WO2025008250A1 - Triazole compounds for the control of invertebrate pests - Google Patents

Abstract

The invention relates to compounds of formula (I) wherein the variables have the meanings as defined in the specification, to compositions comprising them, to active compound combinations comprising them, and to their use for protecting growing plants and animals from attack or infestation by invertebrate pests, furthermore, to seed comprising such compounds.

Description

Triazole compounds for the control of invertebrate pests

Description

The invention relates to compounds of formula I

wherein

R¹ is H, OH, NR¹²R¹³, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, Ci-Cs-alkoxy, C1-C4- alkyl-Cs-Ce-cycloalkyl, Ci-C^alkyl-Cs-Ce-halocycloalkyl, Cs-Ce-alkenyl, Cs-Ce-alkynyl, which groups are unsubstituted, or partially or fully substituted with R¹¹; or C(=N-R¹¹)R¹², C(O)R^11a;

R¹¹ is halogen, ON, NO₂, NR¹²R¹³, C(O)NH₂, C(S)NH₂, C(O)OH, OR¹⁴, Si (CH₃)₃; Ci-C₆-alkyl; Ci-C₆-haloal- kyl; C₂-C6-alkenyl; C₂-C6-haloalkenyl; C₂-C6-alkynyl; C₂-C6-haloalkynyl; C3-C4-cycloalkyl-Ci-C₂-alkyl, which ring is unsubstituted or substituted with 1 or 2 halogen; 3- to 6-membered heterocyclyl, 5- or 6- membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-C₃-haloal- kyl, and/or ON;

R^11a is NR¹²R¹³, C(O)NH₂, C(S)NH₂, C(O)OH, OR¹⁴, Si(CH₃)₃; Ci-C₆-haloalkyl; C₂-C₆-alkenyl; C₂-C₆-haloal- kenyl; C₂-C6-alkynyl; C₂-C6-haloalkynyl; C3-C4-cycloalkyl-Ci-C₂-alkyl, which ring is unsubstituted or substituted with 1 or 2 halogen; 3- to 6-membered heterocyclyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or ON;

R¹², R¹³ are independently from each other H, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C₄-haloal- kyl, Ca-Ce-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-C3-C4-halo- cycloalkyl, C(O)NH-Ci-C₄-alkyl, C(O)NH-Ci-C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)-Ci-C₄-alkyl, C(O)N(CI-C₄- haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-haloalkyl, C(O)NH-Ci-C₄-alkoxy, C(O)NH-CI-C₄- haloalkoxy, C(O)NH-Ci-C₄-alkoxy-Ci-C₄-alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH-Ci-C₄-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or 6-membered hetaryl which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-C₄-haloalkyl, S(O)_m-C3-C4-cy- cloalkyl, S(O)_m-C3-C₄-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; or

R¹² and R¹³ together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, or 7-membered saturated, partially or fully unsaturated heterocycle, which heterocycle may additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, 0, S(0)_m, and optionally one or two groups C(O) as ring members, and which heterocycle is unsubstituted or substituted with one or more R^3a;

R¹² and R¹³ together with the nitrogen atom to which they are bound, form a sulfoximino group =S(O)R^12aR^12b; wherein

R^12a, R^12b are independently Ci-Cs-alkyl, or together with the sulfur atom to which they are bound, form a 3-, 4-, 5-, 6-, or 7-membered saturated, partially or fully unsaturated heterocycle; m Is O, 1 , or 2; each R^3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C haloalkyl, C1-C4- alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m- Ci-C₄-haloalkyl, S(O)_m-C3-C₄-cycloalkyl, S(O)_m-C₃-C₄-halocycloalkyl, C(O)NR¹²R¹³, C(O)OR¹⁴¹, C(O)R¹⁵¹, C(=N-OR¹⁴¹)C3-C6-cycloalkyl, C(=N-OR¹⁴¹)NR¹²¹R¹³¹;

R² is H, CN, Ci-Cs-alkyl, Ci-Cs-haloalkyl, or C2-C3-alkynyl; each R³ is independently selected from halogen, CN, NO2; Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce- halocycloalkyl, Ci-Ce-alkenyl, Ci-Ce-alkynyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, Ci-Ce-alkyl-Cs-Ce-cycloalkyl which are unsubstituted or substituted with R^3a; OR¹⁴, NR¹²¹R¹³¹, C(O)NR¹²¹R¹²², C(O)OR¹⁴, C(O)R¹⁵, S(O)_m-R¹⁵, C(=N-OR¹⁴)NR¹²¹R¹³¹, or C(=N-OR¹⁴)C3-C6-cycloalkyl wherein the ring is unsubstituted or substituted with R^3a; R¹²¹, R¹³¹ are independently from each other H, or a group R¹²² or R¹³²;

R¹²², R¹³² are independently from each other Ci-C4-alkyl, Ci-C4-al koxy , Ci -C4-haloalkoxy, Ci-C4-haloalkyl,

Cs-Ce-cycloalkyl, Ci-C4-alkyl-C3-C6-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cy- cloalkyl, C(O)-C₃-C₄-halocycloalkyl, C(O)NH-Ci-C₄-alkyl, C(O)NH-Ci-C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)- Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C4-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C4-haloalkyl, C(O)NH-Ci- C4-alkoxy, C(O)NH-Ci-C4-haloalkoxy, C(O)NH-Ci-C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4- haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH- Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or 6-membered hetaryl which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-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, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; or

R¹²² and R¹³², together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-membered saturated, partially unsaturated or fully unsaturated heterocycle, which heterocycle may additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, 0, S(O)_m, and C(O) as ring members, and which heterocycle is unsubstituted or substituted with one or more substituents R^3a; or

R¹²² and R¹³², together with the nitrogen atom to which they are bound, form a sulfoximino group =S(O)R^12aR^12b;

R¹⁴ is H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C3-C4-cycloalkyl-Ci-C2-alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)- C3-C4-halocycloalkyl, or phenyl which is unsubstituted or partially or fully substituted with R^3a; R¹⁴¹ is H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C3-C4-cycloalkyl-Ci-C2-alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)- C3-C4-halocycloalkyl, or phenyl which is unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN;

R¹⁵ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-mem- bered hetaryl, or phenyl, which rings are unsubstituted or substituted with R^3a;

R¹⁵¹ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-mem- bered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; n Is O, 1 , 2, or 3;

R⁴ is Cs-Ce-cycloalkyl partially or fully substituted with R⁴⁰, or Cs-Ce-cycloalkeny I unsubstituted or partially or fully substituted with R⁴⁰;

R⁴⁰ independently from one another are selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, OR¹⁵, OC(O)OR¹⁵, OC(O)R¹⁵, OC(O)NR¹²R¹³, S(O)_m-R¹⁵, C(O)OR¹⁵, C(O)R¹⁵, C(O)NHR¹²¹, C(O)NR¹²¹R¹³¹, C(O)NR¹⁵NR¹²R¹³, C(=NOR¹⁴)R¹⁵, C(=NOR¹⁴)NR¹²R¹³, NR¹⁵C(O)OR¹⁵, NR¹⁵NR¹²R¹³, 3- or 4-mem- bered heterocycle unsubstituted or substituted with R³, 5- or 6-membered heteroaryl or phenyl unsubstituted or substituted with R³; provided that R⁴ is not unsubstituted cyclopropyl, if Q is N, and R⁵ and R⁶ are both H;

R⁵, R⁶ are independently H, or defined as for R³;

X, Q are independently N, CH, or CR^3b;

R^3b is as defined for R³; and the N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

The invention also provides agricultural compositions comprising at least one compound of formula I, a stereoisomer thereof and/or an agriculturally acceptable salt thereof and at least one liquid and/or solid carrier, especially at least one inert liquid and/or solid agriculturally acceptable carrier.

