WO2023104564A1 - Pyrazine compounds for the control of invertebrate pests - Google Patents

Abstract

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

Description

Pyrazine compounds for the control of invertebrate pests

Description

The invention relates to compounds of formula I

wherein

R¹ is H, OH, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C1-C5- alkoxy, Ci-C4-alkyl-C3-C6-cycloalkyl, Ci-C4-alkyl-C3-C6-halocycloalkyl, which groups are unsubstituted, or partially or fully substituted with R¹¹;

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

R¹², R¹³ are independently from each other H, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloal- koxy, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C₃-C₄-cycloalkyl, C(O)-C₃-C₄-halocycloalkyl, C(O)NH-Ci-C₄-alkyl, C(O)NH-C C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)-Ci-C₄-alkyl, C(O)N(CrC₄-haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-haloalkyl, C(O)NH-Ci-C₄-alkoxy, C(O)NH-C C₄- haloalkoxy, C(O)NH-Ci-C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4-haloal- kyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH-Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-C4-haloalkyl, S(O)m-C3-Ce-cycloalkyl, S(O)m-C3-Ce-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, C1-C3- haloalkyl, and/or CN; or R¹² and R¹³ together with the nitrogen atom they are bound to form a 3-6 membered saturated, partially or fully unsaturated heterocycle, which may contain 1 or 2 additional heteroatoms selected from N, O, and S, wherein S may be oxidized, and which heterocycle is unsubstituted or substituted with R³; or R¹² and R¹³ together with the nitrogen atom they are bound to form a group N=S(=O)R^14aR^14b, wherein R^14a and R^14b are defined as R¹⁴;

R¹⁴ is H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, Cs-C4-cy- cloalkyl-Ci-C2-alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4- haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-C3-C4-halocycloalkyl, or phenyl which is unsubstituted or partially or fully substituted with R³; m is 0, 1 , or 2;

R² is H, CN, Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-Cs-alkenyl, or C2-Cs-alkynyl;

R³ is halogen, CN, NO2, Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, OR¹⁴, S(O)_m-R¹⁴; wherein rings are unsubstituted or substituted with R^3a;

R^3a halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- haloalkoxy, Cs-C4-cycloalkyl, Cs-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4- haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl; n is 0, 1 , 2, or 3;

R⁴ is H, halogen, Ci-Ce-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, C2-C4- alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, each optionally substituted by R⁴¹; S(O)_m-Ci-C4- alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)m-Cs-Ce-cycloalkyl, S(O)m-Cs-Ce-halocycloalkyl, S(O)₂NR¹²R¹³, NR¹²R¹³, C(O)NR¹²R¹³, C(O)OR¹⁴, 3- to 6-membered heterocyclyl, 5- or 6- membered hetaryl, or phenyl, which rings are unsubstituted or substituted with R³;

R⁴¹ is H, OR¹⁵, NR¹²R¹³, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C₃-C₆-cycloalkyl, C(O)-Ci-C₄-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-Cs-C4-cycloalkyl, C(O)-Cs-C4-halocycloalkyl, C(O)NH-Ci- C₄-alkyl, C(O)NH-Ci-C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)-Ci-C₄-alkyl, C(O)N(CI-C₄- haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-haloalkyl, C(O)NH-CI-C₄- alkoxy, C(O)NH-Ci-C4-haloalkoxy, C(O)NH-Ci-C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci- C4-alkoxy-Ci-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH-Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6- membered heterocyclyl or 5- or 6-membered hetaryl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-C4-haloalkyl, S(O)_m-Cs-C4-cycloalkyl, S(O)_m-Cs-C4-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN;

R¹⁵ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Ci-Ce-halocycloalkyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with R³;

Q is O or S; and the N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof. The invention also provides agricultural compositions comprising at least one compound of formula I, a stereoisomer thereof and/or an agriculturally acceptable salt thereof and at least one liquid and/or solid carrier, especially at least one inert liquid and/or solid agriculturally acceptable carrier.

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

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

The invention also relates to plant propagation material, in particular seed, comprising at least one compound of formula I and/or an agriculturally acceptable salt thereof.

The invention further relates to a method for treating or protecting an animal from infestation or infection by parasites which comprises bringing the animal in contact with a parasiticidally effective amount of a compound of formula I or a veterinarily acceptable salt thereof. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal.

WO2021068179, WO2021069575, WO2021037614, and WO2021259997 describe structurally closely related active compounds. These compounds are mentioned to be useful for combating invertebrate pests.

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

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

Compounds I with R¹ being different from H can be obtained by alkylation of a compound II (corresponding to formula I with R¹ = H) with a suitable alkylating agent III (e.g. alkyl halide). In formula III R¹ has the meaning as in formula I, and Y is a nucleophilic leaving group, such as a halide, preferably Br or Cl. The alkylation can be effected under standard conditions known from literature. This transformation is usually carried out at temperatures of from -10°C to +110°C, preferably from 0°C to 25°C, in an inert solvent and in the presence of a base [cf. WO 2002100846, S. M. Somagond, Heterocycl. Commun. 2017, 317],

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

Compounds I with Q=O (formula I.O) can be prepared from the corresponding amidoxime precursors IV by cyclisation with a suitable reagent, such as V or VI.

Reaction of compounds IV with an orthoester (V) leads to compounds I.O in which R⁴ is an alkyl group, e.g. as described in W02009154557. This transformation is usually carried out neat in excess V and in the presence of 0.05 to 1 .0 equivalents of an acid, such as p-toluenesulfonic acid (TsOH), ZnCl2, or BF₃ diethyl etherate, and at temperatures between 0°C and 120°C, preferably between 25°C and 80°C. In terms of yield, it is generally advantageous to employ an excess of V based on IV.

Alternatively, reaction of compounds IV with alkyl 2-chloro-2-oxo-acetates, such as VI, delivers compounds I.O in which R⁴ is an alkyl ester moiety, e.g. as described in J. Med. Chem. 2008, 4392. This transformation is usually carried out in an inert solvent such as 1 ,4-dioxane, tetrahydrofuran (THF), 2-methyl tetrahydrofuran, chloroform, dichloroethane, dichloromethane, or in a mixture of the aforementioned solvents, and in the presence of 1 to 3 equivalents of a base, such as triethylamine, diisopropylethylamine, pyridine, 2 ,6-lutidine, 2,4,6-collidine, or alternatively using the base as the solvent, and at temperatures between 0°C and 170°C, preferably between 25°C and the boiling point of the solvent. In terms of yield, it is generally advantageous to employ an excess of VI based on IV.

