Triazole compounds for controlling invertebrate pests

Abstract

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

Description

[0001] This invention relates to compounds having formula I, their N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts.

[0002]

[0003] in

[0004] R 1 It is H, OH, NR 12 R 13 C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C5-alkoxy, C1-C4-alkyl-C3-C6-cycloalkyl, C1-C4-alkyl-C3-C6-halocycloalkyl, C3-C6-alkenyl, C3-C6-ynyl, these groups are unsubstituted or R 11 To partially or completely replace;

[0005] Or C(=NR) 11 )R 12 C(O)R 11a ;

[0006] R 11 It contains halogens, CN, NO2, and 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-ynyl; C2-C6-haloynyl; C3-C4-cycloalkyl-C1-C2-alkyl, wherein the ring is unsubstituted or substituted with one or two halogens; 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, wherein the ring is unsubstituted or substituted with halogens, C1-C3-haloalkyl, and / or CN;

[0007] R 11a It 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-ynyl; C2-C6-haloynyl; C3-C4-cycloalkyl-C1-C2-alkyl, wherein the ring is unsubstituted or substituted with one or two halogens; 3- to 6-membered heterocyclic groups, wherein the ring is unsubstituted or substituted with halogens, C1-C3-haloalkyl, and / or CN;

[0008] R 12 R13 Independently, they are 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)NH-C1-C4-alkyl, C(O)NH-C1-C4-haloalkyl, C(O)N(C1-C4-alkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl) -C1-C4-haloalkyl, C(O)NH-C1-C4-alkoxy, C(O)NH-C1-C4-haloalkoxy, C(O)NH-C1-C4-alkoxy-C1-C4-alkyl, C(O)NH-C1-C4-alkoxy-C1-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclic or 5- or 6-membered heteroaryl, C(O)NH-C1-C4-alkyl-phenyl, C(O)NH-C1-C4-alkyl-3- or 6-membered heterocyclic or 5- or 6-membered heteroaryl, these rings are unsubstituted or substituted with halogen, C1-C3-haloalkyl, and / or CN; S(O) m -C1-C4-haloalkyl, S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, wherein the rings are unsubstituted or substituted with halogens, C1-C3-haloalkyl groups, and / or CN; or

[0009] R 12 and R 13 Together with the nitrogen atoms they are bonded to, they form 3-, 4-, 5-, 6-, or 7-membered saturated, partially or completely unsaturated heterocycles, which may additionally contain one or two atoms selected from N, O, and S(O). m The heterocycle contains a heteroatom or a heteroatom-containing group, and optionally one or two groups C(O) as ring members, and the heterocycle is unsubstituted or substituted by one or more R groups. 3a Replace; or

[0010] R 12 and R 13 Together with the nitrogen atoms they are bonded to, they form a sulfoxide imine group =S(O)R 12a R 12b ;in

[0011] R 12a R 12bThey are C1-C3-alkyl groups independently, or together with the sulfur atoms to which they are bonded, they form 3-, 4-, 5-, 6-, or 7-membered saturated, partially or completely unsaturated heterocycles.

[0012] m is 0, 1, or 2;

[0013] Each R 3a Independently selected from halogens, CN, NO2, OR 151 C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, 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, C(O)NR 12 R 13 C(O)OR 141 C(O)R 151 C(=N-OR) 141 C3-C6-cycloalkyl, C(=N-OR) 141 )NR 121 R 131 ; or phenyl, which is unsubstituted or substituted with halogen;

[0014] R 2 It is H, CN, C1-C3-alkyl, C1-C3-haloalkyl, or C2-C3-alkynyl;

[0015] Each R 3 Independently selected from halogens, CN, NO2; C1-C4-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, C1-C6-alkenyl, C1-C6-ynyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-alkyl-C3-C6-cycloalkyl, these groups are unsubstituted or R 3a Replace; OR 14 NR 121 R 131 C(O)NR 121 R 122 C(O)OR 15 C(O)R 15 S(O) m -R 15 S(O)2F, C(=N-OR) 14 )NR 121 R 131, or C(=N-OR) 14 C3-C6 cycloalkyl, wherein the ring is unsubstituted or R 3a replace;

[0016] R 121 R 131 They are H or R groups, which are independent of each other. 122 Or R 132 ;

[0017] R 122 R 132 Independently, they are 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)NH-C1-C4-alkyl, C(O)NH-C1-C4-haloalkyl, C(O)N(C1-C4-alkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)- C1-C4-haloalkyl, C(O)NH-C1-C4-alkoxy, C(O)NH-C1-C4-haloalkoxy, C(O)NH-C1-C4-alkoxy-C1-C4-alkyl, C(O)NH-C1-C4-alkoxy-C1-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclic or 5- or 6-membered heteroaryl, C(O)NH-C1-C4-alkyl-phenyl, C(O)NH-C1-C4-alkyl-3- or 5- or 6-membered heteroaryl, where the rings are unsubstituted or substituted with halogens, C1-C3-haloalkyl, and / or CN; S(O) m -C1-C4-haloalkyl, S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, wherein the rings are unsubstituted or substituted with halogens, C1-C3-haloalkyl groups, and / or CN; or

[0018] R 122 and R 132 Together with the nitrogen atoms they are bonded to, they form 3-, 4-, 5-, 6-, or 7-membered saturated, partially unsaturated, or fully unsaturated heterocycles, which may additionally contain one or two atoms selected from N, O, and S(O). m The heteroatom of C(O) or a heteroatom-containing group is a ring member, and the heterocycle is unsubstituted or substituented by one or more R groups. 3a Replace; or

[0019] R 122 and R 132 Together with the nitrogen atoms they are bonded to, they form a sulfoxide imine group =S(O)R 12a R 12b ;

[0020] R 14 It 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, SO m -C1-C4-alkyl, SO m -C1-C4-halogenated alkyl groups, SO m -C3-C6-cycloalkyl or phenyl, which is unsubstituted or R 3a To partially or completely replace;

[0021] R 141 It 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 phenyl, which is unsubstituted or substituted with halogen, C1-C3-haloalkyl, and / or CN;

[0022] R 15 It is H, C1-C4-alkyl, or C1-C4-haloalkyl, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl, where the carbon chains are unsubstituted or R-substituted. 11 Partial or complete substitution; or 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, wherein the rings are unsubstituted or replaced by R. 3a replace;

[0023] R 151 It is H, C1-C4-alkyl, or C1-C4-haloalkyl, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl, where the carbon chains are unsubstituted or R-substituted. 11 Partial or complete substitution; or 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, which are unsubstituted or substituted with halogens, C1-C3-haloalkyl groups, and / or CN;

[0024] n is 0, 1, 2, or 3;

[0025] R 4 Is it unreplaced or replaced by (R) 41 ) o Substituted 5- or 6-membered heteroaryl or phenyl groups, provided that X is CH or N, and Q is N, and R... 5 and R 6 If it is H, then R 4 It is not C6H5;

[0026] Each R 41 Independently selected from halogen, CN, OR 14 Unreplaced or R 3a Substituted C1-C4 alkyl; C1-C4-haloalkyl, and NR 15 C(O)R 151 S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl, S(O) m -C3-C4-cyanocycloalkyl, NR 15 C(O)OR 15 OC(O)OR 15 OC(O)R 15 OC(O)NR 12 R 13 C(O)OR 15 C(O)R 15 C(O)NHR 122 C(O)NR 122 R 132 C(O)NR 15 NR 12 R 13 C(=NOR) 14 )R 15 C(=NOR) 14 )NR 12 R 13 NR 15 NR 12 R 13 Unreplaced or R 3 Substituted 3- or 4-membered heterocycles; replaced by R 3 Partially or completely substituted C3-C4-cycloalkyl groups;

[0027] o is 1, 2, 3, 4, or 5;

[0028] R 5 R 6 H is independent, or as for R 3 Defined;

[0029] X and Q are independently N, CH, or CR 3b ;

[0030] R 3b For R 3 As defined.

[0031] The present invention also provides agricultural compositions comprising at least one compound having formula I, a stereoisomer thereof and / or an agriculturally acceptable salt thereof, and at least one liquid and / or solid carrier, particularly at least one agriculturally acceptable inert liquid and / or solid carrier.

[0032] The present invention also provides a veterinary composition comprising at least one compound having formula I, a stereoisomer thereof and / or a veterinary acceptable salt thereof, and at least one liquid and / or solid carrier, particularly at least one veterinary acceptable inert liquid and / or solid carrier.

[0033] The present invention also provides a method for controlling invertebrate pests, the method comprising treating the pest, its food supply, its habitat or breeding ground or cultivated plants in which the pest grows or may grow, plant propagation material (e.g., seeds), soil, area, material or environment or material, cultivated plants, plant propagation material (e.g., seeds), soil, surface or space, with an effective amount of a compound having Formula I as defined herein, or a salt thereof, to kill the pest.

[0034] The present invention also relates to a plant propagation material, particularly seeds, comprising at least one compound having formula I and / or an agriculturally acceptable salt thereof.

[0035] The present invention further relates to a method for treating or protecting an animal from parasitic infestation or infection, the method comprising contacting the animal with an effective amount of a compound having formula I or a veterinarily acceptable salt thereof. Contacting the animal with compound I of the present invention, its salt, or the veterinary composition means applying or administering it to the animal.

[0036] WO 2021037614, WO 2021122645, WO 2021259997, WO 2023025617, WO2023041422, and WO 2023037249 describe structurally related active compounds. These compounds are mentioned as potentially useful against invertebrate pests.

[0037] However, there remains a need for highly effective and versatile agents against invertebrate pests. Therefore, the object of this invention is to provide compounds that exhibit good pest-killing activity and a broad activity spectrum against a wide variety of invertebrate pests, especially difficult-to-control pests (such as insects).

[0038] These objectives have been found to be achieved by compounds having Formula I as shown below and as defined, as well as their stereoisomers, salts, tautomers, and N-oxides, particularly their agriculturally acceptable salts.

[0039] Having R different from H 1 Compound I can be obtained by alkylating compound II with a suitable alkylating agent III (e.g., an alkyl halide). In formula III, R 1 It has the meaning as in Formula I, and Y is a nucleophilic leaving group, such as a halogen, preferably Br or Cl. Alkylation can be carried out under conditions known from the literature.

[0040]

[0041] This conversion is typically carried out at a temperature of -10°C to +110°C, preferably 0°C to 25°C, in an inert solvent and in the presence of a base [see WO 2002100846].

[0042] The starting materials typically react with each other in equimolar amounts. In terms of yield, using an excess of III (based on II) may be advantageous.

[0043] Compound II (R) 1 = H) and compound I (R) 1 ≠ H) can be obtained by reacting amino compound IV with carboxylic acid V.

[0044]

[0045] This conversion is typically carried out in an inert solvent in the presence of a base at a temperature of -20°C to 50°C, preferably 0°C to 25°C [see WO 2023025617], or alternatively in two steps by preparing an intermediate acyl chloride from V under conditions known from the literature, for example by reacting it with thionyl chloride or oxalyl chloride in dimethylformamide, followed by reacting it with IV in the presence of a base (see WO 2020208036), optionally under Schotten-Baumann conditions. Suitable peptide coupling agents are, for example, dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3'-dimethylaminopropyl)carbodiimide hydrochloride, or chloro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate, which are typically used in combination with catalytic amounts, stoichiometric amounts, and excess additives such as 1-hydroxybenzotriazole, 1-hydroxy-7-aza-benzotriazole, 4-(dimethylamino)pyridine, and / or 1-methylimidazole.

[0046] 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 in an aqueous medium.

[0047] Suitable bases are typically inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as LiOH, NaOH, KOH, or Ca(OH)2; alkali metal and alkaline earth metal carbonates, such as Na2CO3, K2CO3, or Cs2CO3; alkali metal bicarbonates, such as NaHCO3; or organic bases, such as tertiary amines, such as triethylamine, diisopropylethylamine, N-methylpiperidine; or basic aromatic rings, such as pyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, or 4-(dimethylamino)pyridine; or bicyclic amines, such as 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).

[0048] Triethylamine, diisopropylethylamine, and NaOH are particularly preferred.

[0049] Bases are typically used in stoichiometric amounts or in excess; however, they can also be used in catalytic amounts, or, if appropriate, as solvents.

[0050] The starting materials typically react with each other in equimolar amounts. In terms of yield, using an excess of IV (based on V) may be advantageous.

[0051] Compound IV can be obtained by reductive amination of compound VI.