The invention also provides a veterinary composition comprising at least one compound of formula I, a stereoisomer thereof and/or a veterinarily acceptable salt thereof and at least one liquid and/or solid carrier, especially at least one inert veterinarily liquid and/or solid acceptable carrier.

The invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or a salt thereof as defined herein.

The invention also relates to plant propagation material, in particular seed, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof. The invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of formula I or a veterinarily acceptable salt thereof. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal.

WC2021037614, WO2021122645, WO2021259997, WO2023025617, WO2023041422, and WO2023037249 describe structurally closely related active compounds. These compounds are mentioned to be useful for combating invertebrate pests.

Nevertheless, there remains a need for highly effective and versatile agents for combating invertebrate pests. It is therefore an object of the invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.

It has been found that these objects can be achieved by compounds of formula I as depicted and defined below, and by their stereoisomers, salts, tautomers and N-oxides, in particular their agriculturally acceptable salts.

Compounds I with R¹ different from H can be obtained by alkylation of compounds II with suitable alkylating agents III (e.g. alkyl halide). In formula III R¹ 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 effected under conditions known from literature.

This transformation is usually carried out at temperatures of from -10°C to +110°C, preferably from 0°C to 25°C, in an inert solvent and in the presence of a base [cf. WO 2002100846],

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

Compounds II (R¹=H) and compounds I (R¥H) can be obtained by reaction of amino compounds IV with carboxylic acids V

This transformation is usually carried out at temperatures of from -20°C to 50°C, preferably from 0°C to 25°C, in an inert solvent, in the presence of a base [cf. WO2023025617], or alternatively in two steps by preparation of an intermediate acyl chloride from V under conditions known from literature, e.g. by reaction with thionyl chloride or oxalyl chloride in dimethylformamide followed by reaction with IV in the presence of a base (cf. W02020208036), optionally under Schotten-Baumann conditions. Suitable peptide coupling reagents are, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1 -ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride, or chloro-N,N, N', N'-tetra- methylformamidinium hexafluorophosphate, which are commonly 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.

Suitable solvents are halogenated hydrocarbons, such as dichloromethane (DCM) or 1 ,2-dichloroethane, ethers, such as diethylether, tetrahydrofurane (THF) or 1 ,4-dioxane, or high-boiling solvents such as dimethylformamide (DMF), preferably DCM or DMF, or in aqueous media.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as LIOH, NaOH, KOH, or Ca(0H)2, alkali metal and alkaline earth metal carbonates, such as Na2CO3, K2CO3, or CS2CO3, alkali metal bicarbonates, such as NaHCOs, or organic bases, e.g. tertiary amines, such as triethylamine, diisopropylethylamine, N-methylpiperidine, or basic aromatic rings, such as pyridine, 2,4,6-collidine, 2,6-lutidine, or 4- (dimethylamino)pyridine, or bicyclic amines, such as 1,8-diazabicylo[5.4.0]undec-7-ene (DBU), 1,5-diazabicy- clo[4.3.0]non-5-ene (DBN), or 1,4-diazabicyclo[2.2.2]octane (DABCO).

Particular preference is given to triethylamine, diisopropylethylamine, and NaOH.

The bases are generally employed in stoichiometric or excess amounts; however, they can also be used in catalytic amounts or, if appropriate, as the solvent.

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

Compounds IV can be obtained by reductive amination of compounds VI.

This transformation is usually carried out at temperatures of from 0°C to 130°C, preferably from 20°C to 70°C, generally in alcoholic and/or aqueous media and in the presence of a reagent and a reducing agent [cf.

WO2021037614], Suitable solvents are alcohols, such as methanol, ethanol, n-propanol, 2-propanol, or n-butanol, or water, preferably methanol. It is also possible to use mixtures of the aforementioned solvents. Suitable reagents are ammonium acetate (NH4AC), ammonium formate, NH4OH, NH4CI, or ammonia. To obtain compounds I with R¥H, primary amines H2NR¹ can be employed instead. Suitable reducing agents are NaBHsCN, sodium triacetoxyborohy- dride, or NaBH₄ (cf. WO2023025617).

Preference is given to ammonium acetate and NaBHsCN, resp.

Compounds VI are obtainable 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 the ketone VI.

The Stille coupling reaction is usually carried out at temperatures from 50°C to 150°C, preferably from 70°C to 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 [cf. WO2023025617], Suitable solvents are aromatic hydrocarbons such as toluene, o-, m-, p-xy- lene, 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 aforementioned solvents.

Suitable catalysts are palladium complexes, such as tetrakis(triphenylphosphine)palladium, tris(dibenzylideneace- tone)dipalladium, palladium diacetate, dichloro-bis(triphenylphosphine)palladium, and [1 , 1 '-bis(diphe- nylphosphino)ferrocene]dichloropalladium, preferably dichlorobis(triphenylphosphine)palladium. Further suitable optional catalysts are com-mon ligands, such as dicyclohexyl[2',4',6'-tris(propan-2-yl)[1,1'-biphenyl]-2-yl]phosphine or triphenylphosphine. Suitable additives are, in general, inorganic compounds, such as CsF and Cuh. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of VIII, based on VII.

The hydrolysis is usually carried out at temperatures from -20°C to 40°C, preferably from 0°C to 25°C, in aqueous acidic media containing aqueous HCI at concentrations between 0.5M and 3M and optionally containing an organic solvent such as acetonitrile, acetone, THF, or methanol (cf. WO2023025617).

Compounds VII in which R⁴ is a cycloalkyl which is substituted at the 1 -position with an electron-withdrawing substituent R⁴⁰ (e.g. ester) can be obtained from triazoles IX by reaction with a reagent of formula X in which groups Z are leaving groups, e.g. halides, such as I, Br, Cl, or sulfonate groups, such as mesylate or tosylate (cf. WO2022149167).

This transformation is usually carried out at temperatures from 0°C to 100°C, preferably from 10°C to 60°C, in an inert solvent and in the presence of a base [cf. WC2017121700], Suitable solvents are halogenated hydrocarbons, such as DCM, 1 ,2-dichloroethane, or chloroform, ethers, such as diethylether, tert-butylmethylether, dioxane, or THF, nitriles, such as acetonitrile or propionitrile, alcohols, such as methanol or ethanol, and polar aprotic solvents, such as dimethyl sulfoxide (DMSO), DMF, or dimethylacetamide (DMA), preferably acetonitrile. It is also possible to use mixtures of the aforementioned solvents. Preference is given to DMF.

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydrides, such as NaH, KH, alkali metal and alkaline earth metal carbonates, such as Na2CO3, K2CO3, or CS2CO3, alkali metal bicarbonates, such as NaHCOa, or organic bases, e.g. tertiary amines such as triethylamine or diisopropylethylamine. Preference is given to K2CO3. The bases are generally employed in equimolar amounts; however, they can also be used in excess or, if appropriate, as solvent.

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

Triazoles IX are obtainable from compounds XI by reaction with 1 to 1.5 equivalents of hydrazine hydrate XII in acetic acid (AcOH) as solvent, optionally using an alcohol, such as methanol, ethanol, or 2-propanol, or an ether, such as 1 ,4-dioxane, as a cosolvent, at temperatures from 25°C to 110°C, as known from literature (cf. WO2022166866). Alternatively, compounds VII can be directly obtained from compound XI by reaction with a substituted hydrazine R⁴NH-NH2 (c.f. WO2021233397). This transformation generally yields a mixture of regioisomers that are subsequently separated by chromatographic methods.

