoms. Preferably, the term "carbocycle" encompasses cycloalkyl and cycloalkenyl groups as defined above.

[0067] The term "heterocycle" or "heterocyclyl" generally includes 3-12 membered, preferably 3-6 membered, and especially 6 membered, monocyclic heterocyclic non-aromatic groups. Heterocyclic non-aromatic groups usually contain 1, 2, 3, 4 or 5, preferably 1, 2 or 3, heteroatoms selected from N, O and S as ring members, and the S atom as a ring member may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic groups include saturated or unsaturated non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxide (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothietanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidin ... Examples of heterocycles which also contain one or two carbonyl groups as ring members include pyrrolidinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl, etc. Examples of heterocycles which also contain one or two carbonyl groups as ring members include pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl, etc.

[0068] The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic groups containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members. Examples of 5- or 6-membered heteroaromatic groups are pyridyl, i.e. 2-, 3- or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl. oxadiazolyl, for example 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, for example 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, for example 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H- or 4H-1,2,4-triazolyl, and tetrazolyl, i.e. 1H- or 2H-tetrazolyl. The term "hetaryl" also includes bicyclic 8-10 membered heteroaromatic groups containing one, two or three heteroatoms selected from N, O and S as ring members, where the 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or a 5- or 6-membered heteroaromatic group. Examples of 5- or 6-membered heteroaromatic rings fused to a phenyl ring or a 5- or 6-membered heteroaromatic group include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, quinolinyl, isoquinolinyl, purinyl, 1,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl, or pyridoimidazolyl.These fused hetaryl groups may be attached to the remainder of the molecule through any ring atom of the 5- or 6-membered heteroaromatic ring or through a carbon atom of the fused phenyl moiety.

[0069] The terms "heterocyclylalkyl" and "hetarylalkyl" refer to a heterocyclyl or hetaryl as defined above, which is bonded to the remainder of the molecule via a C1-C5 alkyl group or a C1-C4 alkyl group, respectively, in particular a methyl group (=heterocyclylmethyl or hetarylmethyl, respectively).

[0070] The terms "arylalkyl" and "phenylalkyl" refer to aryl and phenyl as defined above, respectively, bonded to the remainder of the molecule via a C1-C5 alkyl group or a C1-C4 alkyl group, in particular a methyl group (=arylmethyl or phenylmethyl), examples include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenoxyethyl, etc.

[0071] The terms "alkylene," "cycloalkylene," "heterocycloalkylene," "alkenylene," "cycloalkenylene," "heterocycloalkenylene," and "alkynylene" refer to alkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl, and alkynyl, as defined above, attached to the remainder of the molecule through two atoms, preferably two carbon atoms, of the respective group such that they serve as linkers between two portions of the molecule.

[0072] In certain embodiments, the variables of the compounds of formula I have the following meanings, which meanings alone and in combination with each other are specific embodiments of the compounds of formula I.

[0073] Embodiments of the present invention and preferred compounds for use in pesticidal methods and insecticidal applications are outlined in the following paragraphs.

[0074] In terms of the variables, particularly preferred embodiments of the intermediates correspond to the embodiments of the compounds of formula I.

[0075] In a preferred embodiment, compound I is present in the form of a mixture of compounds IA and IB, in which compound IA having the S configuration of the carbon atom adjacent to the nitrogen atom is present in an amount of more than 50% by weight, in particular at least 70% by weight, more particularly at least 85% by weight, in particular at least 90% by weight, based on the total weight of compounds IA and IB. [ka]

[0076] In one particularly preferred embodiment of the invention, the method comprises the step of contacting the plant, a part thereof, its plant propagation material, the pest, its food source, habitat or breeding ground with a pesticidally effective amount of a compound of formula IA.

[0077] Preferably, R 1 is H, C1-C6-alkyl, C3-C6-alkynyl, C3-C6-cycloalkyl or C1-C4-alkyl-C3-C6-cycloalkyl.

[0078] Preferably, R 2 is CH3.

[0079] X is preferably CH or CR 3 , in particular CH. Such compounds correspond to formula I.1. [ka]

[0080] In another embodiment, X is N. Such compounds correspond to formula I.2. [ka]

[0081] R 3is preferably halogen, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-cycloalkyl unsubstituted or substituted by one or more CN, C3-C4-halocycloalkyl, S(O) m -C1-C4-Alkyl, S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3-C4-halocycloalkyl. R 3 The index m is preferably 2. The index n is preferably 2.

[0082] In another embodiment, R 3 is preferably halogen, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, unsubstituted or one or more R 3a C-C-cycloalkyl substituted by R 3a is preferably CN, OH, or C1-C4-alkoxy. 3 The index m is preferably 2. The index n is preferably 2.

[0083] In another embodiment, R 3 is preferably located between the 3rd and 5th positions.

[0084] In another embodiment, R 3 is preferably halogen, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O) m -C1-C4-Alkyl, S(O) m -C1-C4-haloalkyl, S(O) m -C3~C4-Cycloalkyl, S(O) m -C3~C4-halocycloalkyl, or S(O) m -R 14 where R 14 is R 3a is phenyl partially substituted by

[0085] In another embodiment of the compound of formula I, R 3 is halogen, CN, NO2, C1-C4-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, OR 14 , S(O) m -R 14 wherein the ring is unsubstituted or R 11 has been replaced by

[0086] R 4 is preferably C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, CH2C(O)NH-C1-C6-alkyl, S(O) m -C1-C4-alkyl or unsubstituted or containing one or more groups R 3 is phenyl substituted by

[0087] In particular, with respect to their use, the compounds of formula I compiled in the following table are preferred, which correspond to formulae I.1* and I.2*, respectively. Each of the radicals described for the substituents in the table is furthermore itself a particularly preferred embodiment of the substituent in question, independently of the combination in which it is described. [ka]

[0088] Table 1 R 4 is CN and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0089] Table 2 R 4 is CH3 and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0090] Table 3 R 4 is C2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0091] Table 4 R 4 is CH2CH2CH3, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0092] Table 5 R 4 is CH(CH3)2, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0093] Table 6 R 4 is cC3H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0094] Table 7 R 4 is CH2CF3, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0095] Table 8 R 4 is CH2OCH3, and R for the compound 1 and (R 3 ) nEach combination of the formula I.1* corresponds to one row of Table A.

[0096] Table 9 R 4 is C(=O)NH2, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0097] Table 10 R 4 is C(=O)NHCH3, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0098] Table 11 R 4 is C(=O)NHC2H5, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0099] Table 12 R 4 is C(=O)N(CH3)2, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0100] Table 13 R 4 is C(=O)N(CH3)C2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0101] Table 14 R 4is C(=O)OCH3, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0102] Table 15 R 4 is C(=O)OC2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0103] Table 16 R 4 is CH2C(=O)NHCH3, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0104] Table 17 R 4 is 4,5-dihydrooxazol-2-yl, and R 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0105] Table 18 R 4 is SO2CH3 and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0106] Table 19 R 4 is SO2C2H5 and R for the compound 1 and (R 3 ) n Each combination of the formula I.1* corresponds to one row of Table A.

[0107] Table 20 R 4 is CN and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0108] Table 21 R 4 is CH3 and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0109] Table 22 R 4 is C2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0110] Table 23 R 4 is CH2CH2CH3, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0111] Table 24 R 4 is CH(CH3)2, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0112] Table 25 R 4 is cC3H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0113] Table 26 R 4 is CH2CF3, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0114] Table 27 R 4 is CH2OCH3, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0115] Table 28 R 4 is C(=O)NH2, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0116] Table 29 R 4 is C(=O)NHCH3, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0117] Table 30 R 4 is C(=O)NHC2H5, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0118] Table 31 R 4 is C(=O)N(CH3)2, and R for the compound 1 and (R 3 ) nEach combination of the formula I.2* corresponds to one row of Table A.

[0119] Table 32 R 4 is C(=O)N(CH3)C2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0120] Table 33 R 4 is C(=O)OCH3, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0121] Table 34 R 4 is C(=O)OC2H5, and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0122] Table 35 R 4 is CH2C(=O)NHCH3, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0123] Table 36 R 4 is 4,5-dihydrooxazol-2-yl, and R 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0124] Table 37 R 4is SO2CH3 and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0125] Table 38 R 4 is SO2C2H5 and R for the compound 1 and (R 3 ) n Each combination of the formula I.2* corresponds to one row of Table A.