[0052]

[0053] This conversion is typically carried out at temperatures from 0°C to 130°C, preferably from 20°C to 70°C, usually in an alcoholic and / or aqueous medium and in the presence of a reagent and a reducing agent [see WO 2021037614]. Suitable solvents are alcohols, such as methanol, ethanol, n-propanol, 2-propanol, or n-butanol, or water, preferably methanol. Mixtures of the above solvents can also be used. Suitable reagents are ammonium acetate (NH4Ac), ammonium formate, NH4OH, NH4Cl, or ammonia. To obtain R 1 Compound I, which is not equal to H, can be replaced by the primary amine H2NR. 1 Suitable reducing agents are NaBH3CN, sodium triacetoxyborohydride, or NaBH4 (see WO2023025617).

[0054] The preferred materials are ammonium acetate and NaBH3CN.

[0055] Compound VI can be obtained from triazole VIa via a nucleophilic aromatic substitution reaction under conditions known in the art. In formula X, group Z is a leaving group, such as a halide, like Cl or F. Compound VIa is known from WO 2023025617.

[0056]

[0057] Alternatively, compound VI can be obtained from compound VII via a two-step sequence, which includes the Stieler coupling of VII with an alkoxyenyltinane such as VIII, followed by partial hydrolysis of the resulting enol ether to ketone VI.

[0058]

[0059] Stieler coupling reactions are typically 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 [see WO2023025617]. Suitable solvents are aromatic hydrocarbons such as toluene, o-xylene, m-xylene, p-xylene, and mesitylene, or ethers such as THF and 1,4-dioxane, preferably toluene or 1,4-dioxane. Mixtures of the above solvents may also be used.

[0060] Suitable catalysts are palladium complexes, such as tetra(triphenylphosphine)palladium, tris(dibenzylacetone)dipalladium, palladium diacetate, dichloro-bis(triphenylphosphine)palladium, and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride, preferably dichlorobis(triphenylphosphine)palladium. Other suitable alternative catalysts are commonly used ligands, such as dicyclohexyl[2',4',6'-tris(propyl-2-yl)[1,1'-biphenyl]-2-yl]phosphine or triphenylphosphine. Suitable additives are typically inorganic compounds, such as CsF and CuI2. The starting materials typically react with each other in equimolar amounts. In terms of yield, using an excess of VIII (based on VII) may be advantageous.

[0061] Hydrolysis is typically carried out at temperatures ranging from -20°C to 40°C, preferably from 0°C to 25°C, in an acidic aqueous medium containing an aqueous solution of HCl at a concentration between 0.5 M and 3 M, and optionally an organic solvent such as acetonitrile, acetone, THF, or methanol (see WO 2023025617).

[0062] Compound VII can be obtained from triazole IX via a nucleophilic aromatic substitution reaction. In formula X, group Z is a leaving group, such as a halide, like Cl or F.

[0063]

[0064] This conversion is typically carried out at a temperature of 0°C to 100°C, preferably 10°C to 60°C, in an inert solvent and in the presence of a base [see WO 2020233641]. Suitable solvents are haloalkanes, such as DCM, 1,2-dichloroethane, or chloroform; ethers, such as diethyl ether, tert-butylmethyl ether, 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. Mixtures of the above solvents may also be used. DMF is preferred.

[0065] Suitable bases are typically inorganic compounds, such as alkali metal hydrides and alkaline earth metal hydrides, like NaH and KH; alkali metal carbonates and alkaline earth metal carbonates, such as Na₂CO₃, K₂CO₃, or Cs₂CO₃; alkali metal bicarbonates, such as NaHCO₃; or organic bases, such as tertiary amines, like triethylamine or diisopropylethylamine. K₂CO₃ is preferred. Bases are usually used in equimolar amounts; however, they can also be used in excess, or, if appropriate, as solvents.

[0066] The starting materials typically react with each other in equimolar amounts. In terms of yield, using an excess of X (based on IX) may be advantageous.

[0067] Alternatively, compound IX can be converted to compound VII by reacting with compound X, in which Z is a halide (such as I or Br). In this case, a copper salt (such as CuI) can be used in combination with a base (such as K2CO3 or Cs2CO3) and optionally in the presence of an amine (such as N,N-dimethyl-1,2-cyclohexanediamine) in an inert solvent (such as DMF or dioxane) (see WO 2020252393).

[0068] Triazole IX can be obtained from compound XI by reacting it with 1 to 1.5 equivalents of hydrazine hydrate XII in acetic acid (AcOH) as solvent, optionally with an alcohol such as methanol, ethanol, or 2-propanol, or an ether such as 1,4-dioxane, as a co-solvent at a temperature of 25°C to 110°C, as is known from the literature (see WO 2022166866). Alternatively, compound VII can be obtained from compound XI by reacting it with a substituted hydrazine R... 4 It is obtained directly by the NH-NH2 reaction (see WO 2021233397). This conversion usually produces a mixture of positional isomers that are subsequently separated by chromatography.

[0069]

[0070] Compound XI can be obtained from commercially available 3-chloropyrazine-2-carboxamide (XII) by reaction with N,N-dimethylformamide dimethyl acetal (DMF-DMA), and is usually used for the next step without purification or both steps are carried out in one pot (see WO 2022166866).

[0071]

[0072] This conversion is typically carried out in an inert solvent at a temperature of 0°C to 100°C, preferably 25°C to 90°C, using 1.5 to 3 equivalents of DMF-DMA. 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.

[0073] The starting materials typically react with each other in equimolar amounts. In terms of yield, using an excess of DMF-DMA (based on XII) may be advantageous.

[0074] Alternatively, compound VII can be synthesized by reacting with appropriately substituted hydrazine R. 4 NHNH2 is reacted directly from compound XI in a manner similar to that described for the synthesis of compound IX. The resulting positional isomers can be separated by chromatography.

[0075] Furthermore, compound I can be obtained from compound Int as described in WO 2023025617 in a manner similar to that described above for the preparation of compound VII from compound IX.

[0076]

[0077] Alternatively, it can be achieved by making R with formula X 4 -Z reacts with the corresponding NH triazole intermediate stage VIa, IX, or Int under conditions known from WO 2023025617 to carry out R. 4 Introduction of functional groups. Substituent R 41 Can be used as R 4 Some of these are introduced or subsequently transformed using methods known from the literature.

[0078] The substituent R can then be converted using methods known from the literature. 3b .

[0079] The reaction mixture is post-treated in a conventional manner, such as by mixing with water, extraction with a suitable organic solvent, separation of the phases, and (if appropriate) chromatographic purification of the crude product. Some intermediates and final products are obtained as colorless or light brown viscous oils, which are purified under reduced pressure and at a gently elevated temperature to remove volatile components. If the intermediates and final products are obtained as solids, they can also be purified by recrystallization or digestion.

[0080] If a single compound I cannot be obtained through the above-mentioned methods, it can be prepared by derivatization of other compounds I.

[0081] However, if the synthesis yields a mixture of isomers, separation is not usually required, as individual isomers may interconvert during post-treatment for use or during application (e.g., under the influence of light, acid, or alkali). Such transformations can also occur post-use, for example in treated plants or in pests to be controlled.

[0082] The organic particulate groups mentioned in the above definitions of variables—like the term halogen—are collective terms that are a single enumeration of individual group members. Prefix C n -C m In each case, it indicates the possible number of carbon atoms in the group.

[0083] The term "partially or completely substituted by a group" means that the group is usually substituted by the same or different groups.

[0084] The term "halogen" in each case refers to fluorine, bromine, chlorine, or iodine, especially fluorine, chlorine, or bromine.

[0085] As used herein and in the alkyl portion of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl, the term "alkyl" in each case means a straight-chain or branched alkyl group that typically has 1 to 10 carbon atoms, often 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-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.

[0086] As used herein and in the halogenated alkyl moiety of halogenated alkyl carbonyl, halogenated alkoxy carbonyl, halogenated alkyl thio, halogenated alkyl sulfonyl, halogenated alkyl sulfinyl, halogenated alkoxy, and halogenated alkoxyalkyl, the term "halogenated alkyl" in each case means a straight-chain or branched alkyl group generally having 1 to 10 carbon atoms, often 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or completely replaced by halogen atoms. Preferred halogenated alkyl moieties are selected from C1-C4-halogenated alkyl groups, more preferably from C1-C3-halogenated alkyl or C1-C2-halogenated alkyl groups, and particularly from C1-C2-fluoroalkyl groups, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, etc.

[0087] As used herein, the term "alkoxy" in each case refers to a straight-chain or branched alkyl group bonded by an oxygen atom and typically having 1 to 10 carbon atoms, often 1 to 6 carbon atoms, and preferably 1 to 4 carbon atoms. Examples of alkoxy groups are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy, tert-butoxy, etc.

[0088] As used herein, the term "alkoxyalkyl" refers to an alkyl group that typically comprises 1 to 10, often 1 to 4, preferably 1 to 2 carbon atoms, wherein one carbon atom carries an alkoxy group as defined above, typically comprising 1 to 4, preferably 1 or 2 carbon atoms. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.

[0089] As used herein, the term "haloalkoxy" in each case refers to a straight-chain or branched alkoxy group having 1 to 10 carbon atoms, often 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or completely replaced by halogen atoms, particularly fluorine atoms. Preferred haloalkoxy moieties include C1-C4-haloalkoxy groups, particularly C1-C2-fluoroalkoxy groups, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, etc.

[0090] As used herein, the term "alkylthio" (alkylthioalkyl: S-alkyl) refers to a straight-chain 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.

[0091] As used herein, the term "haloalkylthio" refers to an alkylthio group as mentioned above, wherein the hydrogen atoms are partially or completely replaced by fluorine, chlorine, bromine and / or iodine.

[0092] As used herein, the term "alkyl sulfinyl" (alkyl sulfinyl: S(=O)-alkyl) refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-alkyl sulfinyl), more preferably 1 to 3 carbon atoms, bonded at any position in the alkyl group by the sulfur atom of the sulfinyl group (as described above).

[0093] As used herein, the term "haloalkylsulfinyl" refers to an alkylsulfinyl group as described above, wherein the hydrogen atoms are partially or completely substituted with fluorine, chlorine, bromine, and / or iodine.

[0094] As used herein, the term "alkylsulfonyl" (S(=O)2-alkyl) refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= C1-C4-alkylsulfonyl), and more preferably 1 to 3 carbon atoms, bonded at any position in the alkyl group via the sulfur atom of the sulfonyl group.

[0095] As used herein, the term "haloalkylsulfonyl" refers to an alkylsulfonyl group as described above, wherein the hydrogen atoms are partially or completely substituted with fluorine, chlorine, bromine, and / or iodine.

[0096] The term "alkyl carbonyl" refers to an alkyl group as defined above, which is bonded to the rest of the molecule via the carbonyl (C=O) carbon atom.

[0097] The term "haloalkylcarbonyl" refers to an alkyl carbonyl group as described above, wherein the hydrogen atoms are partially or completely replaced by fluorine, chlorine, bromine and / or iodine.

[0098] The term "alkoxycarbonyl" refers to an alkyl carbonyl group as defined above, which is bonded to the rest of the molecule via an oxygen atom.

[0099] The term "haloalkoxycarbonyl" refers to an alkoxycarbonyl group as described above, wherein the hydrogen atoms are partially or completely replaced by fluorine, chlorine, bromine and / or iodine.

[0100] As used herein, the term "alkenyl" in each case refers to a monounsaturated hydrocarbon group typically having 2 to 10, often 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, methylallyl (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, etc.

[0101] As used herein, the term "haloalkenyl" refers to an alkenyl group as defined above, in which hydrogen atoms are partially or completely replaced by halogen atoms.

[0102] As used herein, the term "alkynyl" in each case refers to a monounsaturated hydrocarbon group that typically has 2 to 10, often 2 to 6, preferably 2 to 4 carbon atoms, such as ethynyl, propynyl (2-propyn-1-yl, 1-propyn-1-yl, 1-methylpropyn-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-methylbutyn-2-yn-1-yl, 1-ethylpropyn-2-yn-1-yl, etc.

[0103] As used herein, the term "haloalkynyl" refers to an alkynyl group as defined above, in which hydrogen atoms are partially or wholly replaced by halogen atoms.

[0104] As used herein and in the cycloalkyl moiety of cycloalkoxy and cycloalkylthio, the term "cycloalkyl" in each case refers to a monocyclic alicyclic group typically having 3 to 10 or 3 to 6 carbon atoms, such as cyclopropyl (cC3H5), cyclobutyl (cC4H7), cyclopentyl (cC5H9), and cyclohexyl (cC6H5). 11 ), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl, or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0105] As used herein and in the halocycloalkyl portion of halocycloalkoxy and halocycloalkylthio, the term "halocycloalkyl" in each case means a monocyclic alicyclic group generally having 3 to 10 carbon atoms or 3 to 6 carbon atoms, wherein at least one of the hydrogen atoms (e.g., 1, 2, 3, 4 or 5) is replaced by a halogen, particularly by fluorine or chlorine. Examples include 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, etc.

