Pyrimidinone derivatives as pesticidal compounds.

Abstract

The present invention relates to a compound of formula (I) [Formula 1] TIFF2025541282000056.tif19170, where the variables are defined herein. The present invention also relates to pesticidal mixtures comprising a compound of formula (I); the use of a compound of formula (I) as a pesticide pesticide; a method for combating or controlling invertebrate pests, a method for protecting growing plants from attack or infestation by invertebrate pests, seeds comprising a compound of formula (I); the use of a compound of formula (I) to protect growing plants from attack or infestation by invertebrate pests; and a method for treating or protecting animals from infestation or infection by invertebrate pests.

Description

[Technical Field]

[0001] The present invention relates to a compound of formula (I) [ka] where the variables are as defined below. or an agriculturally or veterinarily acceptable salt, stereoisomer, tautomer or N-oxide thereof. The present invention relates to the use of a compound of formula (I) as a pesticide pesticide; a pesticidal composition comprising a compound of formula (I) and another pesticidal component; a method for combating or controlling invertebrate pests, which comprises contacting said pests or their food source, habitat or breeding grounds with a pesticidally effective amount of at least one compound of formula (I), a pesticidal mixture; and a method for protecting growing plants from attack or infestation by invertebrate pests, which comprises contacting the plants, or the soil or water in which the plants are growing, with a pesticidally effective amount of at least one compound of formula (I). and seeds comprising a compound of formula (I) or a pesticidal composition in an amount of from 0.1 g to 10 kg per 100 kg of seed; the use of a compound of formula (I) or a pesticidal composition for protecting growing plants from attack or infestation by invertebrate pests; and a method for treating or protecting animals from infestation or infection by invertebrate pests, which method comprises contacting the animal with a pesticidally effective amount of a compound of formula (I). [Background technology]

[0002] Invertebrate pests, particularly insects, arachnids, and nematodes, destroy growing and harvested crops and attack wooden residential and commercial buildings, thereby causing significant economic loss to food supplies and property. Thus, there is a continuing need for new agents to control invertebrate pests.

[0003] WO 2017 / 167832 and WO 2018 / 206479 disclose bicyclic pyrimidone compounds and their pesticidal activity. 1 This invention differs from these disclosures in that is a halogen.

[0004] WO 2021 / 204577 and WO 2022128524 disclose bicyclic pyrimidone compounds and their pesticidal activity, which are represented by the residue R 1 is selected from halogens, R 7 is in particular "substituted with CN and does not contain any further substituents or is substituted with one or more of the same or different substituents R 9 -C(CN)R further substituted with 7 R 8 and C3-C6-cycloalkyl”. WO 77 discloses that R 1 and R claimed in this application. 7 It does not disclose any particular combination of

[0005] Due to the ability of target pests to develop resistance to pesticidal agents, there is a continuing need to identify additional compounds suitable for controlling invertebrate pests, such as insects, arachnids, and nematodes. Furthermore, there is a need for new compounds that have high pesticidal activity and exhibit a broad spectrum of activity against many different invertebrate pests, particularly difficult-to-control insects, arachnids, and nematodes. Furthermore, there is a need for compounds that are environmentally friendly and exhibit a favorable toxicological profile. Summary of the Invention [Problem to be solved by the invention]

[0006] It is therefore an object of the present invention to identify and provide compounds that exhibit high pesticidal activity, have a broad spectrum of activity against invertebrate pests, and exhibit favorable environmental and toxicological properties. [Means for solving the problem]

[0007] It has been found that these objects can be achieved by substituted bicyclic compounds of formula (I) as shown and defined below, including their stereoisomers, their salts, particularly their agriculturally or veterinarily acceptable salts, their tautomers and their N-oxides. DETAILED DESCRIPTION OF THE INVENTION

[0008] In a first aspect, the present invention provides a compound of formula (I) [ka] (In the formula, Rings A and B are fully unsaturated; Y is C=X, where X is O; E is N(R 3 ) and; Q is N, N(R 5 ) or CH; G is phenyl or pyridyl; W is S, S(O), S(O)2, S(O)(NR W ), S(O)(NH); R 1 is a halogen; R 3 , R 5 are independently unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl; Each R 7 are independently H, halogen, OH, CN; unsubstituted or halogenated C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl; containing one or more of the same or different heteroatoms O, N or S and being unsubstituted or containing one or more R H a 3- to 12-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with; unsubstituted or one or more RJ phenyl substituted with; OR K ; -C(CN)(CH3)2 or 1-cyanocyclopropyl, Each R H are independently halogen, CN; C1-C3-alkyl, C1-C3-haloalkyl; Each R J are independently halogen, CN; unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, or two adjacent substituents R which are C1-C6-alkoxy. J where the substituents form an alkyl bridge between two oxygens, which is unsubstituted or halogenated; Each R K is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, which groups are unsubstituted or substituted with one or more identical or different substituents selected from halogen, CN; Each R W are independently C1-C4 alkyl or cyclopropyl; The subscript n is 1, 2, 3, or 4 when G is phenyl, or 1, 2, or 3 when G is pyridyl. and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