Furthermore, compounds I in which R⁴ is C(O)NR¹²R¹³ can be obtained from compounds I in which R⁴ is C(O)OR¹⁴ by reaction with the corresponding amine HNR¹²R¹³. This transformation is usually carried out in a solvent such as ethanol, methanol, or water, or in a mixture of the aforementioned solvents, either using a stoichiometric amount of the amine HNR¹²R¹³ in the presence of 1 to 3 equivalents of a suitable base, such as triethylamine, diisopropylamine, or pyridine, or using 2 to 4 equivalents of the amine HNR¹²R¹³, and at temperatures between 10°C and 140°C, preferably between 25°C and the boiling point of the solvent, for example as described in J. Med. Chem. 2008, 4377.

Compounds IV can be prepared from compounds VII by reaction with hydroxylamine or a suitable salt thereof.

This transformation is usually carried out in a solvent such as (or solvent mixture composed of) methanol, ethanol, 2-propanol, and/or water, optionally in the presence of 1 to 2 equivalents of a base such as NaOH, KOH, Na2COs, K2CO3, or CS2CO3, and at temperatures ranging from 0°C to the boiling point of the solvent or solvent mixture (cf. Tiemann, Chem. Ber. 1884, 17, 126; Gobis et al., Acta Pol Pharm (Drug Research) 2006, 39).

Compounds VII can be obtained by reaction of compounds VIII with 1 to 2 equivalents of Zn(CN)2 in the presence of 0.01 to 0.2 equivalents of a transition-metal complex, such as palladium diacetate, palladium trifluoroacetate, tris(dibenzylideneacetone)dipalladium, tetrakis(tri- phenylphosphine)palladium, or NiCl2, and 0.01 to 0.2 equivalents of a ligand, such as 2-[di(tert- butyl)phosphino]-1 ,1 '-binaphthyl, 1 ,1-bis(diphenylphosphino)ferrocene, or BINAP, as catalysts, and 0.1 to 0.5 equivalents of zinc powder or zinc flakes as a cocatalyst, and optionally with 1 to 3 equivalents of a base, such as 4-(dimethylamino)pyridine or sodium tert-butoxide, in a solvent such as dimethylformamide (DMF), N,N-dimethylacetamide (DMA), or acetonitrile, at temperatures between 25°C and 150°C, preferably between 25°C and the boiling point of the solvent (cf. A. Littke et al., Org. Lett. 2007, 1711). Compounds VIII are known from W02020070049.

Compounds I with Q=S can be prepared by acylation of the corresponding amines IX:

Such compounds of formula I correspond to formula I.S.

This transformation is usually carried out at temperatures of from -20°C to 50°C, preferably from 0°C to 25°C, in an inert solvent, in the presence of a peptide coupling reagent and optionally in the presence of a base [cf. A. El-Faham, Chem. Rev. 2011 , 6557], or in two steps by preparation of an intermediate acyl chloride from X under conditions known from literature, e.g. by reaction with SOCh or oxalyl chloride in DMF (cf. Schaefer et al, Organic Syntheses 1929, 32), followed by reaction with IX in the presence of a base, optionally under Schotten- Baumann conditions (Baumann, Chem. Ber. 1886, 3218). Suitable peptide coupling reagents are, e.g., dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3'-dimethylaminopro- pyl)carbodiimide hydrochloride, or chloro-N,N,N',N'-tetramethylformamidinium hexafluorophosphate, which are commonly used together with catalytic, stoichiometric, excess amounts of additives, such as 1 -hydroxybenzotriazole, 1-hydroxy-7-aza-benzotriazole, 4-(dimethylamino)pyri- dine, and/or 1 -methylimidazole.

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

Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as LiOH, NaOH, KOH, or Ca(OH)2, alkali metal and alkaline earth metal carbonates, such as Na₂COs, K2CO3, or CS2CO3, alkali metal bicarbonates, such as NaHCOs, or organic bases, for example tertiary amines, such as triethylamine, diisopropylethylamine, N- methylpiperidine, or basic aromatic rings, such as pyridine, 2,4,6-collidine, 2,6-lutidine, or 4-(di- methylamino)pyridine, or bicyclic amines, such as 1 ,8-diazabicylo[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). Particular preference is given to triethylamine, diisopropylethylamine, and NaOH. The bases are generally employed in stoichiometric or excess amounts; however, they can also be used in catalytic amounts or, if appropriate, as the solvent.

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

Compounds IX can be prepared by reductive amination of a compound XI:

This transformation is usually carried out at temperatures of from 0°C to 130°C, preferably from 20°C to 70°C, generally in alcoholic and/or aqueous media and in the presence of a reagent and a reducing agent [cf. WO2021037614], Suitable solvents are alcohols, such as methanol, ethanol, n-propanol, 2-propanol, or n-butanol, or water, preferably methanol. It is also possible to use mixtures of the aforementioned solvents. Suitable reagents are ammonium acetate (NH4AC), ammonium formate, NH4OH, NH4CI, ammonia, or primary amines R¹NH2. Suitable reducing agents are NaBH₃CN, sodium triacetoxyborohydride, or NaBH₄. Preference is given to ammonium acetate and NaBHsCN, resp.

Compounds XI can be obtained by reaction of XII with an appropriately substituted nitrile XIII, in which W can be, for example, CH2CO2Et or CC Et, with subsequent conversion of W into the desired substituent R⁴ following standard methods known from literature.

W-CN

XIII

XI

This transformation is generally carried out in a high-boiling hydrocarbon solvent, such as decaline, or aromatic solvent, such as 1 ,2-dichlorobenzene, in a sealed flask and at high temperatures ranging from 120°C to 200°C, as described in WO2013031694.

Compounds XII can be prepared from compounds XIV by cyclisation with (chlorocarbonyl)sul- fenyl chloride (XV) as described in Bioorg. Med. Chem. Lett. 2013, 1424.

Compounds XIV can be prepared from compounds XVI by reaction with ammonia or an ammonium salt, whereas the latter are known from Bioorg. Med. Chem. Lett. 2014, 4490.

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

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

The organic moieties groups mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.

The term “partially or fully substituted” by a radical means that in general the group is substituted with same or different radicals.

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

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

The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-Cs-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.

The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like. The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2- OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.

The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alkoxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include C1-C4- haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-flu- oroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

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

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

The term "alkylsulfinyl" (alkylsulfoxyl: S(=O)-alkyl), as used herein refers to a straight-chain or branched saturated alkyl group (as mentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group.

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

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

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

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

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

The term "alkoxycarbonyl" refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule. The term "haloalkoxycarbonyl” refers to an alkoxycarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.

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

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

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

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

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

The term "halocycloalkyl" as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 1- and 2-fluo- rocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2, 2, 3, 3- tetrafl uo- rocyclpropyl, 1- and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 , 2, 2-tri chlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlo- rocyclopentyl and the like.