IX

Compounds XI are obtainable from commercially available 3-chloropyrazine-2-carboxamide (XII) by reaction with N,N-dimethylformamide dimethyl acetal (DMF-DMA) and is usually employed in the next step without purification or both steps are performed in one pot (cf. WO2022166866).

This transformation is usually carried out using 1 .5 to 3 equivalents of DMF-DMA at temperatures from 0°C to 100°C, preferably from 25°C to 90°C, in an inert solvent. 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.

The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of DMF-DMA, based on XII.

Alternatively, compounds VII can be directly obtained from compounds XI by reaction with a suitably substituted hydrazine R⁴NHNH2 in analogous manner as described for the synthesis of compounds IX. The resulting regioisomers can be separated by chromatography.

Alternatively, compounds VII can be obtained from compounds XIII by a formal cycloaddition with N-methylimidaz- ole in acetonitrile as described in the literature (Yavari et al., Chem Commun 2020, 56, 9150). VII

In turn, compounds XIII can be obtained from compounds XV in two steps via acyl hydrazine intermediates XIV. The first step is analogous to the reaction of V with IV as described above. Depending on the steric bulk of substituent R⁴, protection of the NH might be required to ensure selective reaction at the NH2. Usual protecting groups are Boc and Fmoc. The second step is conversion of acyl hydrazine intermediate XIV into hydrazonoyl chloride XIII under Appel-type conditions, in the presence of stoichiometric or excess amounts of a phosphine, such as tri- phenylphospine, and CCI4 in acetonitrile (cf. Yavari et al., Chem Commun 2020, 56, 9150).

Further, compounds I can be obtained from compounds Int with compounds R⁴-Z under conditions known from WO2023025617, and analogous as described above for the preparation of compounds VII from compounds IX.

This transformation is usually carried out at temperatures from 0°C to 100°C, preferably from 10°C to 60°C, in an inert solvent and in the presence of a base [cf. W02017121700], Suitable solvents are halogenated hydrocarbons, such as DCM, 1 ,2-dichloroethane, or chloroform, ethers, such as diethylether, tert-butylmethylether, dioxane, or THF, nitriles, such as acetonitrile or propionitrile, alcohols, such as methanol or ethanol, and polar aprotic solvents, such as dimethyl sulfoxide (DMSO), DMF, or dimethylacetamide (DMA), preferably acetonitrile. It is also possible to use mixtures of the aforementioned solvents. Preference is given to DMF.

Further, compounds I with an electron-withdrawing R⁴⁰ in 1 -position of R⁴ can be obtained from compounds Int or IX with compounds Xa, wherein n is 1 , 2, 3 or 4, and Z is a leaving group such as halogen, under conditions as described above, or known from WO2023025617.

The transformation of VII to I is described above.

Moreover, compounds I can be obtained from compounds Int by reaction with a boronic acid R⁴-B(OH)2, or a bo- ronic ester derivative thereof (formula Xb), in the presence of a copper salt, such as Cu(0Ac)2, and a base, such as pyridine, triethylamine or diisopropylethylamine, in a solvent such as dichloromethane or dichloroethane (c.f. WO2013178572).

Alternatively, introduction of R⁴ groups can be performed by reaction of R⁴-Z of formula X with the corresponding NH triazoles intermediates' stages Via, IX, or Int under conditions known from WO2023025617. Substituents R⁴⁰ as part of R⁴ can be introduced in or transformed subsequently using methods known from literature.

Substituents R^3b can be transformed subsequently using methods known from literature.

In addition, substituent R⁴⁰ can be derivatized to other groups R⁴⁰ at various stages of the synthetic route following conventional procedures known from literature.

The reaction mixtures are worked up in a customary manner, e.g. by mixing with water, extracting with an appropriate organic solvent, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.

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

However, if the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the pest to be controlled.

The organic moieties groups mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix C_n-C_m indicates in each case the possible number of carbon atoms in the group. The term "partially or fully substituted” by a radical means that in general the group is substituted with same or different radicals.

The term "halogen” denotes in each case fluorine, bromine, chlorine, or iodine, in particular fluorine, chlorine, or bromine.

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

1.2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl,

1.1.2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, and 1-ethyl-2-methylpropyl.

The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalkoxycarbonyl, haloal- kylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C haloalkyl, more preferably from Ci-Ca-haloalkyl or Ci-C2-haloal- kyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoro- ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.

The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-buty loxy, iso-butyloxy, tert.-butyloxy, and the like.

The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethy I .

The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include Ci-C4-haloalkoxy, in particular Ci-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, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

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

The term "haloalkylthio" as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. The term "alkylsulfinyl" (alkylsulfoxyl : S(=O)-alkyl), as used herein refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group.

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

The term "alkylsulfonyl" (S(=O)2-alkyl) as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.

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

The term "alkylcarbonyl" refers to an alkyl group as defined above, which is bonded via the carbon atom of a carbonyl group (C=O) to the remainder of the molecule.

The term "haloalkylcarbonyl" refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkoxycarbonyl" refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.

The term "haloalkoxycarbonyl” refers to an alkoxycarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. 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-methyl- but-2-en-1-yl, 2-ethylprop-2-en-1 -yl and the like.

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

The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. 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.

The term "haloalky ny I" as used herein refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.

The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl (CC3H5), cyclobutyl (CC4H7), cyclopentyl (CC5H9), cyclohexyl (cCeHn), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

The term "halocycloalkyl" as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloal- kylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 1- and 2-fluorocyclopropyl, 1,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocy- clopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1- and 2-chlorocyclopropyl, 1,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-tri- chlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluoro- cyclopentyl, 1-,2- and 3-chlorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlorocyclopentyl and the like.

The term “halocycloalkenyl” as used herein and in the halocycloalkenyl moieties of halocycloalkenyloxy and halocy- cloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms, wherein at least one, e.g. 1, 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 3,3-difluo- rocyclopropen-1-yl and 3,3-dichlorocyclopropen-1-yl.

The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded via an alkyl group, such as a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkenylmethyl), to the remainder of the molecule.

The term "carbocycle” or "carbocyclyl” includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms. Preferably, the term "carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above.

The term "heterocycle” or "heterocyclyl" includes in general 3- to 12-membered, preferably 3- to 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1, 2, 3, 4 or 5, preferably 1, 2 or 3 heteroatoms selected from N, 0, and S as ring members, wherein S- atoms as ring members may be present as S, SO, or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihy- drothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1 ,4-dioxanyl, thiopyranyl, S. oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihy- drothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothi- opyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin- 2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-only, and the like.

The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3 or 4 heteroatoms selected from N, 0, and S. Examples of 5- or 6-membered heteroaromatic radicals include 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, isoxa- zolyl, 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, e.g. 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1 ,2,3-oxadia- zol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or 5-(1 ,3,4-thiadiazol)yl, thiadiazolyl, e.g. 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, e.g. 1 H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1 H-, 2H-, or 4H-1,2,4-triazolyl and tetrazolyl, i.e. 1 H- or 2H-tetrazolyl. The term "hetaryl" also includes bicyclic 8 to 10- membered heteroaromatic radicals comprising as ring members 1, 2 or 3 heteroatoms selected from N, 0, and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, ben- zoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1 ,8-naphthyridyl, pteridyl, pyr- ido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.

The terms "heterocyclylalkyl" and "hetarylalkyl" refer to heterocyclyl or hetaryl, respectively, as defined above which are bonded via a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= heterocyclylmethyl or he- tarylmethyl, respectively), to the remainder of the molecule.