[0009] In another aspect, the present invention provides a compound of formula (I): [ka] (In the formula, Rings A and B are fully unsaturated; Y is C=X, where X is O; E is N(R 3 ) and; Q is N, N(R 5 ) or CH; G is phenyl or pyridyl; W is S, S(O), S(O)2, S(O)(NR W ) and; R 1 is a halogen; R 3 , R 5 are independently unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl; Each R 7 are independently H, halogen, OH, CN; unsubstituted or halogenated C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl); containing one or more of the same or different heteroatoms O, N or S and being unsubstituted or containing one or more R H a 3- to 12-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with; unsubstituted or one or more R J phenyl substituted with; OR K ; -C(CN)(CH3)2 or 1-cyanocyclopropyl, Each R H are independently halogen, CN; C1-C3-alkyl, C1-C3-haloalkyl; Each R J are independently halogen, CN; unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy; Each R K is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, which groups are unsubstituted or substituted with one or more identical or different substituents selected from halogen, CN; Each R W are independently C1-C4 alkyl, cycloalkyl, or cyclopropyl; The subscript n is 1, 2, 3, or 4 when G is phenyl, or 1, 2, or 3 when G is pyridyl. and the N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

[0010] The compounds of formula (I) and their agriculturally acceptable salts are highly active against animal pests, ie arthropod and nematode pests, particularly insects and acaridae that are difficult to control by other means.

[0011] Furthermore, the present invention relates to and includes the following embodiments: - a composition comprising at least one compound of formula (I) as defined above and a liquid or solid carrier; agricultural and veterinary compositions comprising an amount of at least one compound of formula (I) as defined above or an enantiomer, diastereomer or salt thereof; - a method for combating invertebrate pests, infestations or infections by invertebrate pests, which method comprises contacting said pests or their food sources, habitats or breeding sites with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition thereof; - a method for controlling invertebrate pests, infestations or infections by invertebrate pests, which method comprises contacting said pests or their food sources, habitats or breeding sites with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I); - a method for preventing or protecting against invertebrate pests, comprising contacting the invertebrate pests or their food sources, habitats or breeding sites with a substituted imidazolium compound of general formula (I) as defined above, or a composition comprising at least one compound of formula (I) as defined above, or at least one compound of formula (I); - a method for protecting crops, plants, plant propagation material and / or growing plants from attack or infestation by invertebrate pests, which method comprises contacting or treating crops, plants, plant propagation material and / or growing plants or the soil, material, surface, space, area or water in which crops, plants, plant propagation material are stored or in which plants are growing, with a pesticidally effective amount of at least one compound of formula (I) as defined above or a composition comprising at least one compound of formula (I); - a non-therapeutic method for treating an animal infested or infected with a parasite or for preventing or protecting an animal from being infested or infected by a parasite, which method comprises orally, topically or parenterally administering or applying to the animal a parasiticidally effective amount of a compound of formula (I) or a composition comprising at least one compound of formula (I) as defined above; - a method for treating, controlling, preventing or protecting animals against infestation or infection by parasites by administering or applying orally, topically or parenterally to the animals a compound of general formula (I) as defined above or a composition comprising at least one compound of formula (I); seeds containing a compound of formula (I) as defined above in an amount of 0.1 g to 10 kg per 100 kg of seeds; - the use of compounds of formula (I) as defined above for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests; - the use of compounds of formula (I) or their enantiomers, diastereomers or veterinarily acceptable salts for combating parasites in and on animals; - a process for preparing a veterinary composition for treating, controlling, preventing or protecting animals from parasitic infestation or infection, which process comprises adding to a carrier composition suitable for veterinary use a parasiticidally effective amount of a compound of formula (I) or an enantiomer, diastereomer and / or a veterinarily acceptable salt thereof; - Use of a compound of formula (I) or an enantiomer, diastereomer and / or a veterinarily acceptable salt thereof for the preparation of a medicament for the treatment, control, prevention or protection of an animal from infestation or infection by a parasite.

[0012] All compounds of formula (I) and optionally their stereoisomers, tautomers, salts or N-oxides, and compositions thereof, are particularly useful for controlling invertebrate pests, particularly arthropods and nematodes, especially insects. The present invention therefore relates to the use of compounds of formula (I) as agricultural pesticides, preferably for combating or controlling invertebrate pests, especially invertebrate pests of the insect, arachnid or nematode group.