[0126] [Table 1]

[0127] [Table 2]

[0128] [Table 3]

[0129] [Table 4]

[0130] [Table 5]

[0131] [Table 6]

[0132] The term "compounds of the invention" refers to compounds of Formula I, or "Compound I," including salts, tautomers, stereoisomers, and N-oxides thereof.

[0133] The present invention also relates to an agrochemical composition comprising an adjuvant and at least one compound I.

[0134] The pesticidal composition comprises a pesticidally effective amount of Compound I.

[0135] The pesticidal composition comprises a pesticidally effective amount of Compound I.

[0136] The compounds I can be converted into conventional types of pesticide compositions, such as, for example, solutions, emulsions, suspensions, dusts, powders, pastes, granules, compacts, capsules and mixtures thereof. Examples of types of compositions are suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsifiable concentrates (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, pastilles, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), compacts (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal articles (e.g., LN), and gel formulations (e.g., GF) for the treatment of plant propagation materials (e.g., seeds). These and further types of compositions are defined in “Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.

[0137] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, moisturizers, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers and binders.

[0138] Suitable solvents and liquid carriers are water and organic solvents. Suitable solid carriers or fillers are minerals.

[0139] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants. Surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (international or North American edition). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates. Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants. Suitable cationic surfactants are quaternary surfactants.

[0140] The agrochemical composition generally contains 0.01 to 95% by weight, preferably 0.1 to 90% by weight, most preferably 0.5 to 75% by weight of the active substance. The active substance is used with a purity of 90% to 100%, preferably 95% to 100%.

[0141] Various kinds of oils, wetting agents, adjuvants or fertilizers can be added to the active substances or compositions containing them, either as a premix or, if appropriate, immediately before use (tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1.

[0142] The user usually applies the composition according to the invention from a pre-dosing device, a backpack sprayer, a spray tank, a spray plane or an irrigation system. Usually, the agrochemical composition is brought to the desired application concentration with water, buffers and / or further adjuvants, thus obtaining a ready-to-use spray solution or an agrochemical composition according to the invention. Usually, 20 to 2000 liters of ready-to-use spray solution are applied per hectare of agricultural land.

[0143] Compound I is suitable for use in protecting crops, plants, plant propagation materials (e.g. seeds), or the soil or water in which the plants are growing, from attack or infestation by animal pests. The present invention therefore also relates to a method for protecting plants, which comprises contacting a crop, plant, plant propagation material, such as seeds, or the soil or water in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of compound I.

[0144] Compound I is also suitable for use in combating or controlling animal pests.Accordingly, the present invention also relates to a method for combating or controlling animal pests, which comprises contacting animal pests, their habitats, breeding places or food sources, or crops, plants, plant propagation materials, such as seeds, or soil or areas, materials or environments in which animal pests grow or may grow, with a pesticidal amount of compound I.

[0145] Compound I is effective against any and all developmental stages, including eggs, larvae, pupae, and adults, both through contact and ingestion.

[0146] The compounds I can be applied on their own or in the form of compositions which contain them.

[0147] Application can be carried out both before and after infestation of the crops, plants or plant propagation materials by pests.

[0148] The term "contacting" includes both direct contact (applying a compound / composition directly onto an animal pest or plant) and indirect contact (applying a compound / composition to a locus).

[0149] The term "animal pests" includes arthropods, gastropods and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, especially insects.

[0150] The term "plants" includes but is not limited to cereals such as durum and other wheat, rye, barley, triticale, oats, rice, or corn (fodder and sugar / sweet corn and field corn); beets, such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits, or soft fruits, such as apple, pear, plum, peach, nectarine, almond, cherry, papaya, strawberry, raspberry, blackberry, or gooseberry; legumes, such as beans, lentils, peas, alfalfa, or soybeans; oil plants, such as rapeseed (oilseed rape), turnip, or other oilseeds. rape), mustard, olive, sunflower, coconut, cocoa bean, castor bean, oil palm, groundnut, or soybean; cucurbits, such as squash, pumpkin, cucumber, or melon; fibre plants, such as cotton, flax, hemp, or jute; citrus fruits, such as orange, lemon, grapefruit, or mandarin; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbage, carrot, onion, These include garlic, leek, tomato, potato, cucurbits, or sweet pepper; lauraceae, such as avocado, cinnamon, or camphor; energy plants and source plants, such as corn, soybean, rapeseed, sugarcane, or oil palm; tobacco; nuts, such as walnuts; pistachios; coffee; tea; bananas; vines; hops; sweetleaf (stevia); rubber plants, or ornamental and forest plants, shrubs, broadleaf or evergreen trees, eucalyptus; turf; lawn; grasses. Preferred plants include potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugarcane; fruits; vines, ornamentals; or vegetables such as cucumbers, tomatoes, beans or pumpkins.

[0151] The term "seed" encompasses seeds and plant propagation bodies (including true seeds, seed pieces, suckers, corms, bulbs, fruits, tubers, grains, cuttings and cut shoots), preferably meaning true seeds.

[0152] "Pesticidal effective amount" means the amount of active ingredient required to obtain an observable effect on growth, including the effect of necrosis, killing, hindering, preventing, and removing, destroying, or otherwise gradually reducing the appearance and activity of the target organism. Pesticidal effective amount may vary for various compounds / compositions used in the present invention. Pesticidal effective amount of the composition also varies according to the prevailing conditions (e.g., desired pesticidal effect and duration, weather, target species, location, mode of application).

[0153] When used in treating crop plants (e.g. by foliar application), the rate of application of the active ingredient of the invention may range from 0.0001 g to 4000 g per hectare, for example from 1 g to 2 kg per hectare, or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.

[0154] Compound I is also suitable for use against non-crop insect pests, in which case it can be used as a bait composition, gel, general insect spray, aerosol, ultra-low volume application and mosquito net (impregnation or surface application).

[0155] The term "non-crop insect pest" refers to pests that are particularly associated with non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitoes, bedbugs, crickets, or cockroaches, such as Aedes aegypti, Musca domestica, Tribolium spp.; termites, such as Reticulitermes flavipes, Coptotermes formosanus; cockroaches, such as Blatella germanica, Periplaneta Americana; ants, such as Solenopsis invicta, Linepithema humile, and Camponotus pennsylvanicus.

[0156] The bait can be a liquid, solid, or semi-solid preparation (e.g., a gel).When used in a bait composition, the typical content of the active ingredient is 0.001% to 15% by weight of the active compound, preferably 0.001% to 5% by weight.

[0157] Compound I and compositions thereof can be used to protect wooden materials (e.g., trees, fence boards, sleepers, framing, artistic artifacts, etc.) and buildings, as well as construction materials, furniture, leather, textiles, vinyl products, electrical wires and cables, etc., from ants, termites, and / or wood- or fabric-destroying beetles, and to inhibit ant and termite damage to crops or humans (e.g., when the pests have invaded homes and public facilities or nested in gardens, orchards, or parks).

[0158] Customary application rates for the protection of materials are, for example, 1 m of treated material. 2 0.001g to 2000g or 0.01g to 1000g of active compound per m 2 Each serving weighs 0.1g to 50g.

[0159] The insecticide composition used for impregnating the material typically contains from 0.001 to 95% by weight, preferably from 0.1 to 45% by weight, more preferably from 1 to 25% by weight of at least one repellent and / or insecticide.

[0160] The compounds of the invention are effective against animal pests, for example insects of the suborder Auchenorrhyncha, for example Amrasca biguttula, Empoasca spp., Nephotettix virescens, Sogatella furcifera, Mahanarva spp., Laodelphax striatellus, Nilaparvata lugens, Diaphorina citri; Lepidoptera, e.g. Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticarsia gemataris gemmatalis), Agrotis ipsilon, Chrysodeixis includens; Hemipteran insects, such as Lygus spp., stink bugs, such as Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus; Thrips, e.g. Frankliniella spp., Thrips spp., Dichromothrips corbettii; Aphids, e.g. Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae; Whiteflies, e.g. Trialeurodes vaporariorum, Bemisia spp.; Coleoptera, e.g. Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa ​​decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.; Flies, e.g. Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp.; Mosquitoes (Diptera), e.g., Aedes aegypti, A. albopictus, A. vexans, Anastrepha ludens, Anopheles maculipennis, A. crucians, A. albimanus, A. gambiae, A. freeborni, A. leucosphyrus, A. minimus, A. quadrimaculatus; Coccoidea, e.g., Aonidiella aurantia, Ferrisia virgate; Arachnida anthropods (mites), for example Penthaleus major, Tetranychus spp.; It is particularly suitable for efficiently combating Nematodes, such as Heterodera glycines, Meloidogyne sp., Pratylenchus spp., Caenorhabditis elegans.