The term "arylalkyl” and "phenylalkyl" refer to aryl as defined above and phenyl, respectively, which are bonded via Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= arylmethyl or phenylmethyl), to the remainder of the molecule, examples including benzyl, 1 -phenylethyl, 2-phenylethyl, 2-phenoxyethyl etc.

The terms "alkylene”, “cycloalkylene”, "heterocycloalkylene”, "alkenylene”, "cycloalkenylene”, "heterocycloal- kenylene” and "alkynylene” refer to alkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl and alkynyl as defined above, respectively, which are bonded to the remainder of the molecule, via two atoms, preferably via two carbon atoms, of the respective group, so that they represent a linker between two moieties of the molecule.

In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I.

Embodiments and preferred compounds of the invention for use in pesticidal methods and for insecticidal application purposes are outlined in the following paragraphs.

With respect to the variables, the particularly preferred embodiments of the intermediates correspond to those of the compounds of the formula I.

In a preferred embodiment, the compounds I are present in form of a mixture of compounds I.S and I.R, wherein compound I.S with S-configuration of the carbon atom neighboring the nitrogen is present in an amount of more than 50% by weight, in particular of at least 70% by weight, more particularly of at least 85% by weight, more particularly of at least 90% by weight, more particularly of at least 95% by weight, specifically of at least 99% by weight, based on the total weight of compounds I.S and I.R.

In one particularly preferred embodiment of the invention, the method comprises the step of contacting the plant, parts of it, its propagation material, the pests, their food supply, habitat or breeding grounds with a pesticidally effective amount of a compound of formula I.S.

R¹ is preferably H, Ci-Ce-alkyl, Cs-Ce-alkynyl, Cs-Ce-cycloalkyl, or Ci-C alkyl-Cs-Ce-cycloalkyl, particularly selected from H, CH3, C2H5, and CH2CC3H5. H is a particularly preferred R¹.

R² is preferably CH3.

X is preferably CH or CR³, particularly CH. Such compounds correspond to formula 1.1

In another embodiment X is N. Such compounds correspond to formula 1.2.

In a preferred embodiment each R³ is independently selected from halogen, CN, NO2; Ci-C alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, which are unsubstituted or substituted with R^3a; OR¹⁰, S(O)_m-R¹⁵, C(=N- OR¹⁴)C3-C6-cycloalkyl, or C(=N-OR¹⁴)NR¹²¹R¹³¹. In a particular embodiment at least one R³ group is selected from C(=N-OR¹⁴)NR¹²¹R¹³¹ and C(=N-OR¹⁴)C3-C6-cycloalkyl, wherein the ring is unsubstituted or substituted with R^3a.

In a preferred embodiment each R^3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloalkyl, or S(O)_m-C3-C4-halocycloalkyl.

Each R³ is preferably independently selected from halogen, CN, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl unsubstituted or substituted with one or more CN or halogen, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4- haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, S(O)_m-(substituted phenyl), C(=N-OR¹⁴)NR¹²¹R¹³¹, C(=N-OR¹⁴)C3-C6-cycloalkyl wherein the ring is unsubstituted or substituted with R^3a. Particularly each R³ is independently selected from F, Cl, Br, I, CN, CF3, CHF2, OCH3, OC2H5, OCC3H5, O(4-F-C6H4), OCF3, OCHF2, 1-CN- CC3H4, 2,2-F₂-CC3H₃, 2,2-CI2-CC₃H3, SCF3, S(O)CF₃, SO2CH3, SO₂C₂H₅, SO₂CH(CH₃)2, SO2CF3, SO₂(4-F-C₆H4), and C(CH₃)2CN.

In a preferred embodiment at least one R³ group is selected from C(=N-OR¹⁴)NR¹²¹R¹³¹ and C(=N-OR¹⁴)C3-C6-cy- cloalkyl wherein the ring is unsubstituted or substituted with R^3a.

Index m in R³ is preferably 2. Index n in R³ is preferably 2.

R³ groups stand preferably in positions 3 and 5.

In one embodiment, at least one R³ is independently selected from S(O)m-Ci-C4-haloalkyl and index m in R³ is 0 or 1. In another embodiment, at least one R³ is independently selected from S(O)CF3 and S(O)CHF2.

In another embodiment each R³ is preferably independently selected from halogen, CN, Ci-C4-haloalkyl, C1-C4- haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, or S(O)_m-R¹⁴, wherein R¹⁴ is phenyl, which is partially substituted with R^3a.

R^3b is preferably halogen, Ci-C4-alkyl, or Cs-Ce-cycloalkyl, particularly F, Cl, CH3, or CC3H5.

In a preferred embodiment R⁴ is unsubstituted C4-C6-cycloalkyl.

In another preferred embodiment R⁴ is unsubstituted Cs-Ce-cycloalkyl, and Q is not N.

In another preferred embodiment R⁴ is unsubstituted Cs-Ce-cycloalkyl, and one of R⁵ and R⁶ is different from H.

In another preferred embodiment R⁴ is Cs-Ce-cycloalkyl substituted with one R⁴⁰, particularly substituted in the 1- position.

In another embodiment R⁴ is Cs-Ce-cycloalkenyl unsubstituted or substituted with one R⁴⁰, particularly substituted in the 1 -position.

In an embodiment R⁴ is Cs-Ce-cycloalky I unsubstituted or partially or fully substituted with one or more R⁴⁰ being independently selected from halogen, CN, C(O)OR¹⁵, C(O)NR¹²R¹³, S(O)_mR¹⁵, C(O)R¹⁵, C(=N-OR¹⁴)R¹⁵, C(=N- OR¹⁴)NR¹²R¹³, and 5- or 6-membered hetaryl. Preferably one group R⁴⁰ is present, particularly in the 1 -position of R⁴ cycloalkyl.

Particularly preferred R⁴ are unsubstituted or partially or fully substituted cyclopropyl and cyclobutyl. R⁴⁰ are preferably independently selected from CN, C(O)OR¹⁵, C(O)NR¹²¹R¹³¹, C(O)R¹⁵, C(=N-OR¹⁴)R¹⁵, and C(=N-OR¹⁴)NR¹²R¹³. R⁴⁰ are independently selected from CN, C(O)NR¹²¹R¹³¹, and C(O)OR¹⁵ are more preferred. In another embodiment R⁴⁰ is preferably independently selected from 2-pyridine, 2-pyrimidine, and 2-pyrazine. One R⁴⁰ is bound preferably in 1 -position of cycloalkyl, such as cyclopropyl or cyclobutyl. 1-cyano-cyclopropane is particularly preferred.

In a preferred embodiment R⁴ is cyclopropyl substituted with one substituent R⁴⁰. In another preferred embodiment R⁴ is cyclopropyl or cyclobutyl each substituted in the 1 -position with CN, CO2R¹⁵, or C(O)NR¹²¹R¹³¹.

In another preferred embodiment R⁴ is cyclopropyl substituted at the 2-position with one or two halogen. In another preferred embodiment R⁴ is cyclobutyl substituted at the 2- or 3-position with one or two halogen.

In another preferred embodiment R⁴ is cyclopropyl or cyclobutyl each substituted at the 1 -position with a 6-mem- bered heteroaryl containing 1 or 2 N atoms as ring members.

In another preferred embodiment R⁴ is cyclopropyl or cyclobutyl each substituted at the 1 -position with a 5-mem- bered heteroaryl containing 2 or 3 heteroatoms independently selected from N, 0, SO_m.

In a preferred embodiment R⁴⁰ is/are independently selected from halogen, CN, OR¹⁵, Ci-C^alkyl, and C1-C4- haloalkyl. In another embodiment, R⁴¹ is/are independently selected from F, Cl, Br, CN, OCHF2, OCF3, C(O)NHCH3 or C(O)N(CH₃)₂.