The term “halocycloalkenyl” as used herein and in the halocycloalkenyl moieties of halocyclo- alkenyloxy and halocycloalkenylthio denotes in each case a monocyclic singly unsaturated nonaromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 3,3-difluorocyclopropen- 1-yl and 3,3-dichlorocyclopropen-1-yl. The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded via an alkyl group, such as a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkenylmethyl), to the remainder of the molecule.

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

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

The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1, 2, 3 or 4 heteroatoms selected from N, O, and S. Examples of 5- or 6-mem- bered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5- pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadia- zolyl, 4- or 5-(1 ,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1 ,3,4-thiadiazol)yl, thiadia- zolyl, e.g. 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, tria- zolyl, e.g. 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or 4H-1,2,4-triazolyl and te- trazolyl, i.e. 1H- or 2H-tetrazolyl. The term "hetaryl" also includes bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 heteroatoms selected from N, O, and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6- membered heteroaromatic radical. Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1 ,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.

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

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

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

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

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

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

In a preferred embodiment, the compounds I are present in form of a mixture of compounds I. A and I.B, wherein compound I.A with S-configuration of the carbon atom neighboring the nitrogen is present in an amount of more than 50% by weight, in particular of at least 70% by weight, more particularly of at least 85% by weight, specifically of at least 90% by weight, based on the total weight of compounds I.A and I.B. In one particularly preferred embodiment of the invention, the method comprises the step of contacting the plant, parts of it, its propagation material, the pests, their food supply, habitat or breeding grounds with a pesticidally effective amount of a compound of formula I. A.

Preferably R¹ is H, Ci-Ce-alkyl, Cs-Ce-alkynyl, Cs-Ce-cycloalkyl, or Ci-C4-alkyl-C3-C6-cycloalkyl.

Preferably R² is CH3.

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

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

R³ is preferably halogen, CN, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl unsubstituted or substituted with one or more CN, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4- haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, S(O)_m-(substituted phenyl). Index m in R³ is preferably 2. Index n is preferably 2.

R³ groups stand preferably in positions 3 and 5.

In another embodiment R³ is preferably halogen, CN, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, C3-C4- cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloal- kyl, S(O)m-C3-C4-halocycloalkyl, or

S(O)_m-R¹⁴, wherein R¹⁴ is phenyl, which is partially substituted with R¹¹. In another embodiment R³ is preferably halogen, CN, Ci-C4-haloalkyl, Ci-C4-haloalkoxy, C3- C4-cycloalkyl, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cy- cloalkyl, S(O)_m-C3-C4-halocycloalkyl, or

S(O)m-R¹⁴, wherein R¹⁴ is phenyl, which is partially substituted with R^3a.

In another embodiment of formula I compounds R³ is halogen, CN, NO2, Ci-C4-alkyl, C3-C6- cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, OR¹⁴, S(O)_m-R¹⁴; wherein rings are unsubstituted or substituted with R¹¹.

R⁴ is preferably H, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci-Ce-alkyl, S(O)_m-Ci-C4-alkyl, or phenyl unsubstituted or substituted with one or more groups R³.

In one embodiment of formula I, Q is O. Such compounds correspond to formula I.O

in another embodiment of formula I, Q is S. Such compounds correspond to formula I.S

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

Table 1

Compounds of formula 1.10* in which R⁴ is H, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 2

Compounds of formula 1.10* in which R⁴ is CH3, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 3

Compounds of formula 1.10* in which R⁴ is Cl, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 4

Compounds of formula 1.10* in which R⁴ is C(O)N(CH3)(C2Hs), and the combination of R¹ and

(R³)_n for a compound corresponds in each case to one row of Table A

Table 5

Compounds of formula 1.10* in which R⁴ is C(O)NHCHs, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 6

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

Table 7

Compounds of formula I.1S* in which R⁴ is CH₃, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 8

Compounds of formula I.1S* in which R⁴ is Cl, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 9

Compounds of formula I.1S* in which R⁴ is C(O)N(CH3)(C2Hs), and the combination of R¹ and

(R³)_n for a compound corresponds in each case to one row of Table A

Table 10

Compounds of formula I.1S* in which R⁴ is C(O)NHCHs, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 11

Compounds of formula 1.20* in which R⁴ is H, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A Table 12

Compounds of formula 1.20* in which R⁴ is CH3, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 13

Compounds of formula 1.20* in which R⁴ is Cl, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 14

Compounds of formula 1.20* in which R⁴ is C(O)N(CH3)(C2Hs), and the combination of R¹ and

(R³)_n for a compound corresponds in each case to one row of Table A

Table 15

Compounds of formula 1.20* in which R⁴ is C(O)NHCHs, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 16

Compounds of formula I.2S* in which R⁴ is H, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 17

Compounds of formula I.2S* in which R⁴ is CH₃, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 18

Compounds of formula I.2S* in which R⁴ is Cl, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table 19

Compounds of formula I.2S* in which R⁴ is C(O)N(CH3)(C2Hs), and the combination of R¹ and

(R³)_n for a compound corresponds in each case to one row of Table A

Table 20

Compounds of formula I.2S* in which R⁴ is C(O)NHCHs, and the combination of R¹ and (R³)_n for a compound corresponds in each case to one row of Table A

Table A

The term “compound(s) of the invention” refers to compound(s) of formula I, or “compound(s) I”, and includes their salts, tautomers, stereoisomers, and N-oxides.

The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The term “seed” embraces seeds and plant propagules including true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots, and means preferably true seeds. "Pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions e.g. desired pesticidal effect and duration, weather, target species, locus, mode of application.

For use in treating crop plants, e.g. by foliar application, the rate of application of the active ingredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.

The compounds I are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds I can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied).

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

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

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

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

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

The compounds of the invention are especially suitable for efficiently combating animal pests e.g. arthropods, and nematodes including: insects from the sub-order of Auchenorrhyncha, e.g. Amrasca biguttula, Empoasca spp., Ne- photettix virescens, Sogatella furcifera, Mahanarva spp., Laodelphax striatellus, Nilaparvata lugens, Diaphorina citrr,

Lepidoptera, e.g. Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plu-tella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichop- lusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticar- sia gemmatalis, Agrotis ipsilon, Chrysodeixis includens',

True bugs, e.g. Lygus spp., Stink bugs such as Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus',

Thrips, e.g. Frankliniella spp., Thrips spp., Dichromothrips corbettii;

Aphids, e.g. Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schi- zaphis graminum, Megoura viciae.,

Whiteflies, e.g. Trialeurodes vaporariorum, Bemisia spp.;

Coleoptera, e.g. Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa decimline- ata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.;

Flies, e.g. Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp.;

Mosquitoes (Diptera), e.g. Aedes aegypti, A. albopictus, A. vexans, Anastrepha ludens, Anopheles maculipennis, A. crucians, A. albimanus, A. gambiae, A. freeborni, A. leucosphyrus, A. minimus, A. quadrimaculatus;

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

Anthropods of class Arachnida (Mites), e.g. Penthaleus major, Tetranychus spp.;

Nematodes, e.g. Heterodera glycines, Meloidogyne sp., Pratylenchus spp., Caenorhabditis el- egans.