[0161] Compound I is suitable for use in the treatment or protection of animals against parasitic infestation or infection. Thus, the present invention also relates to the use of the compounds of the present invention for the manufacture of a medicament for the treatment or protection of animals against parasitic infestation or infection. Furthermore, the present invention relates to a method for the treatment or protection of animals against parasitic infestation and infection, comprising administering or applying to an animal a parasiticidally effective amount of compound I orally, topically or parenterally.

[0162] The present invention also relates to the non-therapeutic use of the compounds of the present invention for treating or protecting animals against parasitic infestation and infection.Furthermore, the present invention relates to a non-therapeutic method of treating or protecting animals against parasitic infestation and infection, which comprises applying to a locus a parasiticidally effective amount of compound I.

[0163] The compounds of the invention are further suitable for use in combating or controlling parasites in and on animals.Furthermore, the invention relates to a method for combating or controlling parasites in and on animals, comprising contacting the parasites with a parasiticidally effective amount of compound I.

[0164] The present invention also relates to the non-therapeutic use of compound I for combating or eliminating parasites. Furthermore, the present invention relates to a non-therapeutic method for combating or controlling parasites, which comprises applying a parasiticidally effective amount of compound I to a locus.

[0165] Compound I can be effective both through contact (via soil, glass, walls, bed nets, carpets, blankets, or animal parts) and ingestion (e.g., bait).Furthermore, Compound I can be applied to any and all developmental stages.

[0166] The compounds I can be applied on their own or in the form of compositions which contain them.

[0167] The term "habitat" refers to a habitat, food source, breeding ground, area, material, or environment outside an animal in which a parasite lives or can live.

[0168] As used herein, the term "parasites" includes endoparasites and ectoparasites. In some embodiments of the invention, endoparasites may be preferred. In other embodiments, ectoparasites may be preferred. Infestations of warm-blooded animals and fish include lice, bite lice, ticks, botfly, pediculid flies, stable flies, blowflies, flies, myiasis fly larvae, chiggers, black flies, mosquitoes, and fleas.

[0169] The compounds of the present invention are particularly useful for controlling the following parasites: bedbugs (Cimex lectularius), brown dog ticks (Rhipicephalus sanguineus) and cat fleas (Ctenocephalides felis).

[0170] As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Mammals such as cattle, sheep, pigs, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, buffalo, donkeys, fallow deer and reindeer, as well as fur animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks, and fish such as freshwater and saltwater fish, for example trout, carp and eel, are preferred. Domestic animals such as dogs or cats are particularly preferred.

[0171] Compound I may be applied in a total amount of 0.5 mg / kg to 100 mg / kg per day, preferably 1 mg / kg to 50 mg / kg per day.

[0172] For oral administration to warm-blooded animals, Compound I may be formulated as animal feed, animal feed premix, animal feed concentrate, pill, liquid, paste, suspension, drench, gel, tablet, bolus, and capsule. For oral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of Compound I per kg of animal body weight per day, preferably 0.5 mg to 100 mg per kg of animal body weight per day.

[0173] Alternatively, Compound I may be administered to animals parenterally (e.g., by intraruminal, intramuscular, intravenous, or subcutaneous injection). Compound I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, Compound I may be formulated into an implant for subcutaneous administration. Additionally, Compound I may be administered transdermally to animals. For parenteral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of Compound I per kg of animal body weight per day.

[0174] Compound I can also be applied topically to animals in the form of dips, powders, dusts, collars, medals, sprays, shampoos, spot-on formulations and pour-on formulations, as well as ointments or oil-in-water or water-in-oil emulsions.For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm, preferably 1 ppm to 3,000 ppm, of Compound I.In addition, Compound I can be formulated as an ear tag for animals, particularly quadrupeds (e.g., cattle and sheep).

[0175] Oral solutions are administered directly.

[0176] Solutions for application to the skin may be dripped, spread, rubbed, sprinkled or sprayed.

[0177] The gel is applied or spread onto the skin or introduced into a body cavity.

[0178] Pour-on formulations are applied or sprayed onto limited areas of the skin, allowing the active compound to penetrate the skin and act systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture.

[0179] The emulsion may be administered orally, transdermally, or as an injection.

[0180] Suspensions may be administered orally or topically / dermally.

[0181] Semisolid preparations may be administered orally or topically / dermally.

[0182] For the production of solid preparations, the active compound is mixed with suitable excipients and, if appropriate with the addition of auxiliaries, brought into the desired form.

[0183] The compositions that can be used in the present invention can generally contain Compound I at about 0.001 to 95%.

[0184] The ready-to-use preparations contain the compound acting against parasites (preferably ectoparasites) in a concentration of 10 ppm to 80% by weight, preferably 0.1 to 65% by weight, more preferably 1 to 50% by weight, most preferably 5 to 40% by weight.

[0185] Preparations which are diluted before use contain the compound acting against ectoparasites in a concentration of 0.5 to 90% by weight, preferably 1 to 50% by weight.

[0186] Furthermore, the preparation comprises a compound of the formula I acting against endoparasites in a concentration of 10 ppm to 2% by weight, preferably 0.05 to 0.9% by weight, very particularly preferably 0.005 to 0.25% by weight.

[0187] The solid formulations releasing the compounds of the invention may be applied in a total amount of 10 mg to 300 mg, preferably 20 mg to 200 mg, most preferably 25 mg to 160 mg per kg of body weight of the animal to be treated, for a period of 3 weeks. EXAMPLES

[0188] A. Preparation example The compounds were characterized by their mass-to-charge ratio ([m / z]) and retention time (RT; [min]) determined by melting point determination, NMR spectroscopy or mass spectrometry (MS) combined with HPLC analysis (HPLC-MS = high performance liquid chromatography coupled to mass spectrometry) or LC analysis (LC-MS = liquid chromatography coupled to mass spectrometry).

[0189] Method A: HPLC: Shimadzu Nexera UHPLC + Shimadzu LCMS-2020, ESI; Column: Phenomenex Kinetex 1.7 μm XB-C18 100A, 2.1 × 50 mm; Mobile phase: A: water + 0.1% TFA; B: ACN; Temperature: 60 °C; Gradient: 5% B to 100% B in 1.5 min; 0.25 min at 100% B; Flow rate: 0.8 mL / min to 1.0 mL / min in 1.51 min; MS: ESI positive; Mass range (m / z): 100-700.

[0190] Method B: LC: Shimadzu LC-30AD, ESI; Column: Kinetex EVO C18.5 μm 2.1 × 30 mm; Mobile phase: A: water + 0.04% TFA; B: ACN + 0.02% TFA; Temperature: 40 °C; Gradient: 5% B to 100% B in 2.5 min; 100% B to 5% B in 0.02 min; 5% B for 0.5 min; Flow rate: 0.8 mL / min; MS: ESI positive; Mass range: 100-2000.

[0191] Method C: HPLC / MS: Agilent 1260 HPLC MSD: 6125B single quadrupole MSD; Column: Luna C18 2.0 x 50 mm 5 μm; Mobile phase: A: 0.04% TFA in water; B: 0.02% TFA in ACN; Temperature: 40 °C; Gradient: 5% B for 0.4 min; 5% B to 95% B in 2.6 min; 95% B for 1 min; 95% B to 5% B in 0.01 min; 5% B for 0.5 min; Flow rate: 1.0 mL / min; MS: ES-API positive; Mass range: 100-1000.

[0192] Example 1: Preparation of 3-bromo-N-[1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [I1-1] Step 1: Synthesis of (N)-3-chloro-N-(dimethylaminomethylene)pyrazine-2-carboxamide To a solution of 3-chloropyrazine-2-carboxamide (3 g, 0.0191 mol) in DCM (30 mL) was added DMF-dimethylacetal (4.5 g, 0.0382 mol) at 20° C. The mixture was stirred at 50° C. for 2 h, and LCMS showed the reaction was complete. The reaction mixture was concentrated to give the title compound (3 g, yield: crude) as a white solid, which was used directly in the next step.