In another preferred embodiment R⁴⁰ is/are independently selected from S(O)_m-R¹⁵, C(0)0R¹⁵, C(O)NHR¹²¹, C(O)NR¹²¹R¹³¹, C(=NOR¹⁴)R¹⁵, and C(=NOR¹⁴)NR¹²R¹³.

In another preferred embodiment R⁴⁰ is/are independently selected from 5- or 6-membered heteroaryl or phenyl unsubstituted or substituted with halogen, CN, or OR¹⁵.

R⁵ is preferably H, halogen, Ci-C4-alkyl, or Cs-Ce-cycloalkyl, particularly H, Br, Cl, or CC3H5. In another preferred embodiment R⁵ is halogen. In another preferred embodiment R⁵ is H.

R⁶ is preferably H, halogen, or Ci-C4-alkyl, particularly H, F, Cl, or CH3. In another preferred embodiment R⁶ is halogen. In another preferred embodiment R⁶ is H.

In another preferred embodiment one of R⁵ and R⁶, preferably R⁵, is different from H.

In another preferred embodiment R⁵ and R⁶ are both H.

Q is preferably CF or N.

In a preferred embodiment Q is N.

In another preferred embodiment Q is CF.

Particularly preferred embodiment are compounds I wherein

R¹ is H, CH₃, or CH2-CC3H5,

R² is CH₃, n is 2,

R³ are bound in positions 3 and 5, and are halogen, halomethyl, halomethoxy, cyclopropyl unsubstituted and substituted with halogen or cyano, phenylsulfone being substituted with halogen, halomethylsulfone,

R⁴ is cyclopropyl unsubstituted or substituted with halogen, CN, C(O)NR¹²R¹³, wherein R¹² and R¹³ are Ci-C4-alkyl, Cs-Ce-cycloalkyl, or C6-C6-cycloalkyl-Ci-C4-alkyl.

In particular with a view to their use, preference is given to the compounds of formula I com-piled in the tables below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.

Table 1 : Compounds of formula I. A* in which X is CH, R¹ is H, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 2 : Compounds of formula I. A* in which X is CH, R¹ is H, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and

R⁴ for a compound corresponds in each case to one row of Table A

Table 3 : Compounds of formula I. A* in which X is CH, R¹ is CH3, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 4 : Compounds of formula I. A* in which X is CH, R¹ is CH3, R⁵ is Cl, R⁶ is H R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 5 : Compounds of formula I. A* in which X is CH, R¹ is CH2-CC3H5, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 6 : Compounds of formula I. A* in which X is CH, R¹ is CH2-CC3H5, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 7 : Compounds of formula I. A* in which X is N, R¹ is H, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 8 : Compounds of formula I. A* in which X is N, R¹ is H, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 9 : Compounds of formula I. A* in which X is N, R¹ is CH3, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 10 : Compounds of formula I.A* in which X is N, R¹ is CH3, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 11 : Compounds of formula I.A* in which X is N, R¹ is CH2-CC3H5, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 12 : Compounds of formula I.A* in which X is N, R¹ is CH2-CC3H5, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 13 : Compounds of formula I.B* in which X is CH, R¹ is H, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 14 : Compounds of formula I.B* in which X is CH, R¹ Is H, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 15 : Compounds of formula I.B* in which X is CH, R¹ is CH3, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 16 : Compounds of formula I.B* in which X is CH, R¹ is CH3, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A Table 17 : Compounds of formula I.B* in which X is CH, R¹ is CH2-CC3H5, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 18 : Compounds of formula I.B* in which X is CH, R¹ is CH2-cC3H5, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A Table 19 : Compounds of formula I.B* in which X is N, R¹ is H, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 20 : Compounds of formula I.B* in which X is N, R¹ is H, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and

R⁴ for a compound corresponds in each case to one row of Table A

Table 21 : Compounds of formula I.B* in which X is N, R¹ is CH3, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of T able A

Table 22 : Compounds of formula I.B* in which X is N, R¹ is CH3, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table 23 : Compounds of formula I.B* in which X is N, R¹ is CH2-CC3H5, R⁵ and R⁶ are H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A Table 24 : Compounds of formula I.B* in which X is N, R¹ is C^-cCsHs, R⁵ is Cl, R⁶ is H, and the combination of (R³)_n and R⁴ for a compound corresponds in each case to one row of Table A

Table A

The term "compound(s) of the invention” refers to compound(s) of formula I, or "compound(s) I”, and includes their salts, tautomers, stereoisomers, and N-oxides. The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.

An agrochemical composition comprises a pesticidally effective amount of a compound I.

The compounds I can be converted into customary types of agro-chemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, CD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EC, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials e.g. seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system”, Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. The compositions are prepared in a known manner, e.g. described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.

Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.

Suitable solvents and liquid carriers are water and organic solvents. Suitable solid carriers or fillers are mineral earths.

Suitable surfactants are surface-active compounds, e.g. anionic, cationic, nonionic, and amphoteric surfactants, block polymers, polyelectrolytes. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, carboxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants. Suitable cationic surfactants are qua-ternary surfactants.

The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100%.

Various types of oils, wetters, adjuvants, or fertilizer may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1.

The user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agro-chemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.

The compounds I are suitable for use in protecting crops, plants, plant propagation materials, e.g. seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the invention also relates to a plant protection method, which comprises contacting crops, plants, plant propagation materials, e.g. seeds, or 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 a compound I.

The compounds I are also suitable for use in combating or controlling animal pests. There-fore, the invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, e.g. seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound I.

The compounds I are effective through both contact and ingestion to any and all developmental stages, such as egg, larva, pupa, and adult.

The compounds I can be applied as such or in form of compositions comprising them.

The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials by the pests.

The term "contacting" includes both direct contact (applying the compounds/compositions directly on the animal pest or plant) and indirect contact (applying the compounds/compositions to the locus).

The term "animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.

The term "plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize I sweet and field corn); beet, e.g. sugar beet, or fodder beet; fruits, e.g. pomes, stone fruits, or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, e.g. beans, lentils, peas, alfalfa, or soybeans; oil plants, e.g. rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts, or soybeans; cucurbits, e.g. squashes, pumpkins, cucumber or melons; fiber plants, e.g. cotton, flax, hemp, or jute; citrus fruit, e.g. oranges, lemons, grape-fruits or mandarins; vegetables, e.g. eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, e.g. avocados, cinnamon, or camphor; energy and raw material plants, e.g. corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines; hop; sweet leaf (Stevia); natural rubber plants or ornamental and forestry plants, , shrubs, broad-leaved trees or evergreens, eucalyptus; turf; lawn; grass. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee, or sugar cane; fruits; vines; ornamentals; or vegetables, e.g. cucumbers, tomatoes, beans or squashes.

The term "seed” embraces seeds and plant propagules including true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots, and means preferably true seeds.

"Pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions e.g. desired pesticidal effect and duration, weather, target species, locus, mode of application.

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. 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. The compounds I are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds I can be used as bait composition, gel, general insect spray, aero-sol, as ultra-low volume application and bed net (impregnated or surface applied).

The term "non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, e.g. ants, termites, wasps, flies, ticks, mosquitoes, bed bugs, crickets, or cockroaches, such as: Aedes aegypti, Musca domestica, Tribolium spp.; termites such as Reticulitermes flavipes, Coptotermes formosanus,' roaches such as Blatella german- ica, Periplaneta Americana,' ants such as Solenopsis invicta, Linepithema humile, and Camponotus pennsylvanicus.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). For use in bait compositions, the typical content of active ingredient is from 0.001 wt% to 15 wt%, desirably from 0.001 wt% to 5 wt% of active compound.