[0013] The term "compound according to the invention" or "compound of formula (I)" as used herein means and includes a compound as defined herein and / or its stereoisomers, salts, tautomers, or N-oxides. The term "compound of the invention" is understood to be equivalent to the term "compound according to the invention," and therefore also includes stereoisomers, salts, tautomers, or N-oxides of a compound of formula (I). As used herein, the term "compound of the invention" or "compound according to the invention" means a compound of formula (I) as defined above, also referred to as "compound of formula I," or "compound I," or "formula I compound," including salts, tautomers, stereoisomers, and N-oxides thereof.

[0014] The term "composition according to the invention" or "composition of the invention" encompasses compositions comprising at least one compound of formula (I) according to the invention as defined above, and therefore also includes stereoisomers, agriculturally or veterinarily acceptable salts, tautomers or N-oxides of compounds of formula (I).

[0015] The compounds of the invention may be amorphous or may exist in one or more different crystalline states (polymorphs) or variants which may have different macroscopic properties, such as stability, or which may exhibit different biological properties, such as activity. The invention includes both amorphous and crystalline compounds of formula (I), mixtures of different crystalline states or variants of each compound I, and amorphous or crystalline salts thereof.

[0016] Compounds of formula (I) may have one or more centers of chirality depending on the substitution pattern, in which case they exist as mixtures of enantiomers or diastereomers. The present invention provides both single pure enantiomers or pure diastereomers of compounds of formula (I) and mixtures thereof, as well as the use of pure enantiomers or pure diastereomers of compounds of formula (I) or mixtures thereof in accordance with the present invention. Suitable compounds of formula (I) also include all possible geometric stereoisomers (cis / trans isomers) and mixtures thereof. Cis / trans isomers may exist with respect to an alkene, a carbon-nitrogen double bond, or an amide group. The term "stereoisomer" encompasses both optical isomers, such as enantiomers or diastereomers (the latter occurring due to multiple centers of chirality in the molecule), and geometric isomers (cis / trans isomers). The present invention relates to all possible stereoisomers of compounds of formula (I), i.e., single enantiomers or diastereomers, as well as mixtures thereof.

[0017] Depending on the substitution pattern, the compounds of formula (I) may exist in their tautomeric forms. The present invention therefore also relates to the tautomers of formula (I) and to the stereoisomers, salts, tautomers and N-oxides of said tautomers.

[0018] Salts of compounds of formula (I) are preferably agriculturally and / or veterinarily acceptable salts, which may be formed in conventional manner, for example by reacting a compound of formula (I) with an acid of the anion if the compound contains a basic functionality, or by reacting an acidic compound of formula (I) with a suitable base.

[0019] Suitable agriculturally or veterinarily useful salts are, in particular, salts of the cations or acid addition salts of the acids, whose cations and anions, respectively, do not adversely affect the action of the compounds according to the invention. Suitable cations are, in particular, ions of alkali metals, preferably lithium, sodium and potassium, alkaline earth metals, preferably calcium, magnesium and barium, and transition metals, preferably manganese, copper, zinc and iron, and ammonium (NH + and substituted ammonium ions in which one to four hydrogen atoms have been replaced by C1-C4-alkyl, C1-C4-hydroxyalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl, or benzyl. Examples of substituted ammonium ions include methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium, and benzyltriethylammonium, as well as phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.

[0020] Useful anions of acid addition salts include primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate, and butyrate, which can be formed by reacting a compound of formula I with an acid of the corresponding anion, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, or nitric acid.

[0021] The term "N-oxide" includes any compound of the present invention having at least one tertiary nitrogen atom oxidized to an N-oxide moiety.

[0022] The organic moiety groups mentioned in the above definitions of variables, such as the term halogen, are generic to individual lists of members of the individual groups. x ~C y The prefix indicates in each case the number of possible carbon atoms in the group. "Halogen" will be taken to mean F, Cl, Br and I, preferably F.

[0023] The terms compound of formula (x) and compound (x), where x is a Roman or Arabic numeral, are used interchangeably herein to refer to a single compound or multiple compounds defined by the respective formula (x).

[0024] The term "substituted by," as used, for example, in "partially or fully substituted by," means that one or more, for example 1, 2, 3, 4, or 5 or all, of the hydrogen atoms of a given group are replaced by one or more of the same or different substituents defined below. Thus, for a substituted cyclic moiety, for example 1-cyanocyclopropyl, one or more of the hydrogen atoms of the cyclic moiety may be replaced by one or more of the same or different substituents.

[0025] The term "halogen" means fluoro, chloro, bromo, iodo, preferably fluoro, chloro, bromo. Other radical groups may be halogen-substituted, i.e., halogenated, and unless otherwise indicated, are understood to be fully or partially substituted with one or more halogen atoms.