[0193] Step 2: Synthesis of 2-chloro-3-(1H-1,2,4-triazol-3-yl)pyrazine To a solution of (N)-3-chloro-N-(dimethylaminomethylene)pyrazine-2-carboxamide (3 g, 0.0141 mol) in 1,4-dioxane (30 mL) was added NH2NH2xH2O (1.4 g, 0.0283 mol) and AcOH (30 mL) at 20 °C. The mixture was stirred at 80 °C for 2 h and LCMS showed the reaction was complete. The reaction mixture was concentrated to give crude 2-chloro-3-(1H-1,2,4-triazol-3-yl)pyrazine (3 g, crude) as a yellow solid. A small amount was crystallized for characterization. 1H-NMR (400MHz, DMSO-d6): δ=8.64(m,2H),8.80(d,1H).

[0194] Step 3: Synthesis of 2-chloro-3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazine To a mixture of 2-chloro-3-(1H-1,2,4-triazol-3-yl)pyrazine (1.6 g, 0.0088 mol) in MeCN (80 mL) was added 2,2,2-trifluoroethyl trifluoromethanesulfonate (2.45 g, 0.0106 mol) and K2CO3 (2.276 g, 0.0176 mol) at 20° C. The reaction mixture was stirred at 25° C. for 12 h. LCMS showed 70% product. The reaction mixture was quenched with H2O (20 mL), extracted with EtOAc (3×80 mL), and the separated organic layer was washed with brine (20 mL), dried over Na2SO4, and concentrated. The residue was purified by silica gel column (PE:EtOAc=100:0 gradient to 20:80) to give 2-chloro-3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazine (0.600 g, yield: 26%). 1 H NMR (400MHz, CDCl3): δ=5.24(q,2H),8.17(s,1H),8.57(d,1H),8.64(d,1H).

[0195] Step 4: Synthesis of 2-(1-ethoxyvinyl)-3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazine To a solution of 2-chloro-3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazine (3.8 g, 0.0144 mol) in toluene (100 mL) was added tributyl(1-ethoxyvinyl)stannane (5.21 g, 0.0144 mol) and Pd(PPh3)2Cl2 (1 g) at 25° C. The reaction mixture was stirred at 110° C. for 12 h. LCMS showed the reaction was complete. After the reaction mixture was cooled to room temperature, saturated KF water (150 mL) was added to the reaction mixture and stirred for another 30 min. The mixture was filtered through a Celite pad and the filtrate was extracted with EtOAc (3×50 mL). The separated organic phase was washed with brine (60 mL), dried over Na2SO4 and concentrated. The residue was purified by silica gel column (PE:EtOAc=gradient from 100:0 to 10:90) to give the title compound (3.1 g, yield: 72%). 1 H NMR (400MHz, CDCl3): δ=1.01(t,3H),3.78(q,2H),4.49(d,1H),4.84-4.88(m,1H),4.89-4.94(m,2H),8.30(s,1H),8.61(m,2H).

[0196] Step 5: Synthesis of 1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone To a solution of 2-(1-ethoxyvinyl)-3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazine (3.1 g, 0.0103 mol) in THF (30 mL) was added aqueous HCl (2 M, 30 mL) dropwise at 25° C. The mixture was stirred at 25° C. for 16 h. LCMS showed the reaction was complete. The reaction mixture was diluted with H2O (50 mL) and extracted with EtOAc (3×20 mL). The separated organic phase was washed with brine (40 mL), dried over Na2SO4, and concentrated to give the title compound (2.9 g, crude). 1 H-NMR (400MHz, CDCl3): δ=2.70(s,3H),4.97(q,2H),8.69(s,2H),8.80(br s,1H).

[0197] Step 6: Synthesis of 1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine To a solution of 1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (1.3 g, 4.79 mmol) in MeOH (50 mL) was added NHOAc (3.69 g, 48 mmol), NaBHCN (602 mg, 9.59 mmol) at 20° C., and the reaction mixture was stirred for 16 h. TLC (DCM:MeOH=10:1) showed the reaction was complete. The reaction mixture was concentrated, quenched with HO (50 mL), and the pH was adjusted to about 10 with aqueous NaOH. The mixture was extracted with DCM / iPrOH (3 / 1, 3×20 mL) and the combined organic phases were dried over NaSO and concentrated to give crude 1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine (500 mg, crude), which was used in the next step without further purification.

[0198] Step 7: Synthesis of 3-bromo-N-[1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide To a solution of 3-bromo-5-(trifluoromethyl)benzoic acid (0.494 g, 0.00184 mol) in MeCN (10 mL) was added N,N,N',N'-tetramethylchloroformamidinium hexafluorophosphate (0.773 g, 0.00276 mol), N-methylimidazole (0.453 g, 0.0055 mol) and 1-[3-[1-(2,2,2-trifluoroethyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine (0.5 g, 0.00184 mol) at 20° C. The mixture was stirred at 20° C. for 1 h. LCMS showed the reaction was complete. The reaction mixture was quenched with H2O (10 mL) and extracted with EtOAc (3×30 mL). The combined organic layers were washed with brine (10 mL), dried over Na2SO4, and concentrated. The residue was purified by Prep-HPLC (NH4HCO3) to give the title compound (I1-1, 0.375 g, yield: 39%) as a white solid. 1 H-NMR (400MHz, CDCl3): δ=1.63(d,3H),4.98(m,2H),5.23(quin,1H),7.84(br d,1H),7.90(s,1H),8.02(s,1H),8.15(s,1H),8.43(s,1H),8.67(d,1H),8.74(d,1H). LCMS (Method B): (Desired mass: m / z=523; Observed mass: m / z=523.525).

[0199] Example 2: Preparation of 2,6-dichloro-N-[1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]pyridine-4-carboxamide [I2-1] Step 1: Preparation of 2-chloro-3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazine To a solution of 3-chloro-N-(dimethylaminomethylene)pyrazine-2-carboxamide (84 g, 376.2 mmol) in 1,4-dioxane (840 mL) was added [(4-methoxyphenyl)methylamino]ammonium chloride (142 g, 752.4 mmol) at 15° C. and stirred for 30 min. Acetic acid (840 mL) was added and the mixture was stirred at 15° C. for another 2 h. The reaction mixture was then heated to 80° C. and stirred for 16 h. LC-MS showed the reaction was complete. The reaction was quenched with water (600 mL). The resulting mixture was extracted with EtOAc (3×1 L). The combined organic phase was washed with brine (300 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by column (EtOAc) to give a mixture of 2-chloro-3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazine and 2-chloro-3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazine (66 g crude) as a yellow oil. 1 H-NMR (400MHz, CDCl3): δ=8.62(d,J=2.38Hz,1H),8.48(d,J=2.38Hz,1H),8.0 8(s,1H),7.06(d,J=8.66Hz,2H),6.75-6.80(m,2H),5.45(s,2H),3.75(s,3H).

[0200] Step 2: Preparation of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone: To a solution of a mixture of 2-chloro-3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazine and 2-chloro-3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazine (66 g, 218.7 mmol) in DMF was added Pd(PPh3)2Cl2 (15.3 g, 21.87 mmol) and tributyl(1-ethoxyvinyl)stannane (18.5 g, 328.1 mmol) at 15° C. The reaction mixture was heated to 100° C. and stirred for 16 h. TCL (EtOAc) showed the reaction was complete. The reaction mixture was poured into KF (aq, sat, 1 L) and stirred for 2.5 h. The mixture was filtered and the filtrate was extracted with EtOAc (3×1 L). The combined organic phases were dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column (EtOAc) to give a mixture of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone and 1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (57 g crude) as a yellow solid. 1 H-NMR (400MHz, CDCl3): δ=8.75(d,J=2.38,1H),8.66(d,J=2.50Hz,1H),7.96(s,1 H),7.18-7.24(m,2H),6.78-6.86(m,2H),5.60(s,2H),3.77(s,3H),2.72(s,3H).

[0201] Step 3: Preparation of 1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanone: A solution of 1-[3-[1-(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone and 1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (5.7 g, 18.43 mmol) in TFA (57 ml) was stirred at 80° C. for 16 h. LC-MS showed the reaction was complete. The mixture was concentrated under reduced pressure and purified by column (EtOAc:EtOH=3:1) to give 1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanone (3.4 g, crude) as a pale yellow solid. 1 H-NMR (400MHz, CDCl3): δ=8.81(d,J=2.50Hz,1H),8.71(d,J=2.50Hz,1H),8.46(br s,1H),2.69(s,3H).