The compounds I and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants, termites and/or wood or textile destroying beetles, and for controlling ants and termites from doing harm to crops or human beings (e.g. when the pests invade into houses and public facilities or nest in yards, orchards or parks).

Customary application rates in the protection of materials are, e.g., from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m² treated material, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 wt%, preferably from 0.1 to 45 wt%, and more preferably from 1 to 25 wt% of at least one repellent and/or insecticide.

The compounds of the invention are especially suitable for efficiently combating animal pests e.g. arthropods, and nematodes including: insects from the sub-order of Auchenorrhyncha, e.g. 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, Pseu- doplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medians, Cydia pomonella, Chilo suppressalis, Anticarsia gemmatalis, Agrotis ipsilon, Chrysodeixis includens,'

True bugs, e.g. 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.;

Coccoidea, e.g. Aonidiella aurantia, Ferrisia virgate;

Anthropods of class Arachnida (Mites), e.g. Penthaleus major, Tetranychus spp.; Nematodes, e.g. Heterodera glycines, Meloidogyne spp., Pratylenchus spp., Caenorhabditis elegans.

The compounds I are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the invention also relates to the use of a compound of the invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the invention relates to a method of treating or protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound I.

The invention also relates to the non-therapeutic use of compounds of the invention for treating or protecting animals against infestation and infection by parasites. Moreover, the invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound I.

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 of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound I.

The invention also relates to the non-therapeutic use of compounds I for controlling or combating parasites. Moreover, the invention relates to a non-therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound I.

The compounds I can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds I can be applied to any and all developmental stages.

The compounds I can be applied as such or in form of compositions comprising them.

The term "locus" means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.

As used herein, the term "parasites” includes endo- and ectoparasites. In some embodiments of the invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. Infestations in warm-blooded animals and fish include lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.

The compounds of the invention are especially useful for combating the following parasites: Cimex lectularius, Rhip- icephalus sanguineus, and Ctenocephalides felis.

As used herein, the term "animal” includes warm-blooded animals (including humans) and fish. Preferred are mammals, such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in furbearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Particularly preferred are domestic animals, such as dogs or cats.

The compounds I may be applied in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.

For oral administration to warm-blooded animals, the compounds I may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds I, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the compounds I may be administered to animals parenterally, e.g., by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds I may be formulated into an implant for subcutaneous administration. In addition the compounds I may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds I.

The compounds I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in 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 and preferably 1 ppm to 3,000 ppm of the compounds I. In addition, the compounds I may be formulated as ear tags for animals, particularly quadrupeds e.g. cattle and sheep.

Oral solutions are administered directly.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.

Gels are applied to or spread on the skin or introduced into body cavities.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures.

Emulsions can be administered orally, dermally or as injections.

Suspensions can be administered orally or topically/dermally .

Semi-solid preparations can be administered orally or topically/dermally.

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

The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound I.

Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80% by weight, preferably from 0.1 to 65% by weight, more preferably from 1 to 50% by weight, most preferably from 5 to 40% by weight.

Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90% by weight, preferably of 1 to 50% by weight.

Furthermore, the preparations comprise the compounds of formula I against endoparasites in concentrations of 10 ppm to 2% by weight, preferably of 0.05 to 0.9% by weight, very particularly preferably of 0.005 to 0.25% by weight.

Solid formulations which release compounds of the invention may be applied in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks. Preparation examples

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

Method A: Shimadzu LC-30AD MSD: LCMS-2020; Column: Luna-C18 3pim 2.0x30mm; Mobile phase: A: water + 0.04% TFA; B: ACN + 0.02% TFA; Temperature: 40°C; Gradient: 5% B to 95% B in 1.6min; 95% B to 100% B in 0.9 min; 100% B to 5% B in 0.02min; 5% B for 0.48min; Flow: 0.8mL/min; MS: ESI positive; Mass range: 50-2000.

Method B: Agilent 1200 + MS Agilent 6100; Column: XBridge C18 2.1x50mm 5pim; Mobile phase: A: 10mM NH4CO3 in water, B: ACN; Temperature: 40°C; Gradient: 5% B to 95% B in 0.7min; 95% B for 0.46min; 95% B to 5% B in 0.34 min; Flow: 1.5mL/min; MS: ES-API positive; Mass range (m/z): 50-1500.

Method C: Shimadzu Nexera UHPLC + Shimadzu LCMS-2020, ESI; Column: Kinetex 1 ,7 XB-C18 100A, 2.1x50mm; Mobile phase: A: water + 0.1 % TFA; B: ACN; Temperature: 60°C; Gradient: 5% B to 100% B in 1.5 min; 100% B 0.25 min; Flow: 0.8 mL/min to 1.0 mL/min in 1.5 min; MS: ESI positive; Mass range (m/z): 100-700.

With appropriate modification of the starting materials, the procedures given in the synthesis description were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data.

Example 1 : Preparation of N-[1-[3-[1-(1 -cyanocyclopropyl)- 1 ,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluorome- thyl)benzamide (I-3)

To a solution of N-[1-[3-[1-(1-carbamoylcyclopropyl)-1 ,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)ben- zamide (I-2, 240 mg, 0.46 mmol) in DCM/ACN (1 :1 v/v, 5 mL) was added 1-methoxy-N-triethylammoniosulfonyl- methanimidate (Burgess reagent, 225 mg, 0.94mmol) and the resulting mixture was stirred at 25°C for 16 h until completion was determined by TLC (EtOAc). The mixture was quenched with H2O (10mL) and extracted with DCM (10mLx2). The combined organic phase was washed with brine (10mL), dried over Na2SO4, filtered, and concentrated. The residue was purified by column chromatography on silica gel (PE/EtOAc 1 :1) to furnish N-[1-[3-[1-(1-cya- nocyclopropyl)-1 ,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (i-3, 90mg, 39% yield) as a white solid.

¹H-NMR (CDCI3, 400MHz) 5 = 8.75 (d, J=2.3Hz, 1 H), 8.67 (d, J=2.4 Hz, 1 H), 8.55 (s, 1 H), 8.28 (s, 2H), 8.02 (s, 1 H), 7.86 (br d, J=8.0Hz, 1 H), 6.58-6.46 (m, 1 H), 2.08-1.99 (m, 4H), 1.65 (d, J=6.5 Hz, 3H).

Example 2: methyl 1-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1- yl]cyclopropanecarboxylate (1-1)

To a solution of N-[1-[3-(1 H-1 ,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)-benzamide (1 g, 2.3 mmol) in DMF (10 mL) was added Na2CO3 (740 mg, 6.9 mmol). The mixture was warmed to 60°C and methyl 2,4- dibromobutanoate (600 mg, 2.3 mmol) was added dropwise as a solution in DMF (5 mL). The mixture was stirred at 60°C for 16 h, at which time complete conversion was determined by TLC (PE:EtOAc 0: 1). The reaction mixture was quenched with H2O (50 mL) and extracted with EtOAc (2x50 mL). The combined organic layers were washed with brine (50 mL), dried over Na2SO4, filtered, and concentrated. The residue was purified by column chromatography on silica gel (PE:EtOAc 1 :1) to deliver methyl 1-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1 ,2,4- triazol-1-yl]cyclopropane-carboxylate (1-1 , 550 mg, 45%) as a yellow solid.