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

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

The compounds of the invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasit- ically effective amount of a compound I.

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

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

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

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

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

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

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

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

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

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

The compounds I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds I. In addition, the compounds I may be formulated as ear tags for animals, particularly quadrupeds e.g. cattle and sheep.

Oral solutions are administered directly.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Gels are applied to or spread on the skin or introduced into body cavities.

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

Emulsions can be administered orally, dermally or as injections.

Suspensions can be administered orally or topically/dermally.

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

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

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

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

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

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

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

A. Preparation examples

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

Method A: HPLC/MS: Agilent 1200 HPLC MSD:6120 single quadrupole MSD, ES-API; Column: XBridge C18 2.1x50mm 5pm; Mobile phase: A: H2O+10mM NH4HCO3; B: ACN; Temperature: 40°C; Gradient: 5% B to 95% B in 3.4min; 95% B for 0.45min; 95% B to 5% B in 0.01 min; 5% B for 0.64min; Flow: 0.8mL/min; MS: ES-API positive; Mass range: 50-2200.

Method B: LC: Shimadzu LC-30AD, ESI; Column: Kinetex EVO C18 5pm 2.1x30mm; Mobile phase: A: water + 0.04% TFA; B: ACN + 0.02% TFA; Temperature: 40°C; Gradient: 5% B to 100% B in 2.5min; 100% B to 5% B in 0.02min; 5% B for 0.5min; Flow: 0.8mL/min; MS: ESI positive; Mass range: 100-2000.

Method C: HPLC/MS: Agilent 1200 HPLC MSD:1956A single quadrupole MSD, ES-API; Column: Luna C18 2.0x50mm 5pm; Mobile phase: A: 0.04% TFA in water; B: 0.02% TFA in ACN; Temperature: 40°C; Gradient: 5% B for 0.4min; 5% B to 95% B in 2.6 min; 95% B for 1 min; 95% B to 5% B in 0.01 min; 5% B for 0.5min; Flow: 1.0mL/min; MS: ES-API positive; Mass range: 50-1500.

Example 1 : preparation of N-[1-[3-(5-methyl-1 ,2,4-oxadiazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(tri- fluoromethyl)benzamide (1-1)

Step 1 : preparation of 1-(3-chloropyrazin-2-yl)ethanamine

To a mixture of 1-(3-chloropyrazin-2-yl)ethanone (10g, 63.8mmol) and NH4OAC (60.4g, 957.8mmol) in EtOH (500mL) were added NaBH₃CN (12.04g, 191.4mmol) and NH₃/MeOH (150mL, 7N) at 30°C. The mixture was stirred at 50°C until completion was determined by LCMS (16h). The reaction mixture was quenched with H2O (100mL) and concentrated to remove MeOH and EtOH. 6N aq. NaOH was added to adjust the pH of the residue to 11 and the resulting mixture was extracted with EtOAc (3x100mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated. The crude product was purified by preparative HPLC (NH4HCO₃) to deliver 1-(3-chloropyrazin-2-yl)ethanamine (10g, 50% yield) as a white solid.

¹H-NMR (400MHz, DMSO-cfe): 6= 8.70 (d, J=2.4Hz, 1 H), 8.47 (d, J=2.5Hz, 1 H), 4.50 (q, J=6.7Hz, 1 H), 1.37 (d, J=6.8Hz, 3H).

Step 2: preparation of N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide

To a mixture of 3,5-bis(trifluoromethyl)benzoic acid (19.65g, 76.14mmol) and chloro-N,N,N’,N’- tetramethylformamidinium hexafluorophosphate (21.36g, 76.14mmol) in MeCN (200mL) were added /V-methylimidazole (16.7g, 203.2mmol) and 1-(3-chloropyrazin-2-yl)ethanamine (8.0g, 50.8mmol) at 30°C. The reaction mixture was stirred until completion was determined by TLC (PE:EtOAc=3:1 , Rf =0.45; 16h). The reaction mixture was quenched with H₂O (50mL) and extracted with EtOAc (3x100mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated. The crude product was purified by chromatographic column on silica gel (eluent: 12% EtOAc in PE) to deliver N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)ben- zamide (13g, 43% yield) as a yellow solid.

¹H-NMR (400MHz, DMSO-cfe): 6= 9.53 (d, J=6.8 Hz, 1 H), 8.65 (d, J=2.5Hz, 1 H), 8.55 (s, 2H), 8.46 (d, J=2.5Hz, 1 H), 8.33 (s, 1 H), 5.53 (dq, J=6.8Hz, J=6.9Hz, 1 H), 1.56 (d, J= 6.9Hz, 3H).

Step 3: preparation of N-[1-(3-cyanopyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide To a solution of N-[1-(3-chloropyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (1.0g, 2.51 mmol) in DMF (10mL) were added Zn(CN)2 (330mg, 2.76mmol) and Pd(PPhs)4 (350mg, 0.30mmol) at 20°C, and the resulting mixture was purged with N2 for 3 min. The vial was sealed and subjected to microwave irradiation (Biotage Smith Synthesis, 130°C, 10min). Completion was determined by TLC (PE:EtOAc=3:1 , Rf =0.4). The reaction mixture was filtered through a celite pad, the filter cake was washed with EtOAc (50mL), and the filtrate was concentrated. The crude product was purified by chromatographic column on silica gel (17% EtOAc in PE) to deliver N-[1-(3-cyanopyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (2.6g, 45% yield) as a yellow solid.

¹H-NMR (400MHz, CDCI3): 6 8.77 (d, J=2.3Hz, 1 H), 8.70 (d, J=2.4Hz, 1 H), 8.28 (s, 2H), 8.04 (s, 1 H), 7.37-7.28 (m, 1 H), 5.84-5.73 (m, 1 H), 1.74 (d, J=6.8Hz, 3H).