[0202] Step 4: Preparation of 1-[3-[1-(4-nitrophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethenone: To a solution of 1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanone (3 g, 15.86 mmol) in DMF was added NaH (571 mg, 23.79 mmol) at 0° C. A solution of 1-fluoro-4-nitro-benzene (2.91 g, 20.62 mmol) in DMF (10 mL) was added. The reaction mixture was stirred at 15° C. for 16 h. TLC (EtOAc:EtOH=3:1) showed the reaction was complete. The mixture was quenched with water (120 mL) and extracted with EtOAc (3×80 mL). The combined organic phase was washed with brine (3×80 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography (EtOAc:EtOH=3:1) to give 1-[3-[1-(4-nitrophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (4.5 g, 91.5% yield) as a yellow solid. 1H-NMR (400MHz, CDCl3): δ=8.83(d,J=2.38Hz,1H),8.79(s,1H),8.69(d,J=2.38Hz,1H),8.40-8.45(m,2H),7.96-8.00(m,2H),2.80(s,3H).

[0203] Step 5: Preparation of 1-[3-[1-(4-aminophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone: To a solution of 1-[3-[1-(4-nitrophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (4.4 g, 14.18 mmol) in MeOH (45 ml) was added SnCl2 (8.067 g, 42.54 mmol) at 15 °C. The reaction mixture was heated to 80 °C and stirred for 3 h. LC-MS showed the reaction was complete. The mixture was concentrated and quenched with water (20 ml). The pH was adjusted to pH 9 with NaOH (aq, 2N) and extracted with EtOAc (3 x 20 mL). The combined organic phase was washed with brine (20 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column (EtOAc:EtOH=3:1) to give 1-[3-[1-(4-aminophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (750 mg, 19% yield) as a yellow solid. 1 H-NMR(400MHz,DMSO-d6):δ=9.15(s,1H),8.89(d,J=2.50Hz,1H),8.76(d,J= 2.50Hz,1H),7.46-7.54(m,2H),6.66-6.72(m,2H),5.49(s,2H),2.64(s,3H).

[0204] Step 6: Preparation of 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanone: To a solution of 1-[3-[1-(4-aminophenyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (720 mg, 2.57 mmol) in DMF (8 mL) was added NaNO2 (355 mg, 5.14 mmol) and Et2O·BF3 (725 mg, 5.14 mmol) at 15 °C. The reaction mixture was heated to 50 °C and stirred for 16 h. LC-MS showed the reaction was complete. The mixture was quenched with water (30 mL) and extracted with EtOAc (3 × 20 mL). The combined organic phase was washed with brine (3 × 20 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by column (EtOAc) to give 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethenone (480 mg, 70% yield) as a yellow solid. 1 H-NMR(400MHz,MeOH-d4):δ=9.18(s,1H),8.84(d,J=2.26Hz,1H),8.74(d,J=2.26Hz, 1H),7.86(d,J=8.16Hz,2H),7.58(t,J=7.78Hz,2H),7.44-7.50(m,1H),2.74(s,3H).

[0205] Step 7: Preparation of 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanamine: To a solution of 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanone (450 mg, 1.70 mmol) in MeOH (30 mL) was added NH3 (7 M, 6 mL) and NHOAc (1.308 g, 17.0 mmol) in MeOH at 15 °C. The reaction mixture was stirred for 3 h. The mixture was then heated to 50 °C and stirred for 16 h. LC-MS showed the reaction was complete. The mixture was quenched with water (90 mL) and extracted with EtOAc (3 x 50 mL). The combined organic phases were washed with brine (50 mL), dried over Na2SO4, filtered and concentrated under reduced pressure to give 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanamine (400 mg, crude) as a yellow solid. 1 H-NMR(400MHz,DMSO-d6):δ=9.51(s,1H),8.73-8.79(m,1H),8.68(d,J=2.25Hz,1H),7.94-7.98(m,2H),7.62 (t,J=7.94Hz,2H),7.47(t,J=7.38Hz,1H),4.77(q,J=6.63Hz,1H),3.10-3.47(m,2H),1.38(d,J=6.63Hz,3H).

[0206] Step 8: Preparation of 2,6-dichloro-N-[1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]pyridine-4-carboxamide [I2-1]: To a solution of 1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethanamine (433 mg, 2.53 mmol) in ACN (4 mL) was added NMI (370 mg, 4.506 mmol) and TCFH (631 mg, 2.253 mmol) at 15° C. A solution of 2,6-dichloropyridine-4-carboxylic acid (400 mg, 1.502 mmol) in ACN (4 mL) was added. The mixture was stirred at 15° C. for 16 h. LC-MS showed the reaction was complete. The mixture was concentrated under reduced pressure and purified by prep-HPLC (NH4HCO3) to give 2,6-dichloro-N-[1-[3-(1-phenyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]pyridine-4-carboxamide (I2-1, 102 mg, 15% yield) as a yellow solid. 1 H-NMR (400MHz, CDCl3): δ=8.74-8.81(m,2H),8.67(d,J=2.26Hz,1H),7.99(br d,J=7.65Hz,1H),7.82(d,J=7.65Hz,2H),7.65(s,2H),7.59(t,J=7.84Hz,2H),7.45-7.51(m,1H),6.54-6.64(m,1H),1.68(d,J=6.53Hz,3H).

[0207] Example 3: Preparation of 3-chloro-N-[1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [I1-4] Step 1: Preparation of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine To a solution of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone and 1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanone (10 g, 32.4 mmol) in MeOH (1 L) was added NH3 in MeOH (7 M, 100 mL) and NHOAc (25 g, 324 mmol) at 15° C. The reaction mixture was stirred for 30 min. The mixture was then heated to 50° C. and stirred for 16 h. LC-MS showed the reaction was complete. The reaction mixture was concentrated under reduced pressure and purified by HPLC to give a mixture of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine and 1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine (10 g, 50% yield) as a yellow oil.

[0208] Step 2: Preparation of 3-chloro-N-[1-[3-[1-(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (I1-4) To a solution of 3-chloro-5-(trifluoromethyl)benzoic acid (10.8 g, 48.3 mmol) in DMF (50 mL) was added TEA (6.5 g, 64.4 mmol) and HATU (18.4 g, 48.4 mmol) under N2 atmosphere at 0° C. The reaction mixture was stirred at this temperature for 30 min. A mixture of 1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine and 1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethanamine (8 g, 32.2 mmol) in DMF (10 mL) was added to the reaction mixture and stirred at 15° C. for 16 h. TLC (EtOAc:EtOH=3:1) showed the reaction was complete. The reaction was quenched with NH4Cl (aq, 50 mL) and extracted with EtOAc (3 x 50 mL). The combined organic phase was washed with brine (3 x 50 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column (EtOAc:EtOH = 3:1) to give 3-chloro-N-[1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (I1-4, 3 g, 18.1% yield) as a yellow oil. 1 H-NMR (400MHz, CDCl3): δ=8.71(d,J=2.38Hz,1H),8.62(d,J=2.38Hz,1H),8.14(s,1H),7.96-8.04(m,3H),7.74(s,1H) ,7.35(d,J=8.66Hz,2H),6.94(d,J=8.66Hz,2H),6.47-6.57(m,1H),5.43(s,2H),3.83(s,3H),1.60(d,J=6.65Hz,3H).

[0209] Example 4: Preparation of 3-chloro-N-[1-[3-[1-[(2,2-dichlorocyclopropyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [I1-14] Step 1: Preparation of 3-chloro-N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [INT] A solution of 3-chloro-N-[1-[3-[1-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide and 3-chloro-N-[1-[3-[2-[(4-methoxyphenyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (11 g, 21.3 mmol) in TFA (10 mL) was heated to 80° C. and stirred for 16 h. LC-MS showed the reaction was complete. The reaction mixture was concentrated under reduced pressure and purified by column (EtOAc:EtOH=3:1) to give 3-chloro-N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (6 g, 71.4% yield) as a grey solid. 1 H-NMR (400MHz, CDCl3): δ=8.69(d,J=2.25Hz,1H),8.65(d,J=2.25Hz,1H),8.37(s,1H),8.25(br dd,J=7.00,1.88HZ,1H),8.03(s,1H),7.99(s,1H),7.75(s,1H),6.51-6.61(m,1H)1.68(d,J=6.75Hz,3H). LCMS (Method B): (Desired mass: m / z=396.0; Observed mass: m / z=397.0)

[0210] Step 2: Preparation of 3-chloro-N-[1-[3-[1-[(2,2-dichlorocyclopropyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [I1-14] To 3-chloro-N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (500 mg, 1.26 mmol) in toluene (10 mL) was added (2,2-dichlorocyclopropyl)methanol (354 mg, 2.5 mmol) and (tributylphosphoranylidene)acetonitrile (600 mg, 2.5 mmol) at 20° C. The reaction mixture was heated to 130° C. and stirred for 12 h. LC-MS showed the reaction was complete. The mixture was concentrated under reduced pressure and purified by prep-HPLC (TFA) to give 3-chloro-N-[1-[3-[1-[(2,2-dichlorocyclopropyl)methyl]-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (I1-14, 80 mg, 12% yield) as a yellow syrup. 1 H-NMR(400MHz,CHCl3-d):δ=8.72(d,1H),8.71(d,1H),8.50(s,1H),8.01-7.96(m,3H),7.72(s,1H),6.54-6.51(M,1 H),4.63-4.57(m,1H),4.52-4.46(m,1H),2.34-2.2.30(m,1H),1.89-1.87(m,1H),1.63(d,3H),,1.54-1.49(m,1H).