[0026] As used herein, "C x ~C y -alkyl" (and also C x ~C y -Alkylamino, di-C x ~C y -Alkylamino, C x~C y -Alkylaminocarbonyl, di-(C x ~C y -alkylamino)carbonyl, C x ~C y -Alkylthio, C x ~C y -alkylsulfinyl and C x ~C y The term (-alkylsulfonyl) means a branched or unbranched saturated hydrocarbon group having n to m carbon atoms, for example 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl C1-C4-Alkyl refers to, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 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, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl, as well as isomers thereof. C1-C4-Alkyl means, for example, methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl.

[0027] As used herein, "C x ~C y The term "-haloalkyl" (and also C x ~C y -haloalkylsulfinyl and C x ~C y-haloalkylsulfonyl), straight-chain or branched alkyl groups having n to m carbon atoms, for example 1 to 10, in particular 1 to 6 carbon atoms (as defined above), in which some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as defined above, such as C1-C4-haloalkyl, for example chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, etc., in particular C1-C 10 The term -haloalkyl includes C1-C2-fluoroalkyl, which is equivalent to methyl or ethyl in which one, two, three, four or five hydrogen atoms are replaced by fluorine atoms, such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.

[0028] Similarly, "C x ~C y -alkoxy" and "C x ~C y -alkylthio" (or C x ~C y -alkylsulfenyl) refers to a straight-chain or branched alkyl group having n to m carbon atoms, for example 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as above), attached via an oxygen (or a sulfur bond, respectively) at any bond of the alkyl group. Examples include C1-C4-alkoxy, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy, and also C1-C4-alkylthio, such as methylthio, ethylthio, propylthio, isopropylthio and n-butylthio.

[0029] Therefore, "C x ~C y -haloalkoxy" and "C x ~C y The term "haloalkylthio" (or C x ~C y -haloalkylsulfenyl) is a straight-chain or branched alkyl group having n to m carbon atoms, for example 1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as defined above), bonded via an oxygen or sulfur bond at any bond of the alkyl group, in which some or all of the hydrogen atoms of these groups may be replaced by halogen atoms as defined above, for example C1-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- ...

[0033] This refers to chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy, as well as C1-C2-haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro2-fluoroethylthio, 2,2,2-trichloroethylthio and pentafluoroethylthio. Similarly, the terms C1-C2-fluoroalkoxy and C1-C2-fluoroalkylthio refer to C1-C2-fluoroalkyl attached to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.

[0030] As used herein, the term "C2-C y"-Alkenyl" means a branched or unbranched unsaturated hydrocarbon group having 2 to m, for example 2 to 10 or 2 to 6, carbon atoms and having a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl -1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl nyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl are intended.

[0031] As used herein, "C2-C y The term "alkynyl" means a branched or unbranched unsaturated hydrocarbon group having 2 to m, e.g., 2 to 10 or 2 to 6, carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, etc.

[0032] As used herein, "C x ~C y -Alkoxy-C x ~C y The term "-alkyl" refers to an alkyl having n to m carbon atoms, such as the specific examples above, in which one hydrogen atom of the alkyl group is C x ~C y - means substituted by an alkoxy group; the values ​​of x and y of the alkoxy group are independently selected from those of the alkyl group.

[0033] Therefore, as used herein, "C x ~C y -Alkoxy-C x ~C y The term "-alkoxy" refers to an alkoxy group having n to m carbon atoms, such as, for example, methoxy or ethoxy, in which one hydrogen atom of the alkoxy group is C x ~C y - means substituted by an alkoxy group; the values ​​of x and y of the alkoxy group are independently selected from those of the alkoxy group.

[0034] The suffix "-carbonyl" or "C(=O)" in a group indicates that the group is attached to the remainder of the molecule via a carbonyl C=O group in each case. This is the case, for example, with alkylcarbonyl, haloalkylcarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylcarbonylamino, and hydroxycarbonyl. For example, a hydroxycarbonyl group refers to a carbonate group -C(=O)OH, and an aminocarbonyl group refers to an amide group -C(=O)NH, both of which are attached to the remainder of the molecule via a carbonyl "C=O" group.

[0035] As used herein, the term "aryl" refers to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon group such as phenyl or naphthyl, especially phenyl (which also refers to C6H5 as a substituent).

[0036] As used herein, "C3-C y The term "cycloalkyl" refers to a single ring of a 3- to y-membered saturated alicyclic group, such as cyclopropyl (cC3H5), cyclobutyl (cC4H7), cyclopentyl (cC5H9), cyclohexyl (cC6H 11 ), cycloheptyl, cyclooctyl and cyclodecyl.

[0037] Therefore, as used herein, "C3-C y The term "cycloalkoxy" refers to a "C3-C alkoxy" group that is attached to the rest of the molecule through an oxygen atom, such as in cyclopropoxy, cyclobutoxy, cyclopentoxy, and cyclohexoxy. y "-refers to a cycloalkyl moiety.