¹H NMR (400MHz, CDCI3) 5 = 8.73 (d, J=2.4 Hz, 1 H), 8.65 (d, J=2.3 Hz, 1 H), 8.41 (s, 1 H), 8.29 (s, 2H), 8.06 (br d, J=7.7 Hz, 1 H), 8.02 (s, 1 H), 6.58-6.48 (m, 1 H), 3.75 (s, 3H), 2.03-1.99 (m, 3H), 1.85-1.80 (m, 2H), 1.65 (d, J=6.7 Hz, 3H).

Example 3: N-[1-[3-[1-(1-carbamoylcyclopropyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5- bis(trifluoromethyl)benzamide (I-2)

A solution of methyl 1-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1 ,2,4-triazol-1- yl]cyclopropane-carboxylate (1-1 , 0.5 g, 0.95 mmol) in 7N NH3 in MeOH (20 mL) was stirred at 25°C for 16 h, at which time completion was determined by LCMS. The mixture was concentrated to give N-[1-[3-[1-(1- carbamoylcyclopropyl)-1 ,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-2, 50 mg, 10%) as white solid.

¹H NMR (400MHz, DMSO-d₆) 5 = 9.44 (br d, J=7.0 Hz, 1 H), 8.90 (s, 1 H), 8.69 (dd, J=2.1, 12.3 Hz, 2H), 8.48 (s, 2H), 8.30 (s, 1 H), 7.52 (br s, 1 H), 6.93 (br s, 1 H), 6.16-6.06 (m, 1 H), 1.69 (br s, 1 H), 1.66 (br s, 1 H), 1.61 (br d, J=6.6 Hz, 3H), 1.58-1.48 (m, 2H).

able I: Compounds of formula I

Biological examples

If not otherwise specified, the test solutions were prepared as follow:

The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vokvol) dis-tilled water : acetone. The test solution was prepared on the day of use.

The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological tests.

B.1 Green Peach Aphid (Myzus persicae)

For evaluating control of green peach aphid (Myzus persicae) through systemic means, the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial mem brane.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.

After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 ± 1 °C and about 50 ± 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.

In this test, compounds 1-1 , 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, and I-9, resp., at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.2 Tobacco budworm (Heliothis virescens)

For evaluating control of tobacco budworm {Heliothis virescens), the test unit consisted of 96-well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10pil, using a custom-built micro atomizer, at two replications.

After application, microtiter plates were incubated at about 28 ± 1 °C and about 80 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

In this test, compounds 1-1 , 1-2, 1-3, 1-5, and I-7 resp., at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.3 Boll weevil (Anthonomus grandis)

For evaluating control of boll weevil (Anthonomus grandis), the test unit consisted of 96-well-microtiter plates containing an insect diet and 5-10 A. grandis eggs.

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5pil, using a custom-built micro atomizer, at two replications.

After application, microtiter plates were incubated at about 25 ± 1 °C and about 75 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed. In this test, compounds 1-1 , 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, and I-9, resp., at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.4. Southern armyworm (Spodoptera eridania), 2nd instar larvae

The active compounds were formulated by a Tecan liquid handler in 100% cyclohexanone as a 10,000-ppm solution supplied in tubes. The 10,000-ppm solution was serially diluted in 100% cyclohexanone to make interim solutions. These served as stock solutions for which final dilutions were made by the Tecan in 50% acetone:50% water (v/v) into 10 or 20ml glass vials. A non-ionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). The vials were then inserted into an automated electrostatic sprayer equipped with an atomizing nozzle for application to plants/insects. Lima bean plants (variety Sieva) were grown 2 plants to a pot and selected for treatment at the 1st true leaf stage. Test solutions were sprayed onto the foliage by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into perforated plastic bags with a zip closure. Ten to 11 armyworm larvae were placed into the bag and the bags zipped closed. Test plants were maintained in a growth room at about 25°C and about 20- 40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (14: 10 lighbdark photoperiod) to prevent trapping of heat inside the bags. Mortality and reduced feeding were assessed 4 days after treatment, compared to untreated control plants.

In this test, compounds 1-1 , 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, and I-9, resp., at 300 ppm showed at least 75 % mortality in comparison with untreated controls.

B.5 Yellow fever mosquito (Aedes aegypti)

For evaluating control of yellow fever mosquito (Aedes aegypti the test unit consisted of 96-well-microtiter plates containing 200pil of tap water per well and 5-15 freshly hatched A. aegypti larvae.

The active compounds were formulated using a solution containing 75% (v/v) water and 25% (v/v) DMSO. Different concentrations of formulated compounds or mixtures were sprayed onto the insect diet at 2.5pil, using a custom-built micro atomizer, at two replications.

After application, microtiter plates were incubated at 28 ± 1 °C, 80 ± 5 % RH for 2 days. Larval mortality was then visually assessed.

In this test, compounds 1-1 , 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, and I-9, resp., at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

B.6 Orchid thrips (Dichromothrips corbetti)

Dichromothrips corbetti adults used for bioassay are obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1 :1 mixture of acetone:water (vokvol), plus Kinetic at a rate of 0.01 % v/v.

Thrips potency of each compound is evaluated by using a floral-immersion technique. Each orchid petal is dipped into treatment solution and allowed to dry in Petri dishes. Treated petals are placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas are held under dark condition and a temperature of about 28°C for duration of the assay. The percent mortality is recorded 72 hours after treatment.

In this test, compounds 1-2, 1-3, 1-5, 1-6, 1-7, and 1-8, resp., at 300 ppm showed at least 75 % mortality in comparison with untreated controls.

Claims

Claims

1. Compounds of formula I

wherein

R¹ is H, OH, NR¹²R¹³, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, Ci-Cs-alkoxy, Ci-C4-alkyl-C3-C6-cycloalkyl, Ci-C^alkyl-Ca-Ce-halocycloalkyl, C₃-C6-alkenyl, C₃-C6-alkynyl, which groups are unsubstituted, or partially or fully substituted with R¹¹; or C(=N-R¹¹)R¹², C(O)R^11a;

R¹¹ is halogen, CN, NO₂, NR¹²R¹³, C(O)NH₂, C(S)NH₂, C(O)OH, OR¹⁴, Si(CH₃)₃; Ci-C₆-alkyl; Ci-C₆- haloalkyl; C₂-C6-alkenyl; C₂-C6-haloalkenyl; C₂-C6-alkynyl; C₂-C6-haloalkynyl; C₃-C4-cycloalkyl- Ci-C₂-alkyl, which ring is unsubstituted or substituted with 1 or 2 halogen; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-C₃-haloalkyl, and/or CN;

R^11a is NR¹²R¹³, C(O)NH₂, C(S)NH₂, C(O)OH, OR¹⁴, Si(CH₃)₃; Ci-C₆-haloalkyl; C₂-C₆-alkenyl; C₂-C₆- haloalkenyl; C₂-C6-alkynyl; C₂-C6-haloalkynyl; C₃-C4-cycloalkyl-Ci-C₂-alkyl, which ring is unsubstituted or substituted with 1 or 2 halogen; 3- to 6-membered heterocyclyl, which rings are unsubstituted or substituted with halogen, Ci-C₃-haloalkyl, and/or CN;

R¹², R¹³ are independently from each other H, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci- C4-haloalkyl, C₃-C6-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C₃-C4-cycloalkyl, C(O)-C₃-C₄-halocycloalkyl, C(O)NH-Ci-C₄-alkyl, C(O)NH-Ci-C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)- Ci-C4-alkyl, C(O)N(Ci-C4-haloalkyl)-Ci-C4-alkyl, C(O)N(Ci-C4-haloalkyl)-Ci-C4-haloalkyl, C(O)NH-Ci-C₄-alkoxy, C(O)NH-Ci-C₄-haloalkoxy, C(O)NH-Ci-C4-alkoxy-Ci-C₄-alkyl, C(O)NH- Ci-C4-alkoxy-Ci-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6- membered hetaryl, C(O)NH-Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or 6-membered hetaryl which rings are unsubstituted or substituted with halogen, C1-C3- haloalkyl, and/or CN; S(O)_m-Ci-C4-haloalkyl, S(O)_m-C₃-C4-cycloalkyl, S(O)_m-C₃-C4-halocycloal- kyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-C₃-haloalkyl, and/or CN; or