[0211] Example 5: Preparation of 3-chloro-N-[1-[3-[1-(3,3-dichloroallyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide [I1-11] To a solution of 3-chloro-N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (1 g, 2.52 mmol) in ACN (20 mL) was added 1,1,3-trichloroprop-1-ene (367 mg, 5.04 mmol) and K2CO3 (696 mg, 5.04 mmol) at 20° C. The reaction mixture was heated to 50° C. and stirred for 12 h. LC-MS showed the reaction was complete. The reaction was quenched with water (20 mL) and extracted with EtOAc (3×8 mL). The combined organic phase was washed with brine (4×20 mL), dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by prep-HPLC (TFA) to give 3-chloro-N-[1-[3-[1-(3,3-dichloroallyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-5-(trifluoromethyl)benzamide (I1-11, 200 mg, 16% yield) as a yellow solid. 1 H-NMR(400MHz,MeOH-d4):δ=8.66-8.70(m,2H),8.63(d,J=2.13Hz,1H),8.10(s,1H),8.07(s,1H),7.8 7(s,1H),6.43(t,J=6.9Hz,1H),6.25(q,J=6.88Hz,1H),5.14(d,H=6.9Hz,2H),1.68(d,J=6.88Hz,3H).

[0212] Example 6: Preparation of 3-chloro-N-[1-[3-(1-isopropyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-N-methyl-5-methylsulfonyl-benzamide [I1-5] To a solution of 3-chloro-N-[1-[3-(1-isopropyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-5-methylsulfonyl-benzamide (I1-7, 300 mg, 0.67 mmol) in DMF (5 mL) was added NaH (24 mg, 1 mmol) in portions at 0° C. The reaction mixture was stirred for 30 min. MeI (73 mg, 0.52 mmol) was added and the mixture was stirred at 15° C. for 16 h. TLC (EtOAc:EtOH=3:1) showed the reaction was complete. The reaction was quenched with water (15 mL) and extracted with EtOAc (3×10 mL). The combined organic phase was washed with brine (3×10 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by prep-HPLC (NH4HCO3) to give 3-chloro-N-[1-[3-(1-isopropyl-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-N-methyl-5-methylsulfonyl-benzamide (I1-5, 280 mg, 90% yield) as a white solid. 1 H-NMR (400MHz, DMSO-d6): δ=8.70(d,J=2.32Hz,1H),8.67(d,J=2.20Hz,1H),8.54(br s,1H),7.91(br s,1H),7.55(br s,2H),5.99-6.31(m,1H),4.63(sept,J=6.7Hz 1H),3.22(s,3H),2.87-3.04(m,3H),1.62(d,J=6.97Hz,3H),1.48(d,J=6.72Hz,6H).

[0213] By appropriately modifying the starting materials and using the procedures described in the synthesis description, further compounds I were obtained. The compounds obtained in this manner are listed in the table below together with their physical data.

[0214] [Table 7]

[0215] [Table 8]

[0216] Biological Examples Unless otherwise specified, test solutions were prepared as follows:

[0217] The active compounds were dissolved at the desired concentration in a 1:1 (volume:volume) mixture of distilled water:acetone. Test solutions were prepared on the day of use.

[0218] The activity of the compounds of formula I according to the invention can be demonstrated and evaluated in the following biological tests.

[0219] B.1 Green Peach Aphid (Myzus persicae) To evaluate control of the peach aphid (Myzus persicae) through systemic means, the test unit consisted of a 96-well microtiter plate containing a liquid artificial bait under an artificial membrane.

[0220] Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Various concentrations of formulated compounds were transferred into the aphid diet in duplicate using a custom-made pipettor.

[0221] After application, 5-8 adult aphids were placed on the artificial membrane within the microtiter plate wells. The treated aphid bait was then fed to the aphids and incubated at approximately 23±1°C and approximately 50±5% relative humidity for 3 days. Aphid mortality and reproduction were then visually assessed.

[0222] In this study, compounds I1-1, I1-2, I1-3, I1-5, I1-6, I1-7, I1-8, I1-9, I1-10, I1-12, I1-13, I1-14, I-15 and I2-1 each showed at least 75% mortality compared to untreated controls at 2500 ppm.

[0223] B.2 Tobacco budworm (Heliothis virescens) To evaluate control of Tobacco budworm (Heliothis virescens), test units consisted of 96-well microtiter plates containing insect bait and 15-25 H. virescens eggs.

[0224] Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Various concentrations of formulated compounds were sprayed in duplicate onto the insect diet in 10 μl volumes using a custom-made microatomizer.

[0225] After application, the microtiter plates were incubated for 5 days at about 28±1° C. and about 80±5% relative humidity, and then visually assessed for egg and larval mortality (mortality).

[0226] In this study, compounds I1-1, I1-2, I1-3, I1-8, I1-9, I1-11, I1-12, I1-13 and I1-14 each showed at least 75% mortality at 2500 ppm compared to untreated controls.

[0227] B.3 Boll weevil (Anthonomus grandis) To evaluate control of boll weevils (Anthonomus grandis), test units consisted of 96-well microtiter plates containing insect bait and 5-10 A. grandis eggs.

[0228] Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Various concentrations of formulated compounds were sprayed in duplicate onto the insect diet in 5 μl volumes using a custom-made microatomizer.

[0229] After application, the microtiter plates were incubated for 5 days at about 25±1° C. and about 75±5% relative humidity, and then visually assessed for egg and larval mortality (mortality).

[0230] In this study, compounds I1-1, I1-2, I1-3, I1-4, I1-5, I1-6, I1-7, I1-8, I1-9, I1-10, I1-11, I1-12, I1-13, I1-14, I-15 and I2-1 each showed at least 75% mortality compared to untreated controls at 2500 ppm.

[0231] B.4. Southern armyworm (Spodoptera eridania) 2nd instar larvae The active compounds were formulated in 100% cyclohexanone as 10,000 ppm solutions delivered in tubes by a Tecan Liquid Handler. The 10,000 ppm solutions were serially diluted in 100% cyclohexanone to make intermediate solutions. These served as stock solutions with the final dilution in 50% acetone:50% water (v / v) by Tecan into 10 or 20 ml glass vials. A non-ionic surfactant (Kinetic®) was included in the solution in an amount of 0.01% (v / v). The vials were then inserted into an automated electrostatic sprayer equipped with a spray nozzle for plant / insect application. Lima bean plants (Sieva variety) were grown in two pots and selected for treatment at the first true leaf stage. The test solutions were sprayed onto the leaves by an automated electrostatic plant sprayer equipped with a spray nozzle. The plants were allowed to dry in the sprayer fume hood and then removed from the sprayer. Each pot was placed in a perforated plastic bag with a zip fastener. Approximately 10-11 armyworm larvae were placed in the bag and the bag was closed with a zip fastener. The test plants were maintained for 4 days in a growth chamber at approximately 25°C and approximately 20-40% relative humidity, avoiding direct exposure to fluorescent lighting (14:10 light:photoperiod). Four days after treatment, mortality and reduced feeding were assessed compared to untreated control plants.

[0232] In this study, compounds I1-1, I1-2, I1-3, I1-4, I1-5, I1-6, I1-7, I1-8, I1-10, I1-12, I1-13 and I1-14 each showed at least 75% mortality at 300 ppm compared to untreated controls.