[0106] As used herein and in the halocycloalkenyl portion of halocycloalkenyloxy and halocycloalkenylthioyl groups, the term "halocycloalkenyl" in each case refers to a monocyclic monounsaturated nonaromatic group generally having 3 to 10 (e.g., 3 or 4 or 5 to 10) carbon atoms, preferably 3 to 8 carbon atoms, wherein at least one (e.g., 1, 2, 3, 4 or 5) of the hydrogen atoms is replaced by a halogen, particularly by fluorine or chlorine. Examples are 3,3-difluorocyclopropen-1-yl and 3,3-dichlorocyclopropen-1-yl.

[0107] The term “cycloalkenylalkyl” refers to 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 or C1-C4-alkyl group, and in particular a methyl group (= cycloalkenylmethyl).

[0108] The term "carbocyclic" or "carbocyclic group" generally includes a 3- to 12-membered, preferably 3- to 8-membered, or more preferably 5- to 6-membered, monocyclic nonaromatic ring comprising 3 to 12, preferably 3- to 8-membered, or more preferably 5- to 6-membered carbon atoms. Preferably, the term "carbocyclic" encompasses cycloalkyl and cycloalkenyl groups as defined above.

[0109] The term "heterocyclic" or "heterocyclic group" typically includes 3- to 12-membered, preferably 3- to 6-membered, and particularly 6-membered, monocyclic heterocyclic nonaromatic groups. Heterocyclic nonaromatic groups typically contain 1, 2, 3, 4, or 5, preferably 1, 2, or 3, heteroatoms selected from N, O, and S as ring members, wherein the S atom as a ring member can exist as S, SO, or SO2. Examples of 5- or 6-membered heterocyclic groups include saturated or unsaturated non-aromatic heterocyclic rings, such as oxetane, oxetane, thiohepane, thiohepane-S-oxide (S-oxothiohepane), thiohepane-S-dioxide (S-dioxothiohepane), pyrrolyl, pyrrololinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxocyclopentane, thiohepane, S-oxothiohepane, S-dioxothiohepane, dihydrothiophene, and S-oxodihydrothiophene. The group includes: α-dioxodihydrothiophene, oxazolyl, oxazolinyl, thiazolinyl, oxathiacyclopentyl, piperidinyl, piperazine, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxoalkyl, thiaranyl, S-oxothiaranyl, S-dioxothiaranyl, dihydrothiaranyl, S-oxodihydrothiaranyl, S-dioxodihydrothiaranyl, tetrahydrothiaranyl, S-oxotetrahydrothiaranyl, S-dioxotetrahydrothiaranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazine, etc. Examples of heterocycles containing one or two carbonyl groups as ring members include pyrrolidine-2-keto, pyrrolidine-2,5-diketo, imidazolidin-2-keto, oxazolidin-2-keto, thiazolidin-2-keto, etc.

[0110] The term "heteroaryl" includes monocyclic 5- or 6-membered heteroaryl 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 include pyridinyl (2-, 3-, or 4-pyridinyl), pyrimidinyl (2-, 4-, or 5-pyrimidinyl), pyrazinyl, pyridazinyl (3-, or 4-pyridazinyl), thiopheneyl (2-, or 3-thiopheneyl), furanyl (2-, or 3-furanyl), pyrroleyl (2-, or 3-pyrroleyl), oxazolyl (2-, 3-, or 5-oxazolyl), isoxazolyl (3-, 4-, or 5-isooxazolyl), thiazolyl (2-, 3-, or 5-thiazolyl), isothiazolyl (3-, 4-, or 5-isothiazolyl), pyrazolyl (1-, 3-, 4-, or 5-pyrazolyl), and 1-, 2-, 4-, or 5-imidazolyl. Oxadiazole, such as 2- or 5-[1,3,4]oxadiazole, 4- or 5-(1,2,3-oxadiazole) group, 3- or 5-(1,2,4-oxadiazole) group, 2- or 5-(1,3,4-thiadiazole) group, thiadiazole, such as 2- or 5-(1,3,4-thiadiazole) group, 4- or 5-(1,2,3-thiadiazole) group, 3- or 5-(1,2,4-thiadiazole) group, triazole, such as 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H- or 4H-1,2,4-triazol, and tetrazol, i.e. 1H- or 2H-tetrazol. The term "heteroaryl" also includes bicyclic 8- to 10-membered heteroaromatic groups comprising one, two, or three heteroatoms selected from N, O, and S as ring members, wherein a 5- or 6-membered heteroaromatic ring is fused to a benzene ring or to a 5- or 6-membered heteroaromatic group. Examples of 5- or 6-membered heteroaromatic rings fused to a benzene ring or to a 5- or 6-membered heteroaromatic group include benzofuranyl, benzothiopheneyl, indolyl, indazoleyl, benzimidazolyl, benzooxazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, quinolinyl, isoquinolinyl, purineyl, 1,8-naphthidyl, pteridinyl, pyrido[3,2-d]pyrimidinyl, or pyridinimidazolyl, etc. These fused heteroaromatic groups can be bonded to the remainder of the molecule via any ring atom of the 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl portion.

[0111] The terms “heterocyclic alkyl” and “heteroaryl alkyl” refer to heterocyclic or heteroaryl groups as defined above, which are bonded to the remainder of the molecule via a C1-C5-alkyl or C1-C4-alkyl group, particularly a methyl group (heterocyclic methyl or heteroaryl methyl, respectively).

[0112] The terms “arylalkyl” and “phenylalkyl” refer to aryl and phenyl groups as defined above, respectively, bonded to the remainder of the molecule via a C1-C5-alkyl or C1-C4-alkyl group, particularly a methyl group (= arylmethyl or phenylmethyl), examples of which include benzyl, 1-phenylethyl, 2-phenylethyl, 2-phenoxyethyl, etc.

[0113] The terms “alkylene,” “cycloalkylene,” “heterocyclic alkylene,” “alkenylene,” “cycloalkenylene,” “heterocyclic alkenylene,” and “alkynylene” refer to the alkyl, cycloalkyl, heterocyclic alkyl, alkenyl, cycloalkenyl, heterocyclic alkenyl, and alkynyl groups as defined above, which are bonded to the remainder of the molecule via two atoms of the respective group, preferably via two carbon atoms of the respective group, and thus they represent the linker between two parts of the molecule.

[0114] In specific embodiments, the variables of compounds having Formula I have the following meanings, which, individually and in combination, are specific embodiments of compounds having Formula I.

[0115] Examples and preferred compounds of the present invention for use in methods of killing pests and for insecticidal applications are summarized in the following paragraphs.

[0116] For variables, particularly preferred embodiments of intermediates correspond to those having compounds of Formula I.

[0117] In a preferred embodiment, compound I is present as a mixture of compounds IS and IR, wherein compound IS having an S-configuration of a carbon atom adjacent to nitrogen is present in an amount greater than 50% by weight, particularly at least 70% by weight, more particularly at least 85% by weight, more particularly at least 90% by weight, more particularly at least 95% by weight, specifically at least 99% by weight, based on the total weight of compounds IS and IR.

[0118]

[0119] In a particularly preferred embodiment of the invention, the method includes the step of contacting a plant, its parts, its propagation material, pests, its food supply, habitat or breeding ground with a pest-killing effective amount of a compound having the formula IS.

[0120] Preferably, R 1 It is H, C1-C6-alkyl, C3-C6-ynyl, C3-C6-cycloalkyl, or C1-C4-alkyl-C3-C6-cycloalkyl, particularly selected from H, CH3, C2H5, and CH2cC3H5. H is a particularly preferred R. 1 .

[0121] R2 CH3 is preferred.

[0122] X is preferably CH or CR. 3 Especially CH. These compounds correspond to formula I.1

[0123]

[0124] In another embodiment, X is N. Such compounds correspond to formula I.2.

[0125]

[0126] In a preferred embodiment, each R 3 Independently selected from halogens, CN, NO2; C1-C4-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, which are unsubstituted or R-substituted. 3a Replace; OR 10 S(O) m -R 15 C(=N-OR) 14 C3-C6-cycloalkyl, or C(=N-OR) 14 )NR 121 R 131 In a specific embodiment, at least one R 3 The radical is selected from C(=N-OR) 14 )NR 121 R 131 and C(=N-OR) 14 C3-C6 cycloalkyl, wherein the ring is unsubstituted or R 3a replace.

[0127] In a preferred embodiment, each R 3a Independently selected from halogens, CN, NO2, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, 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, or S(O) m -C3-C4-halocycloalkyl.

[0128] Each R 3Preferably, it is independently selected from halogens, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, unsubstituted or substituted 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, S(O) m -(substituted phenyl), C(=N-OR) 14 )NR 121 R 131 C(=N-OR) 14 C3-C6 cycloalkyl, wherein the ring is unsubstituted or R 3a Replacement. Specifically, each R 3 It 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-Cl2-cC3H3, SCF3, S(O)CF3, SO2CH3, SO2C2H5, SO2CH(CH3)2, SO2CF3, SO2(4-F-C6H4), and C(CH3)2CN.

[0129] In a preferred embodiment, at least one R 3 The radical is selected from C(=N-OR) 14 )NR 121 R 131 and C(=N-OR) 14 C3-C6 cycloalkyl, wherein the ring is unsubstituted or R 3a replace.

[0130] R 3 The marker m in R is preferably 2. 3 The preferred value for the marker n is 2.

[0131] R 3 The groups are preferably located at the 3 and 5 positions.

[0132] In one embodiment, R 3 The marker m in R is either 0 or 1, and each R 3 Independently selected from S(O)m-C1-C4-haloalkyl groups. In another embodiment, R 3 The marker m in R is either 0 or 1, and each R 3 It is independently selected from S(O)CF3 and S(O)CHF2.

[0133] In another embodiment, each R 3 Preferably, it is independently selected from halogens, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, and 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 It is a phenyl group, which is reacted with R 3a Partially replace.

[0134] In another embodiment, each R 3a Independently selected from halogens, CN, NO2, OH, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, 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, C(O)NR 12 R 13 C(O)OR 141 C(O)R 151 C(=N-OR) 141 C3-C6-cycloalkyl, C(=N-OR) 141 )NR 121 R 131 ;

[0135] R 3b The preferred components are halogens, C1-C4-alkyl groups, or C3-C6-cycloalkyl groups, especially F, Cl, CH3, or cC3H5.

[0136] In a preferred embodiment, R 4 Is it unreplaced or replaced by (R) 41 ) n Substituted 5- or 6-membered heteroaryl groups. These compounds correspond to formula I.4A.

[0137] In one embodiment, R 4Preferably, it is an unsubstituted or substituted 6-membered heteroaryl group having one or two nitrogen atoms. Unsubstituted or substituted 2-pyridyl, 3-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, and 3-pyridazinyl are more preferred. 4 Unsubstituted or substituted 2-pyridyl and 3-pyridyl groups are particularly preferred R groups. 4 In another embodiment, unsubstituted or substituted 4-pyrimidinyl groups are particularly preferred. 4 Unsubstituted or substituted 2-pyridyl groups are particularly preferred R. 4 .

[0138] In another embodiment, R 4 Preferably, it has 1 or 2 nitrogen atoms, and optionally is R 41 The substituted 6-membered heteroaryl group. In another embodiment, R 4 It is 2-pyridyl, 3-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 2-pyrazinyl, or 3-pyridazinyl, optionally with R 41 Replacement. In another embodiment, R 4 It is optional to be R 41 Substituted 2-pyridyl or 3-pyridyl. In another embodiment, R 4 It is optional to be R 41 Substituted 4-pyrimidinyl. In another embodiment, R 4 It is optional to be R 41 Substituted 2-pyridyl group.

[0139] In another embodiment of I.4A, R 4 Is it unreplaced or replaced by (R) 41 ) n Substituted 5-membered heteroaryl groups. Unsubstituted or substituted 5-membered heteroaryl groups having 2 or 3 independently selected heteroatoms chosen from N, O, or S are R in I.4A. 4 Another embodiment. By R 41 The substituted 2-thiazolyl, 2-oxazolyl, and 3-pyrazolyl groups are R in I.4A 4 A particularly preferred embodiment.

[0140] R, a special preference in I.4A 4 It has 1 or 2 substituents R 41 2-Pyridine, wherein these substituents are independently selected from halogens, CN, CHF2, OR 14 NR 15 C(O)OR 15 OC(O)OR 15 OC(O)R 15 OC(O)NR 12 R 13 C(O)NR15 NR 12 R 13 and NR 15 NR 12 R 13 In another embodiment of I.4A, R 4 It has one or two independent substituents R selected from F, Cl, Br, CHF2, OCHF2 and OCF3. 41 2-pyridine, preferably wherein R 41 Located in R 4 The 3 or 5 digits above.