[0038] "C3~C y -Cycloalkoxy-C x ~C y The term "-alkyl" refers to a group in which one hydrogen atom is bonded to a C3-C y -C substituted by an alkoxy group x ~C y- refers to an alkyl moiety, where the subscripts x and y are independently selected according to the indicated meaning.

[0039] The term "cycloalkylalkyl," similar to the term "alkyl which may be substituted by cycloalkyl," refers to an alkyl group substituted by a cycloalkyl ring, where alkyl and cycloalkyl are as defined herein.

[0040] As used herein, "C3-C y The term "-cycloalkenyl" refers to a monocyclic ring of a 3- to y-membered partially unsaturated alicyclic group.

[0041] The term "cycloalkylcycloalkyl," like the term "cycloalkyl that can be substituted by cycloalkyl," refers to cycloalkyl substitution on another cycloalkyl ring, where each cycloalkyl ring independently has 3 to 7 carbon atom ring members, and the cycloalkyls are linked via a single bond or share a common carbon atom. Examples of cycloalkylcycloalkyl include cyclopropylcyclopropyl (e.g., 1,1'-bicyclopropyl-2-yl), cyclohexylcyclohexyl (e.g., 1,1'-bicyclohexyl-2-yl) in which two rings are linked via a single common carbon atom, cyclohexylcyclopentyl (e.g., 4-cyclopentylcyclohexyl) in which two rings are linked via a single bond, and different stereoisomers thereof, such as (1R,2S)-1,1'-bicyclopropyl-2-yl and (1R,2R)-1,1'-bicyclopropyl-2-yl. The term "carbocycle" or "carbocyclyl", unless otherwise specified, generally includes a 3- to 12-membered, preferably 3- to 8-membered or 5- to 8-membered, more preferably 5- or 6-membered monocyclic ring containing 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms.

[0042] Carbocyclic groups can be saturated, partially unsaturated, or fully unsaturated. Preferably, the term "carbocycle" encompasses the cycloalkyl and cycloalkenyl groups defined above, such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane rings. When referring to a "fully unsaturated" carbocycle, the term also includes an "aromatic" carbocycle. In certain preferred embodiments, the fully unsaturated carbocycle is an aromatic carbocycle, preferably a 6-membered aromatic carbocycle, as defined below.

[0043] The term "hetaryl" or "heteroaromatic ring" or "heteroaromatic ring" includes monocyclic 5- or 6-membered heteroaromatic groups containing 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members. Examples of 5- or 6-membered heteroaromatic groups are pyridyl, i.e. 2-, 3- or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxazolyl, i.e. 1-, 3-, 4- or 5-imidazolyl, thiadiazolyl, for example 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, thiadiazolyl, for example 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, triazolyl, for example 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H- or 4H-1,2,4-triazolyl, and tetrazolyl, i.e. 1H- or 2H-tetrazolyl.

[0044] The terms "heterocycle", "heterocyclyl" or "heterocyclic ring", unless otherwise indicated, generally include 3- to 12-membered, preferably 3- to 8-membered, 3- to 7-membered or 5- to 8-membered, more preferably 5- or 6-membered, and especially 6-membered monocyclic heterocyclic groups. Heterocyclic groups can be saturated, partially unsaturated or fully unsaturated. When used in this context, the term "fully unsaturated" also includes "aromatic". In a preferred embodiment, the fully unsaturated heterocycle is therefore an aromatic heterocycle, preferably a 5- or 6-membered aromatic heterocycle containing one or more, for example 1, 2, 3 or 4, preferably 1, 2 or 3, heteroatoms selected from N, O and S as ring members. Examples of aromatic heterocycles are provided above in connection with the definition of "hetaryl". Unless otherwise indicated, "hetaryl" is therefore encompassed by the term "heterocycle". Heterocyclic non-aromatic groups typically contain 1, 2, 3, 4 or 5, preferably 1, 2 or 3, heteroatoms selected from N, O and S as ring members, the S atoms as ring members may be present as S, SO or SO, and the N atoms may be oxidized or unoxidized. Examples of 5- or 6-membered heterocyclic groups include saturated or unsaturated non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxide (S-oxothietanyl), thietanyl-S-dioxide (S-dioxothietanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl. , oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl, and the like.Examples of heterocyclic rings containing one or two carbonyl groups as ring members also include pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl, and the like.

[0045] The terms "alkylene," "alkenylene," and "alkynylene" refer to alkyl, alkenyl, and alkynyl, respectively, as defined above, attached to the remainder of the molecule via two atoms, preferably two carbon atoms, of the respective group, representing the link between the two portions of the molecule. In particular, the term "alkylene" can refer to alkyl chains such as CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and CH2CH2CH2CH2CH2CH2CH2. Similarly, "alkenylene" and "alkynylene" can refer to alkenyl and alkynyl chains, respectively.

[0046] As used herein, the term "5- to 6-membered carbocyclic ring" refers to cyclopentane and cyclohexane rings.