Step 4: preparation of N-[1-[3-[N'-hydroxycarbamimidoyl]pyrazin-2-yl]ethyl]-3,5-bis(trifluorome- thyl)benzamide

To a solution of N-[1-(3-cyanopyrazin-2-yl)ethyl]-3,5-bis(trifluoromethyl)benzamide (1.1g, 2.8mmol) in EtOH (20mL) were added HONH2*HCI (238mg, 3.36mmol) and triethylamine (575mg, 5.6mmol) at 30°C. The resulting mixture was stirred at 80°C for 2.5h, until completion was determined by TLC (PE:EtOAc=3:1 , Rf=0.3). The reaction mixture was quenched with H2O (10mL) and extracted with EtOAc (3x20mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated. The crude product was purified by chromatographic column on silica gel (25% EtOAc in PE) to deliver N-[1-[3-[N'-hydroxycarbamimidoyl]pyrazin-2-yl]ethyl]- 3,5-bis(trifluoromethyl)benzamide (600mg, 51% yield) as a white solid.

¹H-NMR (400MHz, DMSO-cfe) 6= 10.21 (s, 1 H), 9.42 (d, J=7.2Hz, 1 H), 8.62 (d, J=2.4Hz, 1 H), 8.57 (d, J=2.3Hz, 1 H), 8.54 (s, 2H), 8.30 (s, 1 H), 6.12 (dq, J=6.8Hz, J=7.2Hz, 1 H), 5.96 (s, 2H), 1.54 (d, J=6.8Hz, 3H). LCMS: calculated mass: 422.1 ; observed mass: 422.0.

Step 5: preparation of N-[1-[3-(5-methyl-1 ,2,4-oxadiazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluo- romethyl)benzamide (1-1)

To a mixture of N-[1-[3-[N'-hydroxycarbamimidoyl]pyrazin-2-yl]ethyl]-3,5-bis(trifluorome- thyl)benzamide (400mg, 0.95mmol) and 1 ,1 ,1 -tri methoxyethane (8 mL) was added TsOH (245mg, 1.4mmol) at 30°C. The resulting mixture was stirred at 80°C for 16h, until completion was determined by TLC (PE/EtOAc=1 :1, Rf=0.4). The reaction mixture was quenched with H₂O (30mL) and extracted with EtOAc (3x50mL). The combined organic layers were dried over Na₂SO4, filtered, and the filtrate was concentrated. The crude product was purified by column chromatography on silica gel (27% EtOAc in PE) to deliver N-[1-[3-(5-methyl-1 ,2,4-oxadiazol-3- yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (1-1 , 195mg, 46% yield) as a yellow oil.

¹H-NMR (400MHz, CDCI₃) 6= 8.78 (d, J=2.3Hz, 1 H), 8.73 (d, J=2.3Hz, 1 H), 8.27 (s, 2H), 8.02 (s, 1 H), 7.70 (br d, J=7.3Hz, 1 H), 6.37-6.26 (m, 1 H), 2.78 (s, 3H), 1.68 (d, J=6.6Hz, 3H).

LCMS: calculated mass: 446.1 ; observed mass: 446.1.

Example 2: preparation of 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-N- ethyl-N-methyl-1 ,2,4-oxadiazole-5-carboxamide (I-2)

Step 1 : preparation of methyl 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]- 1 ,2,4-oxadiazole-5-carboxylate

To a solution of N-[1-[3-[(Z)-N'-hydroxycarbamimidoyl]pyrazin-2-yl]ethyl]-3,5-bis(trifluorome- thyl)benzamide (500mg, 1.19mmol) in dioxane (3mL) and CHC (3mL) were added triethylamine (360mg, 3.56mmol) and subsequently methyl 2-chloro-2-oxo-acetate (436mg, 3.56mmol) dropwise at 0°C. The resulting mixture was stirred at 20°C for 4h, until disappearance of the starting material was determined by TLC (PE/EtOAc=1 :1 , Rf=0.5). Subsequently, the mixture was stirred at 80°C for further 16h until completion was determined by TLC (PE/EtOAc=1 :1 , Rf=0.5). The reaction mixture was quenched with H₂O (30mL) and extracted with EtOAc (50mL x 3). The combined organic layers were dried over Na₂SO4, filtered, and the filtrate was concentrated. The crude product was purified by column chromatography on silica gel (25% EtOAc in PE) to deliver methyl 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1 ,2,4- oxadiazole-5-carboxylate (375mg, 64% yield) as a yellow solid.

¹H-NMR (400MHz, CDCI3) 6= 8.82 (d, J=2.4 Hz, 1 H), 8.78 (d, J=2.4 Hz, 1 H), 8.25 (s, 2H), 8.03 (s, 1 H), 7.59 (br d, J=7.9 Hz, 1 H), 6.29-6.22 (m, 1 H), 4.14 (s, 3H), 1.71 (d, J=6.7 Hz, 3H).

Step 2: preparation of 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-N- ethyl-N-methyl-1 ,2,4-oxadiazole-5-carboxamide (I-2)

To a solution of methyl 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-1 ,2,4- oxadiazole-5-carboxylate (275mg, 0.56mmol) in EtOH (1.5mL) was added N-methylethanamine (1.5mL) at 0°C. The resulting mixture was stirred at 0°C for 2h, until completion was determined by TLC (PE/EtOAc=1 :1 , Rf=0.5). The volatiles were removed under reduced pressure and the residue subjected to column chromatography on silica gel (23% EtOAc in PE) to furnish 3-[3-[1- [[3,5-bis(trifluoromethyl)benzoyl]amino]ethyl]pyrazin-2-yl]-N-ethyl-N-methyl-1 ,2,4-oxadiazole-5- carboxamide (I-2, 200mg, 35% yield) as a yellow solid.

¹H-NMR (400MHz, CDCI3) 6= 8.82-8.76 (m, 2H), 8.26 (s, 2H), 8.02 (s, 1 H), 7.67 (br m, 1 H), 6.37-6.28 (m, 1 H), 3.78-3.58 (m, 2H), 3.35-3.18 (m, 3H), 1.69 (m, 3H), 1.42-1.27 (m, 3H). LCMS: calculated mass: 517.1 ; observed mass: 517.1.

Example 3: preparation of N-(cyclopropylmethyl)-N-[1-[3-(5-methyl-1 ,2,4-oxadiazol-3-yl)pyra- zin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-3)

Step 1 : preparation of 1-(3-chloropyrazin-2-yl)-N-(cyclopropylmethyl)ethanamine

To a solution of 1-(3-chloropyrazin-2-yl)ethanone (5g, 31.93mmol) and cyclopropylmethana- mine (2.5g, 35.13mmol) in THF (50mL) was added Ti(OEt)4 (10.93g, 47.90mmol) at 20°C under N2 and the resulting mixture was stirred at 80°C for 16h, after which time quantitative formation of the imine intermediate was determined by TLC (PE:EtOAc=3:1 , Rf=0.8). After cooling the reaction mixture to room temperature, EtOH (10mL) and NaBHsCN (4.02g, 63.86mmol) were added. The resulting mixture was stirred at 28°C for 16h, at which time completion was determined by LCMS. After addition of H2O (30mL), the pH of the mixture was adjusted to 11 by addition of aq. NaOH (6N), and the mixture was extracted with EtOAc (3x80mL). The combined organic layers were dried over Na2SCU, filtered, and concentrated to furnish 1-(3-chloropyrazin- 2-yl)-N-(cyclopropylmethyl)ethanamine (5.7g, crude) as a yellow oil. The crude product was employed in the next step without further purification.