[0141] In another embodiment of I.4A, R 4 It has 1 substituent R 41 2-Pyrimidine, wherein R 41 Selected from F, Cl, Br, Me, CHF2, OCHF2, or OCF3, preferably R 41 Located in R 4 The top 5.

[0142] In one embodiment of I.4A, with R 4 The nitrogen atom is bound to R 41 Preferably, they are independently selected from C1-C6-alkyl, C1-C4-haloalkyl, C3-C4-cycloalkyl, C3-C4-cyanocycloalkyl, and C(O)R 15 C(O)NHR 122 C(O)NR 122 R 132 SO2-C3-C4-cycloalkyl, or 4-membered heterocyclic. In a specific embodiment of I.4A, with R 4 The nitrogen atom is bound to R 41 It is independently selected from CH3, CH2CH3, CH(CH3)2, cC3H5, 1-CN-cC3H5, CHF2, C(O)NHCH3, C(O)N(CH3)2 or SO2-cC3H5.

[0143] In one embodiment, with R 4 The carbon atom bonded to R 41 Preferably, it is independently selected from halogen, CN, OR 15 Or S(O) m -C3-C4-cycloalkyl, C(O)NHR 122 、or C(O)NR 122 R 132 In another embodiment, with R 4 The carbon atom bonded to R 41It is independently selected from F, Cl, Br, CN, OCHF2, OCF3, C(O)NHCH3 or C(O)N(CH3)2.

[0144] In another preferred embodiment, R 4 Is it unreplaced or replaced by (R) 41 ) n Partially or completely substituted phenyl groups, provided that X is CH or N, and Q is N, and R... 5 and R 6 If it is H, then R 4 It is not C6H5. This type of compound corresponds to formula I.4B.

[0145] In another preferred embodiment, R 4 Is by (R) 41 ) n A partially or completely substituted phenyl group, wherein o is 1, 2, 3, 4, or 5.

[0146] In a preferred embodiment of compound I.4B, R 41 Preferably in position 2.

[0147] In a preferred embodiment of compound I.4B, (R 41 )2 is preferably in positions 2 and 4.

[0148] In a preferred embodiment of compound I.4B, (R 41 )2 is preferably in positions 2 and 6.

[0149] The index o is preferably 1 or 2.

[0150] In another embodiment, R 41 It is halogen, CN, OR 15 S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl, S(O) m -C3-C4-cyanocycloalkyl, NR 15 C(O)OR 15 OC(O)OR 15 OC(O)R 15 OC(O)NR 12 R 13 C(O)OR 15 C(O)R 15 C(O)NHR 122 C(O)NR 122 R 132 C(O)NR 15 NR 12 R 13C(=NOR) 14 )R 15 C(=NOR) 14 )NR 12 R 13 NR 15 NR 12 R 13 Unreplaced or R 3 Replacement of 3- or 4-membered heterocyclic rings.

[0151] In another embodiment, R 41 Is it partially or completely by R 3 Substituted C3-C4-cycloalkyl groups.

[0152] R 5 Preferably, it is H, a halogen, a C1-C4-alkyl group, or a C3-C6-cycloalkyl group, especially H, Br, Cl, or cC3H5. In another preferred embodiment, R 5 It is H.

[0153] R 6 Preferably, it is H, a halogen, or a C1-C4-alkyl group, especially H, F, Cl, or CH3. In another preferred embodiment, R 6 It is H.

[0154] In another embodiment, R 5 and R 6 Only one, preferred R 5 Unlike H. In another preferred embodiment, R 5 and R 6 Both are H.

[0155] Q is preferably CCl, CF, or N.

[0156] In a preferred embodiment, Q is N.

[0157] In another preferred embodiment, Q is CF.

[0158] A particularly preferred embodiment is compound I, wherein R 1 It is H, CH3, or CH2-cC3H5; R 2 It is CH3; n is 2; R 3 It is bonded at the 3 and 5 positions and is selected from halogens, halomethyl groups, halomethoxy groups, unsubstituted and halogenated or cyano-substituted cyclopropyl groups, and S(O). m - Halomethyl groups, and S(O) groups substituted with halogens. m -phenyl, and R 4 It is unsubstituted or halogenated, CN, C(O)NR 12 R 13Substituted pyridines, pyridazines, or oxazoles, wherein R 12 and R 13 It is C1-C4 alkyl, C3-C6-cycloalkyl, or C6-C6-cycloalkyl-C1-C4-alkyl.

[0159] In particular, compounds having Formula I, compiled in the table below, are preferred in consideration of their intended use. Furthermore, each group mentioned for a substituent in the table (independent of the mentioned combination) is a particularly preferred aspect of that substituent.

[0160]

[0161] Table 1: Compounds with formula IA*, where X is CH, R 1 It is H, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0162] Table 2: Compounds with formula IA*, where X is CH, R 1 It is H, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0163] Table 3: Compounds with formula IA*, where X is CH, R 1 It is CH3, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0164] Table 4: Compounds with formula IA*, where X is CH, R 1 It is CH3, R 5 It is Cl, R 6 It is H, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0165] Table 5: Compounds with formula IA*, where X is CH, R1 It is CH2-cC3H5, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0166] Table 6: Compounds with formula IA*, where X is CH, R 1 It is CH2-cC3H5, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0167] Table 7: Compounds with formula IA*, where X is N, R 1 It is H, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0168] Table 8: Compounds with formula IA*, where X is N, R 1 It is H, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0169] Table 9: Compounds having the formula IA*, where X is N, R 1 It is CH3, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0170] Table 10: Compounds having the formula IA*, where X is N, R 1 It is CH3, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0171] Table 11: Compounds with formula IA*, where X is N, R 1 It is CH2-cC3H5, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0172] Table 12: Compounds with formula IA*, where X is N, R 1 It is CH2-cC3H5, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0173] Table 13: Compounds with the formula IB*, where X is CH, R 1 It is H, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0174] Table 14: Compounds with formula IB*, where X is CH, R 1 It is H, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0175] Table 15: Compounds with formula IB*, where X is CH, R 1 It is CH3, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0176] Table 16: Compounds with the formula IB*, where X is CH, R 1 It is CH3, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4The combinations for each compound correspond to a row in Table A in each case.

[0177] Table 17: Compounds with the formula IB*, where X is CH, R 1 It is CH2-cC3H5, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0178] Table 18: Compounds with the formula IB*, where X is CH, R 1 It is CH2-cC3H5, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0179] Table 19: Compounds with the formula IB*, where X is N, R 1 It is H, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0180] Table 20: Compounds with the formula IB*, where X is N, R 1 It is H, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0181] Table 21: Compounds with the formula IB*, where X is N, R 1 It is CH3, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0182] Table 22: Compounds with the formula IB*, where X is N, R 1 It is CH3, R 5 It is Cl, R 6 It is H, and (R)3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0183] Table 23: Compounds with the formula IB*, where X is N, R 1 It is CH2-cC3H5, R 5 and R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0184] Table 24: Compounds with the formula IB*, where X is N, R 1 It is CH2-cC3H5, R 5 It is Cl, R 6 It is H, and (R) 3 ) n and R 4 The combinations for each compound correspond to a row in Table A in each case.

[0185] Table A

[0186]

[0187]

[0188]

[0189]

[0190]

[0191]

[0192]

[0193] The term "one or more compounds of the present invention" refers to one or more compounds having Formula I or "one or more compounds I", and includes their salts, tautomers, stereoisomers, and N-oxides.

[0194] The present invention also relates to an agricultural chemical composition comprising an adjuvant and at least one compound I.

[0195] The agricultural chemical composition contains an effective amount of compound I for killing pests.

[0196] Compound I can be converted into commonly used types of agrochemical compositions, such as solutions, emulsions, suspensions, powders, pastes, granules, compressed formulations, capsules, and mixtures thereof. Examples of composition types include suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsions (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, tablets, wettable powders or granules (e.g., WP, SP, WS, DP, DS), compressed formulations (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticides (e.g., LN), and gel formulations (e.g., GF) for treating plant propagation material (e.g., seeds). These and other composition types are defined in “Catalogue of pesticide formulation types and international coding system,” Technical Monograph, Vol. 2, 6th edition, May 2008, CropLife International. These compositions are prepared in known ways, for example by the following: 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.

[0197] Suitable additives include solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, auxiliary agents, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, defoamers, colorants, viscous agents, and adhesives.

[0198] Suitable solvents and liquid carriers are water and organic solvents. Suitable solid carriers or fillers are mineral soils.

[0199] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, and polyelectrolytes. These surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or auxiliaries. Surfactants are listed in McCutcheon's, Volume 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, 2008 (international or North American edition). Suitable anionic surfactants are alkali metal salts, alkaline earth metal salts, or ammonium salts of sulfonic acids, sulfuric acids, phosphoric acids, and carboxylic acids. Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, glycosyl surfactants, and polymeric surfactants. Suitable cationic surfactants are quaternary ammonium surfactants.

[0200] Agricultural chemical compositions typically contain an active substance at a weight of between 0.01% and 95%, preferably between 0.1% and 90%, and most preferably between 0.5% and 75%. The active substance is used at a purity of 90% to 100%, preferably 95% to 100%.

[0201] Various types of oils, wetting agents, adjuvants, or fertilizers can be added as premixes or (if appropriate) to the active substance or the composition containing them just before use (in a barrel mix). These agents can be mixed with the compositions according to the invention at a weight ratio of 1:100 to 100:1.

[0202] Users typically apply the compositions according to the invention via pre-dose devices, backpack sprayers, spray cans, spray aircraft, or irrigation systems. Generally, the agricultural chemical composition is prepared with water, buffers, and / or additional adjuvants to the desired application concentration, thereby obtaining the ready-to-use spray liquid or agricultural chemical composition according to the invention. Typically, 20 to 2000 liters of ready-to-use spray liquid are applied per hectare of agriculturally usable area.

[0203] Compound I is suitable for protecting crops, plants, plant propagation material (e.g., seeds), or soil or water bodies in which plants grow from pests to prevent or contamination by animal pests. Therefore, the present invention also relates to a plant protection method comprising contacting the crop, plant, plant propagation material (e.g., seeds), or soil or water body in which the plant is to be protected from pests to an effective amount of the pest-killing compound I.

[0204] Compound I is also suitable for combating or controlling animal pests. Therefore, the present invention also relates to a method for combating or controlling animal pests, the method comprising contacting an animal pest, its habitat, breeding ground, or food supply, or crop, plant, plant propagation material (e.g., seeds), or soil, or an area, material, or environment in which the animal pest grows or may grow, with a pest-killing effective amount of compound I.

[0205] Compound I is effective for any and all developmental stages, such as egg, larva, pupa, and adult, through contact with and uptake of both.

[0206] Compound I may be applied as is or in the form of a composition comprising them.

[0207] It can be applied before and after crops, plants, or plant propagation materials are infected by harmful organisms.

[0208] The term "contact" includes both direct contact (the direct application of a compound / composition to animals, pests, or plants) and indirect contact (the application of a compound / composition to a location).

[0209] The term "animal pests" includes arthropods, gastropods, and nematodes. According to the invention, preferred animal pests are arthropods, especially insects and arachnids, particularly insects.

[0210] The term "plant" includes cereals such as durum wheat and other wheat, rye, barley, triticale, oats, rice, or corn (feed corn and sweet corn / sweet corn and field corn); beets such as sugar beets or feed beets; fruits such as pome, stone fruit, or soft fruit such as apple, pear, plum, peach, nectarine, almond, cherry, papaya, strawberry, raspberry, blackberry, or gooseberry; legumes such as beans, lentils, peas, alfalfa, or soybeans; oilseed plants such as rapeseed (oilseed rape), rapeseed, mustard, olive, sunflower, coconut, cocoa bean, castor oil plants, oil palm, peanut, or soybeans; and cucurbitaceous plants such as squash, pumpkin, cucumber, or melon. Fiber plants, such as cotton, flax, or jute; citrus fruits, such as oranges, lemons, grapefruits, or tangerines; vegetables, such as eggplant, spinach, lettuce (e.g., head lettuce), chicory, cabbage, asparagus, carrots, onions, garlic, leeks, tomatoes, potatoes, gourds, or bell peppers; laurel plants, such as avocados, cinnamon, or camphor; energy and raw material plants, such as corn, soybeans, rapeseed, sugarcane, or oil palm; tobacco; nuts, such as walnuts; pistachios; coffee; tea; bananas; vines; hops; stevia; natural rubber plants or ornamental and forestry plants, shrubs, broadleaf trees or evergreens, eucalyptus; turf; lawns; grasses. Preferred plants include potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee, or sugarcane; fruits; vines; ornamental plants; or vegetables such as cucumbers, tomatoes, green beans, or squash.