[0047] Examples of 5- or 6-membered saturated heterocyclic rings include: 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, dithiazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin-5-yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,- 1,3,4-Oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydro Pyrimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 1-oxothiomorpholin-2-yl, 1-oxothiomorpholin-3-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl.

[0048] Examples of 5- or 6-membered partially unsaturated heterocyclyl or heterocyclic rings include: 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxyl Isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin- 5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahydropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyrazinyl, 1,3,5-di- or tetrahydrotriazin-2-yl.

[0049] Examples of 5- or 6-membered fully unsaturated heterocycles (hetaryl) or heterocyclic aromatics are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.

[0050] "C2~C y "-Alkylene" is a divalent branched or preferably unbranched saturated aliphatic chain having 2 to m, for example 2 to 7, carbon atoms, such as CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2CH2 and CH2CH2CH2CH2CH2CH2CH2.

[0051] As used herein, the term "alkylamino" refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and more preferably 1 to 3 carbon atoms, attached via a nitrogen atom, e.g., an -NH- group.

[0052] As used herein, the term "dialkylamino" refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, bonded via a nitrogen atom, which is substituted by another straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms, such as, for example, a methylamino or ethylamino group.

[0053] As used herein, the term "alkylthio" (alkylsulfanyl: alkyl-S-) 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. Examples include methylthio, ethylthio, propylthio, isopropylthio, and n-butylthio.

[0054] The term "haloalkylthio" as used herein refers to the above alkylthio group in which hydrogen atoms are partially or fully replaced by fluorine, chlorine, bromine and / or iodine. Examples include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1-fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and the like.

[0055] As used herein, the term "alkylsulfinyl" (alkylsulfoxyl: C1-C6-alkyl-S(=O)-) refers to a linear or branched saturated alkyl group (as described above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms, bonded at any position of the alkyl group via the sulfur atom of the sulfinyl group.

[0056] As used herein, the term "(halo)alkylsulfonyl" (alkyl-S(=O)2-) refers to a straight-chain or branched saturated (and halogenated) alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-(halo)alkylsulfonyl), preferably 1 to 3 carbon atoms, attached via the sulfur atom of the sulfonyl group at any position of the (halo)alkyl group.

[0057] As used herein, the term "(halo)alkylsulfanyl" (alkyl-S-) refers to a straight-chain or branched saturated (and halogenated) alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-(halo)alkylsulfanyl), preferably 1 to 3 carbon atoms, bonded via the sulfur atom of a sulfanyl group at any position of the (halo)alkyl group.

[0058] As used herein, the term "(halo)alkylsulfinyl" (alkyl-S(=O)-) refers to a straight-chain or branched saturated (and halogenated) alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (=C1-C4-(halo)alkylsulfinyl), preferably 1 to 3 carbon atoms, attached at any position of the (halo)alkyl group via the sulfinyl group's sulfur atom.

[0059] Thus, the terms (halo)alkylsulfanylalkyl, (halo)alkylsulfinylalkyl and (halo)sulfonylalkyl as used for example in "C1-C4-alkylsulfanyl-C1-C4-alkyl", "C1-C4-alkylsulfinyl-C1-C4-alkyl" and "C1-C4-alkylsulfonyl-C1-C4-alkyl" refer to a (halo)alkylsulfanyl-, (halo)alkylsulfinyl- or (halo)alkylsulfonyl- group which is attached via the sulfur atom of the sulfanyl, sulfinyl or sulfonyl group, respectively, to the alkyl group, which in turn is attached to the rest of the molecule.

[0060] The term "alkylcarbonyl" (C1-C6-C(=O)-) refers to a straight or branched alkyl group as defined above attached to the rest of the molecule via the carbon atom of a carbonyl group (C=O).

[0061] The term "alkoxycarbonyl" refers to an alkoxy group, as defined above, attached to the remainder of the molecule through the carbon atom of a carbonyl group (C=O).

[0062] The term "alkylaminocarbonyl" (C1-C6-NH-C(=O)-) refers to a straight-chain or branched alkylamino group, as defined above, attached to the rest of the molecule through the carbon atom of a carbonyl group (C=O). Similarly, the term "dialkylaminocarbonyl" refers to a straight-chain or branched saturated alkyl group, as defined above, attached to a nitrogen atom that is replaced by another straight-chain or branched saturated alkyl group, as defined above, which is in turn attached to the rest of the molecule through a carbonyl group (C=O).

[0063] "S(O)(NR W )" is a [ka] where R Wis as defined for formula (I), and the symbols "&" and "§" denote bonds to the remainder of the molecule. Thus, the group R attached to ring "G" W -W is R W -S(O)(NR W ), which can have the meaning: [ka] In the formula, each R W are independently as defined for formula (I), and the symbol "§" denotes the connection to the remainder of the molecule, i.e., ring "G."