¹H-NMR (400MHz, DMSO-d₆): 5= 8.68 (d, J=2.4Hz, 1 H), 8.40 (d, J=2.4 Hz, 1 H), 4.24 (q, J=6.7Hz, 1 H), 2.35 (dd, J=6.2Hz, J=11.7Hz, 1 H), 2.05 (dd, J=7.1 Hz, J=11.7Hz, 1 H), 1.26 (d, J=6.8Hz, 3H), 0.82-0.71 (m, 1 H), 0.36-0.28 (m, 2H), 0.01-0.10 (m, 2H).

Step 2: preparation of N-[1-(3-chloropyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5-bis(trifluoro- methyl)benzamide

To a mixture of 3,5-bis(trifluoromethyl)benzoic acid (6.3g, 24.56mmol) and chloro-N,N,N’,N’,- tetramethylformamidinium hexafluorophosphate (6.9g, 24.56mmol) in MeCN (100mL) was added N-methylimidazole (6.1g, 24.56mmol) and 1-(3-chloropyrazin-2-yl)-N-(cyclopropylme- thyl)ethanamine (5.2g, 24.56mmol) at 30°C. The resulting mixture was stirred at 30°C for 16h, after which time completion was determined by TLC (PE: EtOAc=3:1 , Rf=0.5). The reaction mixture was poured into H2O (20mL), and the resulting mixture was extracted with EtOAc (3x50mL). The combined organic layers were washed with brine (20mL), dried over Na2SO4, filtered, and concentrated. The crude product was purified by chromatographic column on silica gel (5% EtOAc in PE) to deliver N-[1-(3-chloropyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5- bis(trifluoromethyl)benzamide (4.8g, 43% yield) as a yellow solid.

¹H-NMR (400MHz, DMSO-d₆): 5= 8.71 (d, J=2.3Hz, 1 H), 8.51 (d, J=1.9Hz, 1 H), 8.25 (s, 1 H), 8.10 (s, 2H), 6.13-4.86 (m, 1 H), 3.15-2.86 (m, 2H), 1.66 (br s, 3H), 0.38-0.00 (m, 3H), 0.13-0.67 (m, 2H).

Step 3: preparation of N-[1-(3-cyanopyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5-bis(trifluoro- methyl)benzamide To a solution of N-[1-(3-chloropyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5-bis(trifluorome- thyl)benzamide (1.0g, 2.21 mmol) in DMF (10mL) were added Zn(CN)2 (286mg, 2.43mmol) and Pd(PPhs)4 (307mg, 0.27mmol) at 20°C. The resulting mixture was purged with N2 for 3 min. The vial was sealed and subjected to microwave irradiation on a Biotage Smith Synthesis at 130°C for 20min, after which time completion was determined by TLC (PE: EtOAc=3:1 , Rf=0.3). The mixture was filtered over diatomite and the filter cake was washed with EtOAc (50 mL). The filtrate was concentrated. The crude product was purified by column chromatography on silica gel (16% EtOAc in PE) to deliver N-[1-(3-cyanopyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5-bis(tri- fluoromethyl)benzamide (3.9g, 85% yield) as a yellow solid.

¹H-NMR (400MHz, CDCI3): 6= 8.78 (d, J=2.4Hz, 1 H), 8.64 (d, J=2.3 Hz, 1 H), 7.99-7.93 (m, 3H), 5.82-5.45 (m, 1 H), 3.42 (dd, J=5.8Hz, J=15.3Hz, 1 H), 3.31-3.22 (m, 1 H), 1.91 (br d, J=6.5Hz, 3H), 0.98-0.88 (m, 1 H), 0.60-0.44 (m, 2H), 0.06 (br d, J=15.5Hz, 1 H), -0.09-0.20 (m, 1 H).

Step 4: preparation of N-(cyclopropylmethyl)-N-[1-[3-[(Z)-N'-hydroxycarbamimidoyl]pyrazin-2- yl]ethyl]-3,5-bis(trifluoromethyl)benzamide

To a mixture of N-[1-(3-cyanopyrazin-2-yl)ethyl]-N-(cyclopropylmethyl)-3,5-bis(trifluorome- thyl)benzamide (3.43g, 7.75mmol) in EtOH (35mL) were added HONH₂xHCI (652mg, 9.38mmol) and triethylamine (1.6g, 15.81 mmol) at 30°C. The mixture was stirred at 80°C for 2.5h, after which time completion was determined by TLC (PE:EtOAc=1 :1 , Rf=0.6). The reaction mixture was quenched with H2O (20mL) and the resulting solution was extracted with EtOAc (3x50mL). The combined organic layers were dried over Na2SO4, filtered, and concentrated. The crude product was purified by chromatographic column on silica gel (25% EtOAc in PE) to furnish N-(cyclopropylmethyl)-N-[1-[3-[(Z)-N'-hydroxycarbamimidoyl]pyrazin-2-yl]ethyl]- 3,5-bis(trifluoromethyl)benzamide (3.7g, 95% yield) as a white solid.

¹H-NMR (400MHz, DMSO-d₆): 5= 9.68 (s, 1 H), 8.64 (d, J=2.3 Hz, 1 H), 8.57 (d, J=2.3 Hz, 1 H), 8.05 (s, 1 H), 7.86 (br s, 2H), 6.08-5.98 (m, 1 H), 5.63 (br s, 2H), 3.41-3.29 (m, 1 H), 3.28-3.19 (m, 1 H), 1.69 (d, J=6.8 Hz, 3H), 0.98-0.86 (m, 1 H), 0.45-0.32 (m, 2H), 0.08-0.13 (m, 2H).