[0233] B.5 Yellow fever mosquito (Aedes aegypti) To evaluate control of yellow fever mosquitoes (Aedes aegypti), test units consisted of 96-well microtiter plates containing 200 μl of tap water and 5-15 newly hatched A. aegypti larvae per well.

[0234] The active compounds were formulated using a solution containing 75% (v / v) water and 25% (v / v) DMSO. Various concentrations of the formulated compounds or mixtures were sprayed in duplicate, 2.5 μL, onto the insect diet using a custom-made microatomizer.

[0235] After application, the microtiter plates were incubated for 2 days at 28+1° C. and 80+5% RH. Larval mortality was then visually assessed.

[0236] In this study, compounds I1-1, I1-2, I1-3, I1-5, I1-6, I1-7, I1-8, I1-9, I1-10, I1-11, I1-12, I1-13, I1-14, I-15 and I2-1 each showed at least 75% mortality compared to untreated controls at 2500 ppm.

[0237] The beneficial activity of the compounds according to the invention having C-linked triazoles over structurally related compounds known from the prior art having N-linked triazoles was demonstrated by the following comparative experiments:

[0238] B.6 ANAPCO (orchid thrips; Dichromothrips corbettii) Dichromothrips corbettii adults used for the bioassay are obtained from a colony continuously maintained under laboratory conditions. For testing purposes, test compounds were diluted in a 1:1 mixture of acetone:water (volume:volume) plus Kinetic at a rate of 0.01% v / v.

[0239] Thrips efficacy of each compound is assessed using a floral immersion technique. Petals of each orchid are dipped into the treatment solution and allowed to dry in a petri dish. Treated petals are placed in individual resealable plastic containers along with approximately 20 adult thrips. All test arenas are maintained under dark conditions and at a temperature of approximately 28° C. during the assay. Mortality is recorded 72 hours after treatment.

[0240] B.7 APHICR (Black bean aphid; Aphis craccivora) The active compound is dissolved at the desired concentration in a 1:1 (vol:vol) mixture of distilled water:acetone. A surfactant (Kinetic) is added at a rate of 0.01% (vol / vol). Test solutions are prepared on the day of use.

[0241] Potted (Kord traditional square pots size 3 inches and 2.5 inches deep) shrub bean plants are cleaned by removing the leaf tips using sharp-tipped forceps, leaving only the cotyledons. 24 hours prior to spraying, plants are inoculated with approximately 30 mixed-stage aphid colonies. Potted bean plants are sprayed with the test solution using a DeVilbiss hand sprayer (20-30 psi). Treated plants are allowed to air dry in the laboratory for approximately 1 hour and then placed in a holding room maintained at 27°C, 50% RH and 72 hours of light. The stems of treated bean plants are inserted into the slits of cut circular filter paper to catch the fallen aphid carcasses. Population reduction (mortality) is assessed after 72 hours.

[0242] The table below shows the % mortality compared to untreated controls.

[0243] [Table 9]

Claims

1. Formula I 【Chemical 1】 (In the formula, R １ is H, OH, C １ ~C ６ -Alkyl, C １ ~C ６ -haloalkyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -halocycloalkyl, C １ ~C ５ -alkoxy, C ２ ~C ４ -alkenyl, C ２ ~C ４ -alkynyl, C １ ~C ４ -Alkyl-C ３ ~C ６ -cycloalkyl, C １ ~C ４ -Alkyl-C ３ ~C ６ -halocycloalkyl (these groups may be unsubstituted or partially or completely substituted with R １１ ; or C(=N-R １１ ) R １２ , C(O)R １１ａ substituted by R １１ CN, NO ２ , N.R. １２ R １３ , C(O)NH ２ , C(S)NH ２ ,C(O)OH,OR １４ , Si(CH ３ ) ３ ; C １ ~C ６ - alkyl; C １ ~C ６ -haloalkyl; C ２ ~C ６ -alkenyl; C ２ ~C ６ -haloalkenyl; C ２ ~C ６ -alkynyl; C ２ ~C ６ -haloalkynyl; C ３ ~C ４ -cycloalkyl-C １ ~C ２ alkyl, the ring of which is unsubstituted or substituted by one or two halogens; 3- to 6-membered heterocyclyl, the ring of which is unsubstituted or substituted by one or two halogens; ａ substituted by R); 5- or 6-membered hetaryl, or phenyl (these rings may be unsubstituted or substituted by R ３ａ substituted by R ａ is halogen, CN, NO ２ , O.H., C. １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C １ ~C ４ -alkoxy-C １ ~C ４ -Alkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy, C ３ ~C ４ -cycloalkyl, C ３ ~C ４ -halocycloalkyl, S(O) ｍ -C １ ~C ４ -Alkyl, S(O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl, and oxo; R １１ａ is NR １２ R １３ , C(O)NH ２ , C(S)NH ２ ,C(O)OH,OR １４ , Si(CH ３ ) ３ ; C １ ~C ６ -haloalkyl; C ２ ~C ６ -alkenyl; C ２ ~C ６ -haloalkenyl; C ２ ~C ６ -alkynyl; C ２ ~C ６ -haloalkynyl; C ３ ~C ４ -cycloalkyl-C １ ~C ２ alkyl, the ring of which is unsubstituted or substituted by one or two halogens; 3- to 6-membered heterocyclyl, the ring of which is unsubstituted or substituted by one or two halogens; ａ substituted by R １２ , R １３ are, independently of each other, H, C １ ~C ４ -Alkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, C(O)NR １２１ R １３１ , S(O)m-C １ ~C ４ -haloalkyl, S(O)m-C ３ ~C ４ -cycloalkyl, S(O)m-C ３ ~C ４ -halocycloalkyl; 3- to 6-membered heterocyclyl (these rings are unsubstituted or ａ substituted by R ３ａ or R １２ and R １３ together with the nitrogen atom to which they are attached form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocycle, which heterocycle contains as ring members N, O and S(O) ｍ and the heterocycle may further contain one or two heteroatoms or heteroatom groups selected from R ａ and is substituted by one or more substituents selected from: R １２１ and R １３１ are, independently of each other, H, C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -halocycloalkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy; C １ ~C ４ -alkyl-phenyl, C １ ~C ４ -alkyl-3 to 6-membered hetaryl, phenyl, 3 to 6-membered heterocyclyl (these rings are unsubstituted or ａ or 5- or 6-membered hetaryl (these rings are unsubstituted or substituted by R ３ａ or R １２１ and R １３１ together with the nitrogen atom to which they are attached form a 3-6 membered saturated, partially or fully unsaturated heterocycle, which may further contain 1 or 2 heteroatom ring members selected from N, O and S, where S is optionally oxidized, and which heterocycle is unsubstituted or ａ is replaced by m is 0, 1 or 2; R １４ is H, C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -halocycloalkyl, C ３ ~C ４ -cycloalkyl-C １ ~C ２ -Alkyl, C ３ ~C ４ -halocycloalkyl-C １ ~C ２ -alkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, or unsubstituted or R ３ａ is phenyl partially or fully substituted by R ２ are H, CN, and C １ ~C ３ -Alkyl, C １ ~C ３ -haloalkyl, C ２ ~C ３ -alkenyl, C ２ ~C ３ -alkynyl; X is CH, CR ３ or N; R ３ is halogen, CN, NO ２ , C １ ~C ４ -Alkyl, C ３ ~C ６ -cycloalkyl, C １ ~C ６ -haloalkyl, C １ ~C ６ -halocycloalkyl, OR １４ , S(O) ｍ -R １４ (These may be unsubstituted or R ３ａ substituted by R ３ａ is halogen, CN, NO ２ , O.H., C. １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C １ ~C ４ -alkoxy-C １ ~C ４ -Alkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy, C ３ ~C ４ -cycloalkyl, C ３ ~C ４ -halocycloalkyl, S(O) ｍ -C １ ~C ４ -Alkyl, S(O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl; n is 0, 1, 2 or 3; R ４ is OR １４ , C.N., C. １ ~C ６ -Alkyl, C ３ ~C ６ -cycloalkyl, C １ ~C ６ -haloalkyl, C １ ~C ６ -halocycloalkyl, C ２ ~C ４ -alkenyl, C ２ ~C ４ -haloalkenyl, C ２ ~C ４ -alkynyl (each unsubstituted or R ４１ (partially or completely replaced by); S (O) ｍ -C １ ~C ４ -Alkyl, S(O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl, NR １２ R １３ , C(O)NR １２ R １３ , C(O)OR １４ , 3- to 6-membered heterocyclyl (these rings are unsubstituted or ａ substituted by R); 5- or 6-membered hetaryl, or phenyl (these rings may be unsubstituted or substituted by R ３ (partially or completely replaced by); R ４１ is H, OR １５ , N.R. １２ R １３ , C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, C(O)NR １２１ R １３１ ; S (O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl; These non-aromatic cyclic R ４１ The group is unsubstituted or partially or fully substituted by Ra; Aromatic R ４１ The group may be unsubstituted or partially or completely R ３ａ is replaced by R １５ is H, C １ ~C ４ - alkyl, or C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C １ ~C ６ -halocycloalkyl (the carbon chains of which are unsubstituted or １１ or 3- to 6-membered heterocyclyl (these rings are unsubstituted or partially or fully substituted by R ａ substituted by R); 5- or 6-membered hetaryl, or phenyl (these rings may be unsubstituted or substituted by R ３ａ is partially or completely replaced by and N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