[0211] The term "seed" includes seeds and plant propagules, including true seeds, seed pieces, suckers, bulbs, tubers, fruits, tubers, grains, cuttings, and cut shoots, and preferably refers to true seeds.

[0212] "Pest-effective dose" refers to the amount of active ingredient required to achieve an observable effect on growth, including necrosis, death, inhibition, prevention and elimination, destruction, or otherwise reduction of the presence and activity of target organisms. The pest-effective dose can vary for the various compounds / compositions used in this invention. The pest-effective dose of a composition will also vary depending on key conditions such as the desired pest-killing effect and duration, climate, target species, location, and method of application.

[0213] For use in treating crop plants, for example by foliar application, the application rate of the active ingredient of the present invention can be in the range of 0.0001 g to 4000 g per hectare, for example 1 g to 2 kg per hectare or 1 g to 750 g per hectare, ideally 1 g to 100 g per hectare.

[0214] Compound I is also suitable for use against non-crop insect pests. For use against said non-crop pests, Compound I can be used as bait compositions, gels, common insect sprays, aerosols, as ultra-low volume applications, and in mosquito nets (impregnation or surface application).

[0215] The term "non-crop insect pests" 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, housefly (Muscadomestica), and Tribolium spp.; termites, such as Reticulitermesflavipes and Coptotermes formosanus; cockroaches, such as German cockroach (Blatellagermanica) and American cockroach (Periplaneta Americana); and ants, such as red imported fire ant (Solenopsis invicta), Argentine ant (Linepithema humile), and Pennsylvania blackwood worker ant (Camponotus pennsylvanicus).

[0216] The bait can be a liquid, solid, or semi-solid formulation (e.g., a gel). For use in bait compositions, the active ingredient typically comprises 0.001 wt% to 15 wt%, ideally 0.001 wt% to 5 wt% of the active compound.

[0217] Compound I and its compositions can be used to protect wood materials, such as trees, wooden fences, railway sleepers, frames, artworks, and buildings, as well as building materials, furniture, leather, fibers, vinyl products, wires and cables, from ants, termites and / or beetles that damage wood or textiles, and to prevent ants and termites from causing damage to crops or humans (e.g. when pests invade houses and public facilities or nest in yards, orchards or parks).

[0218] The conventional application rate in protective materials is, for example, per m 2 For processing materials ranging from 0.001 g to 2000 g or 0.01 g to 1000 g of active compounds, ideally per m 2 0.1 g to 50 g.

[0219] Insecticidal compositions used in impregnated materials typically contain 0.001 to 95 wt%, preferably 0.1 to 45 wt%, and more preferably 1 to 25 wt% of at least one repellent and / or insecticide.

[0220] The compounds of the present invention are particularly suitable for effectively combating animal pests, such as arthropods and nematodes, including:

[0221] Insects from the following suborders: Auchenorrhyncha, such as cotton leafhopper (Amrascabiguttula), species of the genus *Empoasca*, two-spotted black-tailed leafhopper (Nephotettix virescens), white-backed planthopper (Sogatella furcifera), species of the genus *Mahanarva*, gray planthopper (Laodelphaxstriatellus), brown planthopper (Nilaparvata lugens), and citrus psyllid (Diaphorina citri).

[0222] Lepidoptera, such as species of the genus *Helicoverpa*, *Heliothis virescens*, *Lobesia botrana*, *Ostrinianubilalis*, *Plutella xylostella*, *Pseudoplusia includens*, *Scirpophaga incertulas*, species of the genus *Spodoptera*, *Trichoplusia ni*, *Tuta absoluta*, *Cnaphalocrocismedialis*, *Cydia pomonella*, *Chilo suppressalis*, *Anticarsia gemmatalis*, *Agrotis ipsilon*, and *Chrysodeixis includens*.

[0223] True bugs, such as species of the genus *Lygus* spp.; stink bugs, such as species of the genus *Euschistus* spp., *Halyomorpha halys*, *Nezara viridula*, *Piezodorus guildinii*, and *Dichelops furcatus*.

[0224] Thrips, such as species of the genera *Frankliniella*, *Thrips*, and *Dichromothrips corbettii*.

[0225] Aphids, such as the pea aphid (Acyrthosiphon pisum), species of the genus Aphis (Aphis spp.), the peach aphid (Myzus persicae), species of the genus Rhopalosiphum (Rhopalosiphum spp.), the wheat aphid (Schizaphis graminum), and the vegetable aphid (Megoura viciae).

[0226] Whiteflies, such as the greenhouse whitefly (Trialeurodes vaporariorum) and species of the genus Bemisiaspp.

[0227] Coleoptera, including species of the genera *Phyllotreta*, *Melanotus*, *Meligethes aeneus*, *Leptinotarsadecimlineata*, *Ceutorhynchus*, *Diabrotica*, *Anthonomus grandis*, *Atomaria linearia*, *Agriotes*, and *Epilachna*.

[0228] Flies, such as species of the genera *Delia*, *Ceratitis capitate*, *Bactrocera*, and *Liriomyza*.

[0229] The superfamily Coccoidea includes species such as Aonidiella aurantia and Ferrisia virgate.

[0230] Arthropods (mites) of the class Arachnida, such as Penthhaleus major and species of the genus Tetranychus spp.;

[0231] Nematodes, such as soybean cyst nematode (Heterodera glycines), root-knot nematode species (Meloidogynespp.), short-bodied nematode species (Pratylenchus spp.), and Caenorhabditis elegans.

[0232] Compound I is suitable for treating or protecting animals from parasitic infestation or infection. Therefore, the present invention also relates to the use of the compounds of the present invention in the manufacture of medicaments for treating or protecting animals from parasitic infestation or infection. Furthermore, the present invention relates to a method for treating or protecting animals from parasitic infestation and infection, the method comprising administering or applying to an animal, orally, topically, or parenterally, an effective amount of compound I for killing parasites.

[0233] This invention also relates to the non-therapeutic use of the compounds of this invention for treating or protecting animals from parasitic infestation and infection. Furthermore, this invention relates to a non-therapeutic method for treating or protecting animals from parasitic infestation and infection, which comprises applying a parasite-killing effective amount of compound I to the site.

[0234] The compounds of the present invention are further suitable for use in combating or preventing parasites in or on animals. Furthermore, the present invention relates to a method for combating or preventing parasites in or on animals, the method comprising contacting the parasites with a parasite-killing effective amount of compound I.

[0235] This invention also relates to the non-therapeutic use of compound I for the prevention or treatment of parasites. Furthermore, this invention relates to a non-therapeutic method for the prevention or treatment of parasites, comprising applying a parasite-killing effective amount of compound I to the site.

[0236] Compound I is effective through both contact (via soil, glass, walls, mosquito nets, carpets, blankets, or animal parts) and ingestion (e.g., bait). Furthermore, Compound I can be applied to any and all developmental stages.

[0237] Compound I may be applied as is or in the form of a composition comprising them.

[0238] The term “site” means a habitat, food supply, breeding ground, area, material or environment in which a parasite grows or may grow outside of an animal.

[0239] As used herein, the term "parasite" includes both endoparasites and ectoparasites. In some embodiments of the invention, endoparasites may be preferred. In other embodiments, ectoparasites may be preferred. Infections in warm-blooded animals and fish include lice, biting lice, ticks, sheep nasal fly larvae, sheep tick flies, chelicerae, houseflies, flies, maggot fly larvae, chiggers, black flies, mosquitoes, and fleas.

[0240] The compounds of this invention are particularly effective against the following parasites: temperate bed bug (Cimex lectularius), blood-red fan tick (Rhipicephalus sanguineus), and cat cat flea (Ctenocephalides felis).

[0241] As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferred mammals include cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, buffalo, donkeys, fallow deer and reindeer, as well as fur-bearing animals such as mink, chinchillas and raccoons, birds such as hens, geese, turkeys and ducks, and fish such as freshwater and saltwater fish such as salmon, carp and eels. Domesticated animals such as dogs or cats are particularly preferred.

[0242] Compound I can be administered at a total dose of 0.5 mg / kg to 100 mg / kg / day, preferably 1 mg / kg to 50 mg / kg / day.

[0243] For oral administration to warm-blooded animals, compound I can be formulated into animal feed, animal feed premix, animal feed concentrate, pellets, solutions, pastes, suspensions, extracts, gels, tablets, large pellets, and capsules. For oral administration, the selected dosage form should provide the animal with 0.01 mg / kg to 100 mg / kg body weight of compound I per day, preferably 0.5 mg / kg to 100 mg / kg body weight of compound I per day.

[0244] Alternatively, compound I can be administered to animals parenterally, for example, via intracavitary, intramuscular, intravenous, or subcutaneous injection. For subcutaneous injection, compound I can be dispersed or dissolved in a physiologically acceptable carrier. Alternatively, compound I can be formulated into an implant for subcutaneous administration. Additionally, compound I can be administered to animals transdermally. For parenteral administration, the selected dosage form should provide animals with 0.01 mg / kg to 100 mg / kg of compound I daily.

[0245] Compound I can also be applied topically to animals in the form of infusions, powders, gels, rings, medallions, sprays, shampoos, spot-on formulations, and pour-on formulations, as well as in the form of ointments, oil-in-water emulsions, or water-in-oil emulsions. For topical application, infusions and sprays typically contain 0.5 ppm to 5,000 ppm, preferably 1 ppm to 3,000 ppm, of Compound I. Furthermore, Compound I can be formulated into ear tags for animals, particularly tetrapods (e.g., cattle and sheep).

[0246] The oral solution is administered directly.

[0247] The solution is applied by dripping, smearing, rubbing, sprinkling, or spraying onto the skin.

[0248] Apply or coat the gel to the skin or introduce it into the body cavity.

[0249] Spray formulations are applied to or sprayed onto a defined area of ​​skin, where the active compound penetrates the skin and acts internally. Spray formulations are prepared by dissolving, suspending, or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture.

[0250] The emulsion can be administered orally, transdermally, or as an injection.

[0251] The suspension can be administered orally or topically / transdermally.

[0252] Semi-solid dosage forms can be administered orally or topically / transdermally.

[0253] To produce solid dosage forms, the active compound is mixed with a suitable excipient, and if appropriate, auxiliaries are added, and the mixture is prepared into the desired form.

[0254] The compositions that can be used in this invention typically contain about 0.001% to 95% of compound I.

[0255] The ready-to-use formulation contains a compound that acts on parasites, preferably ectoparasites, at a concentration of 10 ppm to 80% by weight, preferably 0.1% to 65% by weight, more preferably 1% to 50% by weight, and most preferably 5% to 40% by weight.

[0256] The preparation diluted before use contains a compound that acts on ectoparasites at a concentration of 0.5% to 90% by weight, preferably 1% to 50% by weight.

[0257] In addition, the formulation contains a compound of formula I that resists endoparasites at a concentration of 10 ppm to 2% by weight, preferably 0.05% to 0.9% by weight, and very particularly preferably 0.005% to 0.25% by weight.

[0258] Solid formulations of the compounds of the invention can be administered over three weeks at a total amount of 10 mg / kg to 300 mg / kg, preferably 20 mg / kg to 200 mg / kg, and most preferably 25 mg / kg to 160 mg / kg of the body weight of the treated animal.

[0259] Preparation Examples

[0260] Compounds are characterized by melting point determination, NMR spectroscopy, or by mass-to-charge ratio ([m / z]) and retention time (RT; [min]), such as by mass spectrometry (MS) combined with HPLC analysis (HPLC-MS = high performance liquid chromatography-mass spectrometry) or LC analysis (LC-MS = liquid chromatography-mass spectrometry).

[0261] Method A: Shimadzu LC-30AD MSD: LCMS-2020; Column: Luna-C18 3 µm 2.0 × 30 mm; Mobile phase: A: Water + 0.04% TFA; B: ACN + 0.02% TFA; Temperature: 40°C; Gradient: 5% B to 95% B in 1.6 min; 95% B to 100% B in 0.9 min; 100% B to 5% B in 0.02 min; 5% B for 0.48 min; Flow rate: 0.8 mL / min; MS: ESI positive; Mass range: 50-2000.

[0262] Method B: Agilent 1200 + MS Agilent 6100; Column: XBridge C18 2.1 × 50 mm 5 µm; Mobile phase: A: 10 mM NH4CO3 in water, B: ACN; Temperature: 40°C; Gradient: 5% B to 95% B over 0.7 min; 95% B for 0.46 min; 95% B to 5% B over 0.34 min; Flow rate: 1.5 mL / min; MS: ES-API positive; Mass range (m / z): 50–1500.