Step 5: preparation of N-(cyclopropylmethyl)-N-[1-[3-(5-methyl-1 ,2,4-oxadiazol-3-yl)pyrazin-2- yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (I-3)

To a solution of N-(cyclopropylmethyl)-N-[1-[3-[(Z)-N'-hydroxycarbamimidoyl]pyrazin-2- yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (600mg, 1.26mmol) in 1 ,1 ,1 -trimethoxyethane (6 mL) was added TsOH (22mg, 0.12mmol) at 25°C. The resulting mixture was stirred at 80°C for 6h after which time completion was determined by LCMS. The reaction mixture was quenched with water (10mL) and extracted with EtOAc (3x20mL). The combined organic layer was washed with brine (10mL), dried over Na₂SO4, filtered, and concentrated. The crude product was purified by preparative HPLC (NH4HCO3, MeCN-H₂O) to deliver N-(cyclopropylmethyl)-N-[1-[3-(5- methyl-1 ,2,4-oxadiazol-3-yl)pyrazin-2-yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (350mg, 56% yield) as a thick yellow oil.

¹H-NMR (400MHz, DMSO-d₆): 5= 8.87 (d, J=2.3Hz, 1 H), 8.77 (d, J=2.4Hz, 1 H), 8.09 (s, 1 H), 7.83 (s, 2H), 5.91 (br d, 1 H), 3.23 (br s, 2H), 2.62 (s, 3H), 1.72 (d, J=7.0Hz, 3H), 0.89-0.68 (m, 1 H), 0.46-0.18 (m, 2H), 0.07-0.23 (m, 2H).

Example 4: preparation of 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]-(cyclopropylmethyl)ami- no]ethyl]pyrazin-2-yl]-N-methyl-1 ,2,4-oxadiazole-5-carboxamide (I-4)

Step 1 : preparation of methyl 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]-(cyclopropylmethyl)ami- no]ethyl]pyrazin-2-yl]-1 ,2,4-oxadiazole-5-carboxylate

To a solution of N-(cyclopropylmethyl)-N-[1-[3-[(Z)-N'-hydroxycarbamimidoyl]pyrazin-2- yl]ethyl]-3,5-bis(trifluoromethyl)benzamide (530mg, 1.13mmol) in 1 ,4-dioxane (3mL) and CHCI3 (3mL) was added triethylamine (337.58mg, 3.35mmol). Subsequently, methyl 2-chloro-2-oxo- acetate (407.3mg, 3.35mmol) was added dropwise at 0°C under N2. The resulting mixture was stirred at 25°C for 12h, and then stirred at 80°C for 32h, after which time completion was determined by LCMS. The reaction mixture was quenched with water (10mL) and extracted with EtOAc (2x20mL). The combined organic layer was washed with brine (30mL), dried over Na₂SC>4, filtered, and concentrated. The crude product was purified by chromatographic column on silica gel (EtOAc in PE = 0% to 100%) to deliver methyl 3-[3-[1-[[3,5-bis(trifluoromethyl)ben- zoyl]-(cyclopropylmethyl)amino]ethyl]pyrazin-2-yl]-1 ,2,4-oxadiazole-5-carboxylate (190mg, 31% yield) as a thick yellow oil.

¹H-NMR (400MHz, CDCI3): 6= 8.78-8.79 (m, 1 H), 8.76 (s, 1 H), 7.79-7.89 (m, 3H), 6.14-6.36 (m, 1 H), 4.07 (s, 3H), 3.24-3.56 (m, 1 H), 2.91-3.23 (m, 1 H), 1.81-1.82 (m, 3H), 0.65-0.83 (m, 1 H), 0.32-0.48 (m, 4H).

Step 2: preparation of 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]-(cyclopropylmethyl)ami- no]ethyl]pyrazin-2-yl]-N-methyl-1 ,2,4-oxadiazole-5-carboxamide (I-4)

To a solution of 3-[3-[1-[[3,5-bis(trifluoromethyl)benzoyl]-(cyclopropylmethyl)amino]ethyl]pyra- zin-2-yl]-1 ,2,4-oxadiazole-5-carboxylate (118mg, 0.218mmol) in THF (3mL) was added MeNH₂ (30% in EtOH, 67mg, 0.653mmol) at 25°C. The resulting mixture was stirred at 25°C for 6h, after which time completion was determined by TLC (PE: EtOAc = 1 :1). The reaction mixture was concentrated and the residue purified by preparative TLC (PE:EtOAc=1 :1) to deliver 3-[3-[1- [[3,5-bis(trifluoromethyl)benzoyl]-(cyclopropylmethyl)amino]ethyl]pyrazin-2-yl]-N-methyl-1 ,2,4- oxadiazole-5-carboxamide (110mg, 93% yield) as a white solid.

¹H-NMR (400MHz, DMSO-d₆): 5= 9.11 (br s, 1 H), 8.91 (d, J=2.32Hz, 1 H), 8.81 (d, J=2.32Hz, 1 H), 8.05 (s, 1 H), 7.83 (s, 2H), 6.03 (br dd, 1 H), 3.20-3.31 (m, 2H), 2.84 (d, J=4.77Hz, 3H), 1.74 (d, J=6.85Hz, 3H), 0.68-0.84 (m, 1 H), 0.19-0.43 (m, 2H), -0.33-0.03 (m, 2H).

Biological examples

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

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

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

B.1 Diamond back moth (Plutella xylostella)

The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vokvol) distilled water : acetone. Surfactant (Kinetic HV) was added at a rate of 0.01% (vol/vol). The test solution was prepared on the day of use.

Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3^rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0- 100%.

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

B.2 Green Peach Aphid (Myzus persicae)

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

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

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

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

B.3 Tobacco budworm (Heliothis virescens)

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

The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 pl, using a custom-built micro atomizer, at two replications. After application, microtiter plates were incubated at about 28 + 1°C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

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

B.4 Boll weevil (Anthonomus grandis)

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

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

After application, microtiter plates were incubated at about 25 + 1°C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

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

B.5. Southern armyworm (Spodoptera eridania), 2nd instar larvae

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

In this test, compounds 1-1, I-3, and I-9, resp., at 300 ppm showed at least 75% mortality in comparison with untreated controls. B.6 Orchid thrips (Dichromothrips corbetti)

Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1 :1 mixture of acetone:water (vokvol), plus Kinetic HV at a rate of 0.01% v/v. Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual re-sealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment.

In this test, compound I-3 at 300 ppm showed at least 75% mortality in comparison with untreated controls.