[0064] Compounds of formula (I) can be prepared by standard methods of organic chemistry. If a particular derivative cannot be prepared by the processes outlined below, it can be obtained by derivatization of other compounds of formula (I) that are accessible by these methods.

[0065] Generally useful preparation methods for the preparation of compounds of formula (I) are disclosed in WO 2017 / 167832, particularly pages 4-6 and the experimental section, WO 2021 / 204577, particularly pages 15-26 and the experimental section, WO 2021 / 099240, and WO 2022128524. In the processes and schemes depicted below, formula variables have the meanings defined for formula (I) unless otherwise stated. The variable "LG" refers to a leaving group such as Cl, Br, I, triflate, tosylate, etc. The variable R 71 and R 72 are each independently a group that, unless otherwise indicated, represents R in formula (I). 7 The variable A is N or CH.

[0066] Compounds of formula (II), which correspond to compounds of formula (I) where Q is CH, can be prepared by the reaction of compounds of formula (III) with compounds of formula (IV), as shown in Process 1. Process 1: [ka]

[0067] All variables in formulas (III), (IV), and (II) have the same meaning as defined for formula (I). Reactions of this type are described in EP 3257853 A1 and WO 2018206479. The reaction is typically carried out in an inert solvent at elevated temperatures of 50 to 160°C. Suitable solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, or petroleum ether; aromatic hydrocarbons such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons or halogenated aromatics C6-C6. 10 hydrocarbons, such as CH2Cl2, CHCl3, CCl4, CH2ClCH2Cl, CCl3CH3, CHCl2CH2Cl, CCl2CCl2 or chlorobenzene; ethers, such as CH3CH2OCH2CH3, (CH3)2CHOCH(CH3)2, CH3OC(CH3)3(MTBE), CH3OCH3(DME), CH3OCH2CH2OCH3, CH3OC(CH3)2CH2CH3, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofuran (THF) and diethylene glycol; nitriles, such as CH3CN, CH3CH2CN; alcohols, such as CH3OH, CH3CH2OH, CH3CH2CH2OH, CH3CH(OH)CH3, CH3(CH2)3OH and C(CH3)3OH, CH2(OH)CH2(OH), CH3CH(OH)CH2OH; amide and urea derivatives, such as dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP), dimethylacetamide (DMA), 1,3-dimethyl-2-imidazolidinone (DMI), 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (DMPU), hexamethylphosphamide (HMPA); and also dimethyl sulfoxide (DMSO), sulfolane, and water. Mixtures of the above solvents are also possible.

[0068] This reaction can be carried out in the presence of a catalyst such as an acid or a base, preferably a base. Suitable bases are generally inorganic bases such as LiOH, NaOH, KOH, and Ca(OH)2; alkali metal and alkaline earth metal oxides such as Li2O, Na2O, CaO, and MgO; alkali metal and alkaline earth metal hydrides such as LiH, NaH, KH, and CaH2; alkali metal and alkaline earth metal carbonates such as Li2CO3, K2CO3, and CaCO3; alkali metal bicarbonates such as NaHCO3; organic bases such as pyrrolidine; tertiary amines such as diisopropylethylamine, trimethylamine, triethylamine, triisopropylamine, and N-methylpiperidine, imidazole, pyridine; substituted pyridines such as Collidine, lutidine, and 4-dimethylaminopyridine, as well as polycyclic amides and amidines, such as 1,8-diazabicycloundec-7-ene (DBU) and 1,4-diazabicyclo[2.2.2]octane (DABCO); alkali metal salts of secondary amines, such as alkali diisopropylamides, alkali bis(trimethylsilyl)amides, and alkali tetramethylpiperidines; alcoholates, such as alkali methanolates, alkali ethanolates, alkali isopropanolates, and alkali tert-butanolates; and alkali metal alkyl and alkali metal aryl salts, such as n-butyllithium, tert-butyllithium, and phenyllithium. Mixtures of the above bases are also possible. The base is generally employed in catalytic amounts, but can also be used in equimolar amounts, in excess, or, where appropriate, as a solvent. The compound of formula (III) and the compound of formula (IV) are typically reacted in equimolar amounts. In terms of yield, it may be advantageous to use an excess of the compound of formula (IV).

[0069] A compound of formula (IVa) falling within the definition of formula (IV), wherein n is 1, W is S(O)2, and R 7 is in the para position) can be prepared, for example, as shown in Scheme 1. [ka]

[0070] Variable A in Scheme 1 is either N or CH, and R 71 and R 72 are independently 7 It falls under the definition of Scheme 1: [ka]

[0071] Compound VI can be prepared by reacting compound V, where X is Cl, Br, I, -OTf (triflate) or a leaving group, with a nitro group (which can also be any other suitable leaving group such as Cl, Br, I, F, -OTf (tosylate)) and HS-R in the presence of a base, such as potassium carbonate, sodium carbonate, cesium carbonate, sodium hydride, etc., in a solvent such as DMF, THF, or DMSO while cooling to ambient temperature. W This method is also described in literature such as Tetrahedron Letters, 2014, vol. 55, #22, pp. 3295-3298.