[0263] Method C: Shimadzu Nexera UHPLC + Shimadzu LCMS-2020, ESI; Column: Kinetex 1.7µXB-C18 100A, 2.1 × 50 mm; Mobile phase: A: Water + 0.1% TFA; B: ACN; Temperature: 60°C; Gradient: 5% B to 100% B over 1.5 min; 100% B over 0.25 min; Flow rate: 0.8 mL / min to 1.0 mL / min over 1.5 min; MS: ESI positive; Mass range (m / z): 100-700.

[0264] By appropriately modifying the starting materials and using the procedure given in the synthesis instructions, another compound I was obtained. The compounds obtained in this manner are listed in the table below along with their physical data.

[0265] Example 1: Preparation of N-[1-[3-[1-(3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-1)

[0266] N-[1-[3-[1-(3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-4, 100 mg, 0.17 mmol) was added to a suspension of Pd / C (500 mg) in MeOH (5 mL), and the resulting mixture was stirred at 25°C for 16 h in H2 (15 Psi) until completion was confirmed by LCMS analysis. The reaction mixture was filtered, and the filtrate was concentrated. The residue was purified by preparative TLC (DCM / MeOH 10:1) to give N-[1-[3-[1-(3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-1, 40 mg, 47% yield) as a yellow solid.

[0267] 1 H-NMR (CD3OD, 400 MHz) δ = 1.74-1.79 (m, 3H) 6.35-6.43 (m, 1H) 7.68(dd, J=8.25, 4.88Hz, 1H) 8.13 (s, 1H) 8.39-8.46 (m, 3H) 8.67 (dd, J=4.82,1.31Hz, 1H) 8.68-8.71 (m, 1H) 8.71-8.76 (m, 1H) 9.19-9.26 (m, 1H) 9.36-9.45(m, 1H).

[0268] Example 2: Preparation of N-[1-[3-[1-(2-amino-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-2)

[0269] Fe (0.81 g, 14.48 mmol) and NH4Cl (0.775 g, 14.48 mmol) were added to a solution of N-[1-[3-[1-(2-nitro-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-3, 1 g, 1.81 mmol) in EtOH / H2O (3:1 v / v, 12 mL). The mixture was stirred at 80°C for 6 h until complete as determined by LCMS analysis. The mixture was quenched with H2O (30 mL) and extracted with EtOAc (30 mL × 3). The combined organic phases were washed with brine (30 mL × 3), dried over Na2SO4, and concentrated. The residue was purified by preparative HPLC (NH4HCO3) to provide N-[1-[3-[1-(2-amino-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-2, 600 mg, 63% yield) as a yellow solid.

[0270] 1 H-NMR (CDCl3, 400 MHz) δ = 8.77 (d, J=2.13Hz, 1H) 8.70 (d, J=2.25Hz, 1H) 8.61 (s, 1H) 8.26 (s, 2H) 8.22 (dd, J=5.07, 1.44Hz, 1H) 8.02 (s, 1H) 7.74(br d, J=8.13Hz, 1H) 7.68 (dd, J=7.69, 1.31Hz, 1H) 6.86 (dd, J=7.69, 5.07Hz,1H) 6.58-6.68 (m, 1H) 5.96 (br d, J=5.63Hz, 2H) 1.69(d, J = 6.63 Hz, 3H).

[0271] Example 3: Preparation of N-[1-[3-[1-(2-nitro-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-3)

[0272] At 20°C, K₂CO₃ (0.481 g, 3.5 mmol) and 3-fluoro-2-nitro-pyridine (0.248 g, 1.7 mmol) were added to a solution of N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (0.5 g, 1.16 mmol) in DMF (10 mL). The mixture was stirred for 12 h until complete as determined by LCMS analysis. The mixture was quenched with H₂O (30 mL) and extracted with EtOAc (30 mL × 3). The combined organic layers were washed with brine (30 mL × 4), dried over Na2SO4, concentrated, and purified by preparative HPLC (NH4HCO3) to obtain N-[1-[3-[1-(2-nitro-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-3, 500 mg, 78% yield) as a yellow solid.

[0273] 1 H-NMR (CDCl3, 400MHz) δ = 8.77 (d, J=2.25Hz, 1H) 8.74 (dd, J=4.56,1.19Hz, 1H) 8.67-8.71 (m, 2H) 8.27-8.30 (m, 3H) 8.02 (s, 1H) 7.89 (dd, J=8.00, 4.63Hz, 1H) 7.82 (br d, J=7.75Hz, 1H) 6.44-6.54 (m, 1H) 1.68 (d, J=6.63Hz, 3H).

[0274] Example 4: Preparation of N-[1-[3-[1-(2-bromo-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-4)

[0275] A mixture of N-[1-[3-[1-(2-amino-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-2, 228 mg, 0.44 mmol), CH2Br2 (8 mL), and CuBr2 (127 mg, 0.57 mmol) was stirred at 50°C for 5 min. Isovalerate (93 mg, 0.79 mmol) was added dropwise at 50°C, and the resulting mixture was stirred at 50°C for 1 h until completion was confirmed by TLC (DCM / MeOH 10:1). The reaction was quenched with H2O (10 mL) and extracted with DCM (10 mL × 2). The combined organic phases were dried over Na2SO4 and concentrated. The residue was purified by silica gel column chromatography (gradient PE / EtOAc 10:1 to DCM / MeOH 20:1) to provide N-[1-[3-[1-(2-bromo-3-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-4, 58 mg, 22% yield) as a yellow solid.

[0276] 1 H-NMR (CD3CN, 400MHz) δ = 1.58-1.67 (m, 3H) 2.19 (s, 1H) 6.15-6.32(m, 1H) 7.54-7.66 (m, 1H) 8.01-8.05 (m, 1H) 8.10-8.14 (m, 1H) 8.32 (s, 2H)8.52-8.57 (m, 1H) 8.64 (q, J=2.38Hz, 2H) 8.78-8.86 (m, 1H).

[0277] Example 5: Preparation of N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-6)

[0278] The synthesis was performed in two parallel batches. K₂CO₃ (195 mg, 1.41 mmol) and 2-fluoropyridine (180.5 mg, 1.86 mmol) were added to a solution of N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (200 mg, 0.47 mmol) in DMSO (4 mL) at 15°C. The mixture was stirred at 140°C for 16 h until completion was confirmed by LCMS analysis. The reaction mixture was quenched with H₂O (10 mL) and extracted with EtOAc (5 mL × 3). The combined organic layers were washed with brine (20 mL), dried over Na₂SO₄, and concentrated. The residue was purified by silica gel column chromatography (PE / (EtOAc / EtOH 3:1) gradient 1:0 to 1:1) to give N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-6, total 180 mg, 38% yield) as a yellow solid.

[0279] 1 H-NMR (CDCl3, 400MHz) δ = 9.39 (s, 1H) 8.80 (br d, J=1.75Hz, 1H) 8.69(d, J=2.38Hz, 1H) 8.50-8.55 (m, 1H) 8.29-8.33 (m, 2H) 8.12 (d, J=8.13Hz, 1H)8.06 (br d, J=7.88Hz, 1H) 8.03 (s, 1H) 7.98 (td, J=7.82, 1.75Hz, 1H) 7.39 (ddd, J=7.41, 4.85, 1.00Hz, 1H) 6.68 (dd, J=7.82, 6.69Hz, 1H) 1.72 (d, J=6.63Hz, 3H).

[0280] Example 6: Preparation of N-methyl-N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-17)

[0281] At 15°C, Cs₂CO₃ (192 mg, 0.59 mmol) and MeI (126 mg, 0.885 mmol) were added to a solution of N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-6, 150 mg, 0.295 mmol) in DMF (3 mL). The mixture was stirred at 60°C for 16 h until complete as determined by LCMS. The reaction mixture was quenched with H₂O (10 mL) and extracted with EtOAc (5 mL × 3). The combined organic layers were washed with brine (20 mL), dried over Na₂SO₄, and concentrated. The residue was purified by preparative reversed-phase HPLC (neutral, MeCN-H2O) to give N-methyl-N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-17, 56 mg, 36% yield) as a yellow solid.

[0282] 1 H-NMR (CDCl3, 400 MHz) δ = 8.98-9.57 (m, 1H) 8.77 (dd, J=14.20, 2.31Hz, 2H) 8.56 (d, J=4.6Hz, 1H) 8.01-8.11 (m, 1H) 7.60-8.01 (m, 4H) 7.45-7.56(m, 1H) 6.00-6.51 (m, 1H) 3.01 (br s, 3H) 1.70 (d, J=6.88 Hz, 3H).

[0283] Example 7: Preparation of 3-chloro-5-(difluoromethoxy)-N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]benzamide (I-24)

[0284] Step 1: Preparation of 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]acetone (Int-3)

[0285] At 25°C, K₂CO₃ (17 g, 122 mmol) and 2-fluoropyridine (7.9 g, 81.5 mmol) were added to a solution of 1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]acetone (7.7 g TFA salt, 26.9 mmol) in DMSO (77 mL). The mixture was stirred at 100°C for 16 h until complete as determined by TLC (EtOAc). The reaction mixture was quenched with H₂O (100 mL), extracted with EtOAc (100 mL × 3), and the combined organic layers were washed with brine (100 mL), dried over Na₂SO₄, and concentrated. The residue was purified by silica gel column chromatography (EtOAc) to give 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl] acetone as a yellow solid (Int-3, 5 g, 69% yield).

[0286] Step 2: Preparation of 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethylamine (Int-4)

[0287] At 25°C, NH3 (7 N in MeOH, 50 mL) and NH4OAc (15 g, 187 mmol) were added to a solution of 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]acetone (Int-3, 5 g, 18.7 mmol) in MeOH (250 mL), and the mixture was stirred for 1 h. NaBH3CN (3.55 g, 56.4 mmol) was added, and the reaction mixture was stirred at 50°C for 16 h, then the completion was determined by TLC (EtOAc). The reaction mixture was quenched with H2O (500 mL) and extracted with EtOAc (300 mL × 3). The combined organic layers were washed with brine (500 mL), dried over Na2SO4, and concentrated. The residue was purified by silica gel column chromatography (DCM / MeOH gradient 50:1 to 10:1) to give 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethylamine (Int-4, 2.6 g, 52% yield) as a white solid.

[0288] Step 3: Preparation of 3-chloro-5-(difluoromethoxy)-N-[1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]benzamide (I-24)

[0289] A mixture of 3-chloro-5-(difluoromethoxy)benzoic acid (83 mg, 0.37 mmol), 1-[3-[1-(2-pyridyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethylamine (Int-4, 100 mg, 0.37 mmol), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (185 mg, 0.48 mmol), and N,N-diisopropylethylamine (0.16 mL, 0.94 mmol) in DMF (4 mL) was stirred at ambient temperature (20°C–25°C) for 22 h. Volatile substances were removed under reduced pressure. The residue was dissolved in EtOAc and washed twice with water. The organic layer was dried over Na2SO4, and volatile substances were removed under reduced pressure. The residue was purified by silica gel column chromatography (eluting with cyclohexane / EtOAc 100:0 to 0:100) to provide 3-chloro-5-(difluoromethoxy)-N-[1-[3-[1-(2-pyridinyl)-1,2,4-triazol-3-yl]pyrazin-2-yl]ethyl]benzamide (I-24) as a white solid (119 mg, 67% yield).

[0290] 1 H NMR (400 MHz, DMSO-d6) δ 9.59 (s, 1H), 9.14 (d, J=6.9Hz, 1H), 8.76 (d, J=2.4Hz, 1H), 8.73 (d, J=2.4Hz, 1H), 8.61 (ddd, J=4.9, 1.9, 0.9Hz, 1H),8.13 (td, J=7.8, 1.9Hz, 1H), 7.95 (dt, J=8.2, 1.0Hz, 1H), 7.78 (t, J=1.6Hz,1H), 7.59-7.52 (m, 2H), 7.48-7.44 (m, 1H), 6.02 (dq, J=6.8Hz, 1H), 1.65 (d, J=6.9Hz, 3H).

[0291] Example 8: Preparation of methyl 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]-pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazole-4-carboxylate (I-83)

[0292] At 10°C, 4A MS (1 g, 232.39 µmol, 1 equivalent) and Cs₂CO₃ (2.12 g, 6.51 mmol, 3.5 equivalent) were added to a solution of N-[1-[3-(1H-1,2,4-triazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)-benzamide (0.8 g, 1.86 mmol, 1 equivalent) in DMF (20 mL) and stirred for 30 min. Methyl 2-chlorothiazol-4-carboxylate (396.24 mg, 2.23 mmol, 1.2 equivalent) was added to the mixture. The mixture was stirred at 80°C for 16 h, at which point completion was determined by LC-MS. The reaction mixture was filtered, the filtrate was poured into H₂O (50 mL), and extracted with EtOAc (2 × 20 mL). The combined organic layers were washed with brine, filtered, and concentrated. The residue was purified by preparative HPLC (HCl / MeCN) to provide methyl 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazole-4-carboxylate as a white solid (I-83, 0.4 g, 699.97 µmol, 38% yield).