Claims

Claims . Compounds of formula I

wherein

R¹ is H, OH, Ci-Ce-alkyl, Ci-Ce-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C1-C5- alkoxy, Ci-C4-alkyl-C3-C6-cycloalkyl, Ci-C4-alkyl-C3-C6-halocycloalkyl, which groups are unsubstituted, or partially or fully substituted with R¹¹;

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

R¹², R¹³ are independently from each other H, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, C(O)-Ci-C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-Cs-C4-cycloalkyl, C(O)-Cs-C4-halocycloalkyl, C(O)NH-CrC₄-alkyl, C(O)NH-CrC₄-haloalkyl, C(O)N(Ci-C₄-alkyl)-CrC₄- alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄- haloalkyl, C(O)NH-Ci-C₄-alkoxy, C(O)NH-Ci-C₄-haloalkoxy, C(O)NH-Ci- C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4-haloalkyl; C(O)NH- phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH-Ci-C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-C4- haloalkyl, S(O)m-C3-Ce-cycloalkyl, S(O)m-C3-Ce-halocycloalkyl; 3- to 6- membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; or R¹² and R¹³ together with the nitrogen atom they are bound to form a 3-6 membered saturated, partially or fully unsaturated heterocycle, which may contain 1 or 2 additional heteroatoms selected from N, O, and S, wherein S may be oxidized, and which heterocycle is unsubstituted or substituted with R³; or R¹² and R¹³ together with the nitrogen atom they are bound to form a group N=S(=O)R^14aR^14b, wherein R^14a and R^14b are defined as R¹⁴;

R¹⁴ is H, Ci-C4-alkyl, Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Cs-Ce-halocycloalkyl, C3-C4-cycloalkyl-Ci-C2-alkyl, C3-C4-halocycloalkyl-Ci-C2-alkyl, C(O)-Ci- C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-C3-C4-cycloalkyl, C(O)-Cs-C4-halo- cycloalkyl, or phenyl which is unsubstituted or partially or fully substituted with R³; m is 0, 1 , or 2;

R² is H, CN, Ci-Cs-alkyl, Ci-Cs-haloalkyl, C2-Cs-alkenyl, or C2-Cs-alkynyl;

R³ is halogen, CN, NO2, Ci-C4-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocyclo- alkyl, OR¹⁴, S(O)_m-R¹⁴; wherein rings are unsubstituted or substituted with R^3a;

R^3a halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1- C4-haloalkoxy, Cs-C4-cycloalkyl, Cs-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4-cycloalkyl, S(O)_m-C3-C4-halocycloalkyl; n is 0, 1 , 2, or 3;

R⁴ is H, halogen, Ci-Ce-alkyl, Cs-Ce-cycloalkyl, Ci-Ce-haloalkyl, Ci-Ce-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, each optionally substituted with R⁴¹; S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)m-Cs-Ce-cycloalkyl, S(O)m-Cs-Ce-halo- cycloalkyl, S(O)₂NR¹²R¹³, NR¹²R¹³, C(O)NR¹²R¹³, C(O)OR¹⁴, 3- to 6-membered het- erocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with R³;

R⁴¹ is H, OR¹⁵, NR¹²R¹³, Ci-C₄-alkyl, Ci-C₄-haloalkyl, C₃-C₆-cycloalkyl, C(O)-Cr

C4-alkyl, C(O)-Ci-C4-haloalkyl, C(O)-Cs-C4-cycloalkyl, C(O)-Cs-C4-halocycloal- kyl, C(O)NH-Ci-C₄-alkyl, C(O)NH-Ci-C₄-haloalkyl, C(O)N(Ci-C₄-alkyl)-Ci-C₄- alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄-alkyl, C(O)N(Ci-C₄-haloalkyl)-Ci-C₄- haloalkyl, C(O)NH-Ci-C₄-alkoxy, C(O)NH-Ci-C₄-haloalkoxy, C(O)NH-CI-C₄- alkoxy-Ci-C4-alkyl, C(O)NH-Ci-C4-alkoxy-Ci-C4-haloalkyl; C(O)NH-phenyl, C(O)NH-3-6-membered heterocyclyl or 5- or 6-membered hetaryl, C(O)NH-Ci- C4-alkyl-phenyl, C(O)NH-Ci-C4-alkyl-3-6-membered heterocyclyl or 5- or e- membered hetaryl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN; S(O)_m-Ci-C4-haloalkyl, S(O)_m-Cs-C4-cycloalkyl, S(O)_m-Cs-C4-halocycloalkyl; 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with halogen, Ci-Cs-haloalkyl, and/or CN;

R¹⁵ is H, Ci-C4-alkyl, or Ci-C4-haloalkyl, Cs-Ce-cycloalkyl, Ci-Ce-halocycloal- kyl, which carbon chains are unsubstituted or partially or fully substituted with R¹¹; or 3- to 6-membered heterocyclyl, 5- or 6-membered hetaryl, or phenyl, which rings are unsubstituted or substituted with R³; Q is O or S; and the N-oxides, stereoisomers, and agriculturally or veterinarily acceptable salts thereof. Compounds of formula I according to claim 1 , wherein R¹ is H or CH2-CC3H5. Compounds of formula I according to claim 1 or 2, wherein R² is CH3. Compounds of formula I according to any of claim 1 to 3, wherein R³ is halogen, CN, C1-

C4-haloalkyl, Ci-C4-haloalkoxy, C3-C4-cycloalkyl unsubstituted or substituted with one or more CN, C3-C4-halocycloalkyl, S(O)_m-Ci-C4-alkyl, S(O)_m-Ci-C4-haloalkyl, S(O)_m-C3-C4- cycloalkyl, S(O)_m-C3-C4-halocycloalkyl, or

S(O)_m-R¹⁴, wherein R¹⁴ is phenyl, which is partially substituted with R^3a. Compounds of formula I according to any of claim 1 to 4, wherein n is 2 and R³ is in positions 3 and 5. Compounds of formula I according to any one of claims 1 to 5, wherein X is CH. Compounds of formula I according to any one of claims 1 to 6, wherein R⁴ is H, Ci-Cs-al- kyl, Ci-Cs-haloalkyl, Ci-C4-alkoxy-Ci-C4-alkyl, C(O)NH-Ci-Ce-alkyl, C(O)N(Ci-Ce-alkyl)2, S(O)_m-Ci-C4-alkyl, or phenyl unsubstituted or substituted with one or more groups R³ as defined in claim 4. Compounds of formula I according to any one of the preceding claims, which correspond to formula I.O

Compounds of formula I according to any one of claims 1 to 7, which correspond to for- mula I.S

I.S

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

11. An agricultural or veterinary composition comprising at least one compound according to any one of claims 1 to 10 and/or at least one agriculturally or veterinarily acceptable salt thereof, and at least one inert liquid and/or solid agriculturally or veterinarily acceptable carrier.

12. An agricultural composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 10 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.

13. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any one of claims 1 to 10.

14. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 10.

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

16. A method for treating or protecting an animal from infestation or infection by invertebrate pests which comprises bringing the animal in contact with a pesticidally effective amount of at least one compound of the formula I as defined in any of claims 1 to 10, a stereoisomer thereof and/or at least one veterinarily acceptable salt thereof.