2. R １１ But CN, NO ２ , N.R. １２ R １３ , C(O)NH ２ , C(S)NH ２ ,C(O)OH,OR １４ , Si(CH ３ ) ３ ; C １ ~C ６ - alkyl; C １ ~C ６ -haloalkyl; C ２ ~C ６ -alkenyl; C ２ ~C ６ -haloalkenyl; C ２ ~C ６ -alkynyl; C ２ ~C ６ -haloalkynyl; C ３ ~C ４ -cycloalkyl-C １ ~C ２ alkyl, the ring of which is unsubstituted or substituted by one or two halogens; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, the ring of which is unsubstituted or substituted by halogens, C １ ~C ３ substituted by haloalkyl and / or CN; R １１ａ But NR １２ R １３ , C(O)NH ２ , C(S)NH ２ ,C(O)OH,OR １４ , Si(CH ３ ) ３ ; C １ ~C ６ -haloalkyl; C ２ ~C ６ -alkenyl; C ２ ~C ６ -haloalkenyl; C ２ ~C ６ -alkynyl; C ２ ~C ６ -haloalkynyl; C ３ ~C ４ -cycloalkyl-C １ ~C ２ - alkyl, the ring of which is unsubstituted or substituted by one or two halogens; 3- to 6-membered heterocyclyl, the ring of which is unsubstituted or substituted by halogens, C １ ~C ３ substituted by haloalkyl and / or CN; R １２ , R １３ However, independently of each other, H, C １ ~C ４ -Alkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, C(O)NR １２１ R １３１ , S(O)m-C １ ~C ４ -haloalkyl, S(O)m-C ３ ~C ４ -cycloalkyl, S(O)m-C ３ ~C ４ -halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl or phenyl (these rings may be unsubstituted or may be substituted with halogen, C １ ~C ３ substituted by haloalkyl and / or CN; R １２１ and R １３１ are independently hydrogen, C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -halocycloalkyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy; C １ ~C ４ -alkyl-phenyl, C １ ~C ４ -alkyl-3 to 6-membered hetaryl, phenyl, 3 to 6-membered heterocyclyl; or 5- or 6-membered hetaryl (these rings are unsubstituted or substituted with halogen, C １ ~C ３ substituted by haloalkyl and / or CN; or R １２１ and R １３１ together with the nitrogen atom to which they are attached form a 3-6 membered saturated, partially or fully unsaturated heterocycle, which may further contain 1 or 2 heteroatom ring members selected from N, O and S, where S may be oxidized, and which may be unsubstituted or may contain halogen, C １ ~C ３ substituted by haloalkyl and / or CN; R １４ is H, C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -halocycloalkyl, C ３ ~C ４ -cycloalkyl-C １ ~C ２ -Alkyl, C ３ ~C ４ -halocycloalkyl-C １ ~C ２ -alkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, or unsubstituted or R ３ is phenyl partially or fully substituted by R ２ are H, CN, and C １ ~C ３ -Alkyl, C １ ~C ３ -haloalkyl, C ２ ~C ３ -alkynyl; R ４ are H, OH, CN, C １ ~C ６ -Alkyl, C ３ ~C ６ -cycloalkyl, C １ ~C ６ -haloalkyl, C １ ~C ６ -halocycloalkyl, C ２ ~C ４ -alkenyl, C ２ ~C ４ -haloalkenyl, C ２ ~C ４ -alkynyl, C １ ~C ４ -alkoxy, C １ ~C ４ -haloalkoxy (each unsubstituted or ４１ and S (O) ｍ -C １ ~C ４ -Alkyl, S(O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl, NR １２ R １３ , C(O)NR １２ R １３ , C(O)OR １４ , 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl (these rings are unsubstituted or ３ (partially or completely replaced by); R ４１ is H, OR １５ , N.R. １２ R １３ , C １ ~C ４ -Alkyl, C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C(O)-C １ ~C ４ -alkyl, C(O)-C １ ~C ４ -haloalkyl, C(O)-C ３ ~C ４ -cycloalkyl, C(O)-C ３ ~C ４ -halocycloalkyl, C(O)NR １２１ R １３１ ; S (O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl; These cyclic R ４１ The group may be unsubstituted or partially or fully halogen, C １ ~C ３ -substituted by haloalkyl and / or CN; R １５ is H, C １ ~C ４ - alkyl, or C １ ~C ４ -haloalkyl, C ３ ~C ６ -cycloalkyl, C １ ~C ６ -halocycloalkyl (the carbon chains of which are unsubstituted or １１ or 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl (these rings are unsubstituted or partially or fully substituted by R ３ is partially or completely replaced by 2. The compound of formula (I) according to claim 1, as well as N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.

3. R １ 2. The compound of formula I according to claim 1, wherein is H.

4. R ２ is CH ３ 2. The compound of formula I according to claim 1, wherein:

5. R ３ But halogen, CN, C １ ~C ４ -haloalkyl, C １ ~C ４ -haloalkoxy, unsubstituted or substituted by one or more CN ３ ~C ４ -cycloalkyl, C ３ ~C ４ -halocycloalkyl, S(O) ｍ -C １ ~C ４ -Alkyl, S(O) ｍ -C １ ~C ４ -haloalkyl, S(O) ｍ -C ３ ~C ４ -cycloalkyl, S(O) ｍ -C ３ ~C ４ -halocycloalkyl, or S (O) ｍ -R １４ and R １４ But, R ３ａ 2. The compound of formula I according to claim 1, wherein the phenyl is partially substituted by:

6. n is 2 and R ３ 2. A compound of formula I according to claim 1, wherein:

7. 2. The compound of formula I according to claim 1, wherein X is CH.

8. 2. The compound of formula I according to claim 1, wherein X is N.

9. R ４ But H, C １ ~C ３ -Alkyl, C １ ~C ３ -haloalkyl, C １ ~C ４ -alkoxy-C １ ~C ４ -Alkyl, CH ２ C(O)NH-C １ ~C ６ -Alkyl, S(O) ｍ -C １ ~C ４ - alkyl, or unsubstituted or one or more groups R as defined in claim 5 ３ 2. The compound of formula I according to claim 1, wherein the phenyl is substituted by:

10. 10. The compound of formula I according to claim 1, consisting predominantly of isomer I.A. 【Chemistry 2】

11. 10. An intermediate compound of formula Int, wherein the variables are defined with respect to formula I in claim 1. 【Chemistry 3】

12. 10. An agricultural or veterinary composition comprising at least one compound according to claim 1 and / or at least one agriculturally or veterinarily acceptable salt thereof and at least one inert liquid and / or solid agriculturally or veterinarily acceptable carrier.

13. 10. An agricultural composition for controlling animal pests, comprising at least one compound according to claim 1, at least one inert liquid and / or solid acceptable carrier, and optionally at least one surfactant.

14. 10. A method for combating or controlling invertebrate pests, comprising contacting the pest or its food source, habitat, or breeding grounds with a pesticidally effective amount of at least one compound of claim 1.

15. 10. A method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting the plants or the soil or water in which the plants are growing with a pesticidally effective amount of at least one compound of claim 1.

16. Seeds comprising the compound of claim 1 or its enantiomer, diastereomer or salt in an amount of 0.1 g to 10 kg per 100 kg of seeds.

17. A method for treating or protecting an animal against infestation or infection by an invertebrate pest, comprising contacting the animal with a pesticidally effective amount of at least one compound of formula I according to claim 1, its stereoisomer and / or at least one veterinarily acceptable salt thereof.

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