[0293] 1 H NMR (400 MHz, DMSO-d6) δ = 9.68 (s, 1H), 9.50 (d, J=6.8 Hz, 1H), 8.77 (dd, J=2.3, 19.1 Hz, 2H), 8.57-8.42 (m, 3H), 8.27 (s, 1H), 6.01 (td, J=6.8, 6.8 Hz, 1H), 3.89 (s, 3H), 1.67 (d, J=6.9 Hz, 3H).

[0294] Example 9: Preparation of 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazolyl-4-carboxylic acid (I-82)

[0295] Add H₂O (1 mL), MeOH (4 mL), and LiOH to a solution of methyl 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazolyl-4-carboxylate (I-83, 0.27 g, 472.48 µmol, 1 equivalent) in THF (4 mL). .H2O (39.65 mg, 944.96 µmol, 2 equivalents). The mixture was stirred at 10°C for 2 h, at which point completion was determined by LCMS. The reaction mixture was poured into H2O (20 mL) and adjusted to pH 3 with HCl (2 N). The resulting solution was extracted with EtOAc (2 × 10 mL), the organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated to provide 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazolyl-4-carboxylic acid (I-82, 0.17 g, 304.97 µmol, 65% yield) as a white solid.

[0296] 1 H NMR (400 MHz, DMSO-d6) δ = 13.74-13.14 (m, 1H), 9.64 (s, 1H), 9.50 (d, J=6.7 Hz, 1H), 8.77 (dd, J=2.4, 18.8 Hz, 2H), 8.46 (d, J=10.0 Hz, 3H), 8.27 (s, 1H), 6.02 (t, J=6.8 Hz, 1H), 1.67 (d, J=7.0 Hz, 3H).

[0297] Example 10: Synthesis of 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]-N,N-dimethyl-thiazolyl-4-carboxamide (I-81)

[0298] 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]thiazolyl-4-carboxylic acid (I-82, 0.1 g, 179.40 µmol, 1 equivalent), NHMe2 .A mixture of HCl (17.55 mg, 215.27 µmol, 1.2 equivalents), 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazole[4,5-b]pyridinium 3-oxide hexafluorophosphate (88.67 mg, 233.21 µmol, 1.3 equivalents), and N,N-diisopropylethylamine (92.74 mg, 717.58 µmol, 124.99 µL, 4 equivalents) in DMF (3 mL) was stirred at 10°C for 2 h, at which point the reaction mixture was determined to be complete by LCMS. The reaction mixture was poured into H2O (20 mL) and extracted with EtOAc (2 × 10 mL). The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated. The residue was purified by preparative TLC (SiO2, EtOAc) to provide 2-[3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1,2,4-triazol-1-yl]-N,N-dimethyl-thiazol-4-carboxamide (I-81, 0.06 g, 102.65 µmol, 57% yield) as a white solid.

[0299] 1 H NMR (400 MHz, CDCl3) δ = 9.15 (s, 1H), 8.80 (d, J=2.4 Hz, 1H), 8.72 (d, J=2.4 Hz, 1H), 8.29 (s, 2H), 8.03 (s, 1H), 7.96-7.77 (m, 2H), 6.77-6.43 (m, 1H), 3.35 (s, 3H), 3.18 (s, 3H), 1.72 (d, J=6.6 Hz, 3H).

[0300] Table Int - Intermediate

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311] Biological examples

[0312] Unless otherwise specified, the test solution shall be prepared as follows:

[0313] Dissolve the active compound at the desired concentration in a 1:1 (volume ratio) mixture of distilled water and acetone. Prepare the test solution on the day of use.

[0314] The activity of the compounds of Formula I of the present invention can be demonstrated and evaluated by the following biological tests.

[0315] B.1 Green Peach Aphid (Peach Aphid)

[0316] To evaluate the control of the green peach aphid (Prunus persica) via systemic absorption, the test unit consisted of a 96-well microtiter plate containing liquid artificial food under an artificial film.

[0317] The compound was prepared using a solution containing 75% v / v water and 25% v / v DMSO. Different concentrations of the prepared compound were pipetted onto aphid feed using a custom-made pipette, repeated twice.

[0318] After application, place 5-8 adult aphids on an artificial membrane inside the well of a microtiter plate. Allow the aphids to suckle the treated aphid feed and incubate for 3 days at approximately 23°C ± 1°C and approximately 50% ± 5% relative humidity. Then visually assess aphid mortality and fertility.

[0319] In this test, compounds I-1, I-2, I-4, I-5, I-6, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-20, I-21, I-22, I-24, I-25, I-26, I-27, I-28, I-30, I-32, I-33, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I-45, I-47, I-48, I-49, I-50, I-56, I-5 8. I-59, I-72, I-73, I-76, I-77, I-79, I-80, I-81, I-82, I-83, I-84, I-85, I-88, I-89, I-90, I-92, I-95, I-98, I-100, I-101, I-102, I- 103, I-108, I-110, I-111, I-113, I-115, I-116, I-117, I-123, I-124, I-126, I-128, I-130, I-132, I-133, I-136, I-137, and I-139 at 2500 each Demonstrates at least 75% mortality at ppm.

[0320] In this test, compounds I-1, I-6, I-12, I-14, I-20, I-21, I-38, I-41, I-44, I-47, I-48, I-49, I-54, I-55, I-57, I-59, I-60, I-61, I-63, I-64, I-65, I-69, I-70, I-72, I-73, I-104, I-105, I-106, I-122, I-134, and I-135 are at 800 Demonstrates at least 75% mortality at ppm.

[0321] B.2 Tobacco budworm

[0322] To evaluate the control of the tobacco budworm (Tobacco budworm), the test unit consisted of a 96-well microtiter plate containing insect feed and 15-25 tobacco budworm eggs.

[0323] The compound was prepared using a solution containing 75% v / v water and 25% v / v DMSO. Different concentrations of the prepared compound were sprayed onto the insect feed in 10 µl amounts using a custom-made micro-atomizer, repeated twice.

[0324] After application, incubate the microtiter plate at approximately 28°C ± 1°C and approximately 80% ± 5% relative humidity for 5 days. Then visually assess the mortality rate of eggs and larvae.

[0325] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23 , I-24, I-25, I-26, I-27, I-28, I-32, I-33, I-34, I-37, I-38, I-39, I-40 , I-41, I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-52, I-53, I-56, I-58, I-59, I-71, I-73, I-74, I-75, I-76, I-81, I-84, I-88, I-90, I-91, I-92, I-93, I-95, I-96, I-97, I-98, I-101, I-102, I-103, I-108, I-110, I-111, I-112, I-113, I-114, I-115, I-116, I-117, I-118, I-119, I-120, I-123, I-126, I-128, I-129, I-130, I-131, I-132, I-136, and I-139 are at 2500 At ppm, it showed a mortality rate of at least 75%.

[0326] In this test, compounds I-1, I-6, I-12, I-14, I-20, I-21, I-38, I-41, I-44, I-47, I-48, I-49, I-54, I-59, I-60, I-61, I-65, I-69, I-70, I-72, I-73, I-104, and I-122 showed a mortality rate of at least 75% at 800 ppm, compared to the untreated control.

[0327] B.3 Boll weevil

[0328] To evaluate the control of the boll weevil, the test unit consisted of a 96-well microtiter plate containing insect feed and 5-10 boll weevil eggs.

[0329] The compound was prepared using a solution containing 75% v / v water and 25% v / v DMSO. Different concentrations of the prepared compound were sprayed onto the insect feed in 5 µl amounts using a custom-made micro-needle, repeated twice.

[0330] After application, the microtiter plate was incubated at approximately 25°C ± 1°C and 75% ± 5% relative humidity for 5 days. After that, the mortality rate of eggs and larvae.

[0331] In this test, compared to the unprocessed compound I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-2 8, I-30, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I- 45, I-46, I-47, I-48, I-49, I-51, I-52, I-53, I-56, I-58, I-59, I-71, I-72, I-73, I-74, I -75, I-76, I-77, I-78, I-79, I-81, I-83, I-84, I-85, I-86, I-87, I-88, I-89, I-90, I-91, I-92, I-93, I-95, I-96, I-98, I-99, I-100, I-101, I-102, I-103, I-108, I-109, I-110, I- 111, I-112, I-113, I-114, I-115, I-116, I-117, I-118, I-119, I-120, I-121, I-123, I-124, I-126, I-127, I-128, I-129, I-130, I-131, I-132, I-133, I-136, I-137, and I-139 all show a minimum mortality rate of 75% under 2500 ppm.

[0332] In this test, compared to unprocessed samples, compounds I-1, I-6, I-12, I-14, I-20, I-21, I-38, I-41, I-44, I-46, I-47, I-48, I-49, I-54, I-55, I-57, I-59, I-60, I-61, I-63, I-64, I-65, I-66, I-68, I-69, I-70, I-72, I-73, I-86, I-104, I-105, I-106, I-107, I-122, I-134, I-135, and I-138 show a minimum mortality rate of 75% under 800 ppm.

[0333] B.4. Southern armyworm (Spodoptera eridania), second instar larvae

[0334] The active compound was formulated into a 10,000-ppm solution in 100% cyclohexanone using a Tecan liquid processor and supplied in tubes. This 10,000-ppm solution was serially diluted in 100% cyclohexanone to prepare transition solutions. These were used as stock solutions and the final dilution was prepared using Tecan in 50% acetone: 50% water (v / v) and placed in 10 or 20 ml glass vials. The nonionic surfactant (Kinetic®) was included in the solution at 0.01% (v / v). The vials were then inserted into an automated electrostatic sprayer equipped with a misting nozzle for application to plants / insects. Two lima bean plants (variety: Sieva) were planted in pots, and treatment was selected at the first true leaf stage. The test solution was sprayed onto the leaves using an automated electrostatic plant sprayer equipped with a misting nozzle. The plants were dried in a sprayer fume hood and then removed from the sprayer. Each pot was placed in a perforated plastic bag with a zip-lock closure. Ten to eleven armyworm larvae were placed in a bag and the bag was zipped shut. The test plants were kept in a growth chamber at approximately 25°C and approximately 20%–40% relative humidity for 4 days, avoiding direct exposure to fluorescence (14:10 bright:dark cycle) to prevent heat retention inside the bag. Four days after treatment, mortality and reduced feeding were assessed compared to untreated control plants.

[0335] In this test, compounds I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-24, I-25, I-26, I-27, I-28, I-32, I-33, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I-46, I-47, I-48, I-51, I-52, and I-53 at 300 Demonstrates at least 75% mortality at ppm.

[0336] In this test, compounds I-1, I-2, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-14, I-15, I-16, I-17, I- 18. I-19, I-20, I-21, I-22, I-24, I-25, I-26, I-27, I-28, I-32, I-33, I-38, I-39, I-40, I-42, I-44, I-47, I-48, I-53, I-54, I-56, I-58, I-59, I-60, I-63, I-64, I-65, I-69, I-70, I-72, I-73, I-74, I-75, I-76, I-7 7. I-81, I-84, I-85, I-91, I-92, I-93, I-95, I-96, I-97, I-98, I-101, I-102, I-103, I-114, and I-119 are respectively at 100 Demonstrates at least 75% mortality at ppm.

[0337] B.5 Yellow fever mosquito (Aedes aegypti)

[0338] To evaluate the control of yellow fever mosquitoes (Aedes aegypti), the test unit consisted of a 96-well microtiter plate containing 200 µl of tap water and 5–15 newly hatched Aedes aegypti larvae per well.

[0339] The active compound was formulated using a solution containing 75% (v / v) water and 25% (v / v) DMSO. Different concentrations of the formulated compound or mixture were sprayed onto the insect feed in 2.5 µl amounts using a custom-made micro-needle, repeated twice.

[0340] After application, the microtiter plate was incubated at 28°C ± 1°C and 80% ± 5% RH for 2 days. Then, the larval mortality rate was visually assessed.

[0341] In this test, compared to the unprocessed compound I-1, I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-20, I-21, I-22, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-3 0, I-31, I-32, I-33, I-34, I-35, I-36, I-37, I-38, I-39, I-40, I-41, I-42, I-43, I-44, I-45, I- 46, I-47, I-48, I-49, I-50, I-51, I-52, I-53, I-56, I-58, I-59, I-71, I-72, I-73, I-74, I-75, I- 76, I-77, I-78, I-79, I-80, I-81, I-82, I-83, I-84, I-85, I-86, I-87, I-88, I-89, I-90, I-91, I -92, I-93, I-94, I-95, I-96, I-97, I-98, I-99, I-100, I-101, I-102, I-103, I-108, I-109, I-11 0, I-111, I-112, I-113, I-114, I-115, I-116, I-117, I-118, I-119, I-120, I-121, I-123, I-124, I-125, I-126, I-127, I-128, I-129, I-130, I-131, I-132, I-133, I-136, I-137, and I-139 all show a minimum mortality rate of 75% under 2500 ppm.