R¹² and R¹³ together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6-, or 7-mem- bered saturated, partially or fully unsaturated heterocycle, which heterocycle may additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, 0, S(0)_m, and optionally one or two groups C(O) as ring members, and which heterocycle is unsubstituted or substituted with one or more R^3a; or

R¹² and R¹³ together with the nitrogen atom to which they are bound, form a sulfoximino group =S(O)R^12aR^12b; wherein

R^12a, R^12b are independently Ci-Cs-alkyl, or together with the sulfur atom to which they are bound, form a 3-, 4-, 5-, 6-, or 7-membered saturated, partially or fully unsaturated heterocycle; m is O, 1 , or 2; each R^3a is independently selected from halogen, CN, NO2, OH, Ci-C4-alkyl, Ci-C haloalkyl, C1- C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4- alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, C(O)NR¹²R¹³, C(O)OR¹⁴¹, C(O)R¹⁵¹, C(=N-OR¹⁴¹)C3-C₆-cycloalkyl, C(=N-OR¹⁴¹)NR¹²¹R¹³¹;

R² is H, CN, Ci-Cs-alkyl, Ci-Cs-haloalkyl, or C2-C3-alkynyl; each R³ is independently selected from halogen, CN, NO2; Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, Ci-Ce-alkenyl, Ci-Ce-alkynyl, Cs-Ce-cycloalkyl-Ci-Ce-alkyl, Ci-Ce-alkyl-Cs-Ce-cy- cloalkyl which are unsubstituted or substituted with R^3a; OR¹⁴, NR¹²¹R¹³¹, C(O)NR¹²¹R¹²², C(O)OR¹⁴, C(O)R¹⁵, S(O)_m-R¹⁵, C(=N-OR¹⁴)NR¹²¹R¹³¹, or C(=N-OR¹⁴)C₃-C₆-cycloalkyl wherein the ring is unsubstituted or substituted with R^3a;

R¹²¹, R¹³¹ are independently from each other H, or a group R¹²² or R¹³²;

R¹²², R¹³² are independently from each other Ci-C4-alkyl, Ci-C4-al koxy , Ci -C4-haloalkoxy, C1-C4- haloalkyl, Cs-Ce-cycloalkyl, Ci-C4-alkyl-C3-C6-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-C3-C4-halocycloalkyl, C(O)NH-Ci-C4-alkyl, C(O)NH-Ci-C4-haloal- kyl, C(O)N(Ci-C₄-alkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)- Ci-C4-haloalkyl, C(O)NH-Ci-C4-alkoxy, C(O)NH-Ci-C4-haloalkoxy, C(O)NH-Ci-C4-alkoxy-Ci-C4- alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocy- clyl or 5- or 6-membered hetaryl, C(O)NH-Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-mem- bered heterocyclyl or 5- or 6-membered hetaryl which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-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, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; or

R¹²² and R¹³², together with the nitrogen atom to which they are bound, form a 3-, 4-, 5-, 6- or 7-mem- bered saturated, partially unsaturated or fully unsaturated heterocycle, which heterocycle may additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, 0, S(O)_m, and C(O) as ring members, and which heterocycle is unsubstituted or substituted with one or more substituents R^3a; or

R¹²² and R¹³², together with the nitrogen atom to which they are bound, form a sulfoximino group =S(O)R^12aR^12b; R¹⁴ is H, Ci-C4-alkyl, Ci-C^haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C3-C4-cycloalkyl-Ci-C2- alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cy- cloalkyl, C(O)-C3-C4-halocycloalkyl, or phenyl which is unsubstituted or partially or fully substituted with R^3a;

R¹⁴¹ is H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C3-C4-cycloalkyl-Ci-C2- alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cy- cloalkyl, C(O)-C3-C4-halocycloalkyl, or phenyl which is unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN;

R¹⁵ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with R^3a;

R¹⁵¹ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; n Is O, 1 , 2, or 3;

R⁴ is Cs-Ce-cycloalkyl partially or fully substituted with R⁴⁰, or Cs-Ce-cycloalkeny I unsubstituted or partially or fully substituted with R⁴⁰;

R⁴⁰ independently from one another are selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, OR¹⁵, OC(O)OR¹⁵, OC(O)R¹⁵, OC(O)NR¹²R¹³, S(O)_m-R¹⁵, C(O)OR¹⁵, C(O)R¹⁵, C(O)NHR¹²¹, C(O)NR¹²¹R¹³¹, C(O)NR¹⁵NR¹²R¹³, C(=NOR¹⁴)R¹⁵, C(=NOR¹⁴)NR¹²R¹³, NR¹⁵C(O)OR¹⁵, NR¹⁵NR¹²R¹³, 3- or 4-membered heterocycle unsubstituted or substituted with R³, 5- or 6-mem- bered heteroaryl or phenyl unsubstituted or substituted with R³; provided that R⁴ is not unsubstituted cyclopropyl, if Q is N, and R⁵ and R⁶ are both H;

R⁵, R⁶ are independently H, or as defined for R³;

X, Q are independently N, CH, or CR^3b;

R^3b is as defined for R³; and the N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof.

2. Compounds of formula I according to claim 1 , wherein R¹ is H or CH2-CC3H5.

3. Compounds of formula I according to claim 1 or 2, wherein R² is CH3.

4. Compounds of formula I according to any of claim 1 to 3, wherein R³ is halogen, CN, Ci-C4-haloalkyl, C1-C4- haloalkoxy, C3-C4-cycloalkyl unsubstituted or substituted with one or more CN or halogen, C3-C4-halocycloal- kyl, S(O)m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, S(O)_m- (substituted phenyl), C(=N-OR¹⁴)NR¹²¹R¹³¹, C(=N-OR¹⁴)C3-C6-cycloalkyl wherein the ring is unsubstituted or substituted with R^3a.

5. Compounds of formula I according to any of claim 1 to 4, wherein n is 2 and R³ is in positions 3 and 5.

6. Compounds of formula I according to any one of claims 1 to 6, wherein at least one R³ is selected from C(=N- OR¹⁴)NR¹²¹R¹³¹ and C(=N-OR¹⁴)C3-C6-cycloalkyl wherein the ring is unsubstituted or substituted with R^3a.

7. Compounds of formula I according to any one of claims 1 to 6, wherein X is CH.

8. Compounds of formula I according to any one of claims 1 to 7, wherein R⁴ is Ca-Ce-cycloal ky I partially or fully substituted with R⁴⁰.

9. Compounds of formula I according to any one of claims 1 to 7, wherein R⁴ is Ca-Ce-cycloal keny I unsubstituted or partially or fully substituted with R⁴⁰.

10. Compounds of formula I according to any one of claims 1 to 9, which correspond to formula I. A

Compounds of formula I according to any one of claims 1 to 9, which correspond to formula I . B

12. Compounds of formula I according to any one of the preceding claims, which consist mainly of the isomer I.S.

13. An agricultural or veterinary composition comprising at least one compound according to any one of claims 1 to 12 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.

14. An agricultural composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 12 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.

15. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidal ly effective amount of at least one compound as defined in any one of claims 1 to 12.

16. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 12.

17. Seed comprising a compound as defined in any of claims 1 to 12, or the enantiomers, diastereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.

18. A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 12, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.