[0342] In this test, compared to the unprocessed compound I-1, I-6, I-12, I-14, I-20, I-21, I-38, I-41, I-44, I-46, I-47, I-48, I-49, I-54, I-55, I-57, I-59, I-60, I-61, I-62, I-63, I-64, I-65, I-69, I-70, I-72, I-73, I-86, I-104, I-107, I-122, I-134, and I-135 showed a mortality rate of at least 75% under 800 ppm.

[0343] B.6 Orchid strips (Dichromothrips corbetti)

[0344] Orchid thrips adults used for bioassays were obtained from populations continuously maintained under laboratory conditions. For testing purposes, the test compound was diluted in a 1:1 mixture of acetone and water (volume ratio) and added to Kinetic at a rate of 0.01% v / v.

[0345] The thrips potency of each compound was evaluated using a flower immersion technique. Each orchid petal was immersed in the treatment solution and then dried in a Petri dish. The treated petals were then placed in separate resealable plastic containers with approximately 20 adult thrips. All test sites were maintained in darkness and at approximately 28°C for the duration of the assay. Percentage mortality was recorded 72 hours post-treatment.

[0346] In this test, compounds I-5, I-12, I-13, I-14, I-17, I-20, I-33, I-42, I-54, I-81, I-101, I-103, I-104, and I-107 showed a mortality rate of at least 75% at 300 ppm, compared to the untreated control.

[0347] Comparison of activity with existing technologies

[0348] The beneficial activity of compounds according to the invention containing a 1-substituted-1,2,4-triazole-3-yl ring relative to structurally similar compounds known from the art that differ in their pyrazine-linked moiety (e.g., N-bound 1,2,4-triazoles, C-bound or N-bound 1,2,3-triazoles, or pyrazoles) is demonstrated by the following comparative experiments:

[0349] The table shows the % mortality rate compared to the untreated control group.

[0350] C-1: Comparison of the 6-membered heteroaryl group according to the present invention with the substituents in the prior art.

[0351]

[0352] C-2: Comparison of the 6-membered heteroaryl group according to the present invention with the unsubstituted phenyl group of the prior art:

[0353]

[0354] C-3: Comparison of the 1,2,4-triazol-3-yl group according to the present invention with the prior art 1,2,3-triazol-4-yl group (N-CH3 pyrazole) having the same substituents:

[0355]

Claims

1. A compound of formula I and N-oxides, stereoisomers and the agriculturally or veterinary acceptable salts thereof, R 1 It is H, OH, NR 12 R 13 C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C1-C5-alkoxy, C1-C4-alkyl-C3-C6-cycloalkyl, C1-C4-alkyl-C3-C6-halocycloalkyl, C3-C6-alkenyl, C3-C6-ynyl, these groups are unsubstituted or R 11 To partially or completely replace; or C(=N-R 11 )R 12 , C(O)R 11a ; R 11 is halogen, CN, N02, NR 12 R 13 , C(0)NH2, C(S)NH2, C(0)OH, OR 14 , 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, the cycle being unsubstituted or substituted by 1 or 2 halogens; 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, these rings being unsubstituted or substituted by halogen, Ci-C3-haloalkyl, and / or CN; 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 cycloalkyl being unsubstituted or substituted by 1 or 2 halogens; 3- to 6-membered heterocyclyl, the rings being unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; R 12 , R 13 are independently of one another 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)NH-C1-C4-alkyl, C(O)NH-C1-C4-haloalkyl, C(O)N(C1-C4-alkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-haloalkyl, C(O)NH-C1-C4-alkoxy, C(O)NH-C1-C4-haloalkoxy, C(O)NH-C1-C4-alkoxy-C1-C4-alkyl, C(O)NH-C1-C4-alkoxy-C1-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3- to 6-membered heterocyclyl or 5- or 6-membered heteroaryl, C(O)NH-C1-C4-alkyl-phenyl, C(O)NH-C1-C4-alkyl-3- to 6-membered heterocyclyl or 5- or 6-membered heteroaryl, which rings are unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; S(O) m -C1-C4-alkyl, S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, which rings are unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; or R 12 and R 13 together with the nitrogen atom to which they are bound form a 3-, 4-, 5-, 6- or 7- membered saturated, partially or fully unsaturated heterocyclic ring, which can additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, O, S(O) m p and optionally one or two groups C(O) as ring members, and which is unsubstituted or substituted by one or more R 3a ; or R 12 and R 13 together with the nitrogen atom to which they are bound form a sulfoximine group =S(O)R 12a R 12b ; wherein R 12a , R 12b independently are C1-C3-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 heterocyclic ring; m is 0, 1, or 2; Each R 3a Independently selected from halogens, CN, NO2, OR 151 C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy-C1-C4-alkyl, 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, C(O)NR 12 R 13 C(O)OR 141 C(O)R 151 C(=N-OR) 141 C3-C6-cycloalkyl, C(=N-OR) 141 )NR 121 R 131 ; or phenyl, which is unsubstituted or substituted with halogen; R 2 is H, CN, C1-C3-alkyl, C1-C3-haloalkyl, or C2-C3-alkynyl; Each R 3 Independently selected from halogens, CN, NO2; C1-C4-alkyl, C3-C6-cycloalkyl, C1-C6-haloalkyl, C1-C6-halocycloalkyl, C1-C6-alkenyl, C1-C6-ynyl, C3-C6-cycloalkyl-C1-C6-alkyl, C1-C6-alkyl-C3-C6-cycloalkyl, these groups are unsubstituted or R 3a Replace; OR 14 NR 121 R 131 C(O)NR 121 R 122 C(O)OR 15 C(O)R 15 S(O) m -R 15 S(O)2F, C(=N-OR) 14 )NR 121 R 131 , or C(=N-OR) 14 C3-C6 cycloalkyl, wherein the ring is unsubstituted or R 3a replace; R 121 , R 131 are independently of one another H, or a group R 122 or R 132 ; R 122 , R 132 are independently of one another 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)NH-C1-C4-alkyl, C(O)NH-C1-C4-haloalkyl, C(O)N(C1-C4-alkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-alkyl, C(O)N(C1-C4-haloalkyl)-C1-C4-haloalkyl, C(O)NH-C1-C4-alkoxy, C(O)NH-C1-C4-haloalkoxy, C(O)NH-C1-C4-alkoxy-C1-C4-alkyl, C(O)NH-C1-C4-alkoxy-C1-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3- to 6-membered heterocyclyl or 5- or 6-membered heteroaryl, C(O)NH-C1-C4-alkyl-phenyl, C(O)NH-C1-C4-alkyl-3- to 6-membered heterocyclyl or 5- or 6-membered heteroaryl, which rings are unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; S(O) m -C1-C4-alkyl, S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, which rings are unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; or R 122 and R 132 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 heterocyclic ring, which can additionally contain 1 or 2 heteroatoms or heteroatom-containing groups selected from N, O, S(O) m and C(O) as ring members, and which is unsubstituted or substituted by one or more substituents R 3a ; or R 122 and R 132 together with the nitrogen atom to which they are bound form a sulfoximine group =S(O)R 12a R 12b ; 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, SO m -C1-C4-alkyl, SO m -C1-C4-haloalkyl, SO m -C3-C6-cycloalkyl, or phenyl, which is unsubstituted or substituted by R 3a moieties or completely; R 141 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 phenyl, which is unsubstituted or substituted by halogen, C1-C3-haloalkyl, and / or CN; R 15 is H, C1-C4-alkyl, or C1-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, these carbon chains being unsubstituted or partially or fully substituted; or 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, these rings being unsubstituted or substituted by R 11 ; or 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, these rings being unsubstituted or substituted by R 3a ; or 3- to 6-membered heterocyclyl, 5- or 6-membered heteroaryl, or phenyl, these rings being unsubstituted or substituted by R R 151 It is H, C1-C4-alkyl, or C1-C4-haloalkyl, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl, where the carbon chains are unsubstituted or R-substituted. 11 Partial or complete substitution; or 3- to 6-membered heterocyclic groups, 5- or 6-membered heteroaryl groups, or phenyl groups, which are unsubstituted or substituted with halogens, C1-C3-haloalkyl groups, and / or CN; n is 0, 1, 2, or 3; R 4 Is it unreplaced or replaced by (R) 41 ) o Substituted 5- or 6-membered heteroaryl or phenyl groups, provided that X is CH or N, and Q is N, and R... 5 and R 6 If it is H, then R 4 Not C6H5; Each R 41 Independently selected from halogen, CN, OR 14 Unreplaced or R 3a Substituted C1-C4 alkyl groups; C1-C4-haloalkyl groups; and NR 15 C(O)R 151 S(O) m -C3-C4-cycloalkyl, S(O) m -C3-C4-halocycloalkyl, S(O) m -C3-C4-cyanocycloalkyl, NR 15 C(O)OR 15 OC(O)OR 15 OC(O)R 15 OC(O)NR 12 R 13 C(O)OR 15 C(O)R 15 C(O)NHR 122 C(O)NR 122 R 132 C(O)NR 15 NR 12 R 13 C(=NOR) 14 )R 15 C(=NOR) 14 )NR 12 R 13 NR 15 NR 12 R 13 Unreplaced or R 3 Substituted 3- or 4-membered heterocycles; replaced by R 3 Partially or completely substituted C3-C4-cycloalkyl groups, o is 1, 2, 3, 4, or 5; R 5 , R 6 are independently H, or as defined for R 3 ; X, Q are independently N, CH, or CR 3b ; R 3b is as defined for R 3 .

2. The compound of formula I according to claim 1, wherein R 1 is H or CH2-cC3H5.

3. The compound of formula I according to claim 1 or 2, wherein R 2 is CH3.

4. The compound of Formula I according to any one of claims 1 to 3, wherein, R 3 halogen, CN, C1-C4-haloalkyl, C1-C4-haloalkoxy, C3-C4-cycloalkyl which is unsubstituted or substituted by one or more CN or halogen, C3-C4-halocycloalkyl, S(0) m -C1-C4-alkyl, S(0) m -C1-C4-haloalkyl, S(0) m -C3-C4-cycloalkyl, S(0) m -C3-C4-halocycloalkyl, S(0) m -(substituted phenyl), C(=N-OR 14 )NR 121 R 131 , C(=N-OR 14 )C3-C6-cycloalkyl, wherein the ring is unsubstituted or substituted by R 3a .

5. The compound of Formula I according to any one of claims 1 to 4, wherein, n is 2 and R 3 is at the 3 and 5 positions.

6. The compound of Formula I according to any one of claims 1 to 6, wherein, at least one R 3 selected from C(=N-OR 14 )NR 121 R 131 and C(=N-OR 14 )C3-C6-cycloalkyl, wherein the ring is unsubstituted or substituted by R 3a substituted.

7. The compound of Formula I according to any one of claims 1 to 6, wherein, X is CH.

8. The compound of Formula I according to any one of claims 1 to 7, wherein, R 4 is 5- or 6-membered heteroaryl which is unsubstituted or substituted by (R 41 ) m is 5- or 6-membered heteroaryl which is unsubstituted or substituted by (R 4 is 2-pyridyl, 3-pyridyl, 2-pyrimidyl, 4-pyrimidyl, 2-pyrazinyl, or 3-pyridazinyl, which is optionally substituted by R 41 .

9. The compound of Formula I according to any one of claims 1 to 7, wherein, R 4 is phenyl which is partially or completely substituted by (R 41 ) o substituted by (R 10. The compound of formula I according to any one of claims 1 to 9, which corresponds to formula I.A.

11. The compound of formula I according to any one of claims 1 to 9, which corresponds to formula I.B.

12. The compound of formula I according to any one of the preceding claims, which consists essentially of 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 veterinary acceptable salt thereof, and at least one agriculturally or veterinary acceptable inert liquid and / or solid carrier.

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

15. A method for combating or controlling invertebrate pests, which comprises contacting the pests or their food supply, habitat, or breeding sites with a pesticidally effective amount of at least one compound according to any one of claims 1 to 12.

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

17. A seed comprising a compound according to any one of claims 1 to 12, or an enantiomer, diastereomer or salt 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 contacting the animal with a pesticidally effective amount of at least one compound of formula I according to any one of claims 1 to 12, a stereoisomer and / or at least one veterinarily acceptable salt thereof.

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