[0072] Compound VII can be prepared by converting compound VI to a cyano group by reacting with the respective Grignard reagent. For this purpose, as described in WO 2018095795, WO 2016012395, and Tetrahedron Letters 1981, vol. 22, 3815-3818, nitrile compound (VI) can be dissolved in a suitable solvent such as THF, MTBE, or toluene at 0°C, followed by treatment with CHMgBr, CHMgCl, and stirring at 20-25°C.

[0073] Compound VII can be further oxidized to SO (sulfone) by oxidation using reagents such as m-chloroperbenzoic acid, hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite, or tert-butyl hypochlorite. Solvents used in the oxidation include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; and water. The amount of oxidizing agent used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, per mole of sulfide compound VII to produce a sulfoxide compound, as described in International Publication Nos. WO 2015 / 091945 A1, WO 2016107742, and WO 2018095795. Preferably, the amount of oxidizing agent used in the reaction is 2 to 2.2 moles per mole of sulfide compound VII, as described in International Publication Nos. WO 2015 / 091945 A1, WO 2016107742, and WO 2018095795.

[0074] Compound X (where X is a leaving group such as, for example, chlorine, bromine or iodine (preferably bromine) or an aryl-, alkyl- or haloalkylsulfonate, for example trifluoromethanesulfonate) can be prepared by reacting compound VIII with a reagent R 71 -B(OH)2, R 71 -B(OR)2, where R can be an alkyl, aryl, cycloalkyl or pinacol type cyclic group of formula IX.

[0075] The reaction may be catalyzed by a palladium-based catalyst, for example with bis(diphenylphosphino)ferrocene]dichloropalladium(II) (1:1) (Pd(dppf)Cl2), preferably under an inert atmosphere, in a solvent or solvent mixture such as dioxane, 1,2-dimethoxyethane or toluene, in the presence of a base such as sodium carbonate, potassium carbonate or cesium carbonate or sodium or potassium tert-butyrate, in the presence of a DCM complex, tetrakis(triphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3; optionally in the form of its chloroform adduct) or palladium acetate(II) and lignoceramide. and for example XantPhos ((5-diphenylphosphanyl-9,9-dimethyl-xanthen-4-yl)diphenylphosphine), RuPhos (2-dicyclohexylphosphino 2',6'-diisopropoxybiphenyl), JohnPhos ([1,1-biphenyl]-2-ylbis(1,1-dimethylethyl)phosphine), BINAP (2,2'-bis(diphenylphosphino)-1,1'-binaphthalene), tol-BINAP ([2,2'-bis(di-p-tolylphosphino)-1,1'-binaphthyl]) or tri-(o-tolyl)phosphine. The reaction temperature may preferentially range from room temperature to the boiling point of the reaction mixture, or the reaction may be carried out under microwave irradiation. Such reactions are described, for example, in Molecules 2012, 17, 4508-4521, Advanced Synthesis & Catalysis (2015), 357(2-3), 361-365, WO 2022025242 A1, Org. Lett., 2001, 3, 2757-2759 or Synlett, 2009, 1761-1764.

[0076] The reaction temperature can preferably range from 20-25°C to the boiling point of the reaction mixture, or the reaction can be carried out under microwave irradiation. Such reactions are described, for example, in Advanced Synthesis & Catalysis, 350(3), 391-394; 2008. Compound IVa can be prepared by dissolving compound X in a suitable solvent, such as ethyl acetate, chloroform, or DCM, and a suitable reagent, such as copper(II) bromide (CuBr2), Br2, HBr in acetic acid, or trimethylphenylammonium tribromide, at ambient temperature or 60°C with monitoring, to obtain bromoketone IV. Such a procedure can be found in WO 2016107742.

[0077] The compounds of formula IX and XII are known compounds that are commercially available or can be prepared by known methods as described in the literature, for example, Green Chemistry (2009), 11(10), 1610-1617, Angewandte Chemie, International Edition (2010), 49(10), 1846-1849, Organic Letters (2011), 13(13), 3312-3315, WO 2011149950 A2, etc.

[0078] Process 2: [ka] Alternatively, a compound of formula (II) falling within the definition of formula (I) can be prepared by reacting a compound of formula (III) with a compound of formula (XI) to produce formula (XIII), as shown in Process 2. The condensation reaction can be carried out as described above to produce compound (II). Compound (XIII) can be prepared by reacting a compound of formula (III) with a compound of formula (XI) to produce compound (XIII), as described above in Process 1 for the synthesis of intermediate (X). 71 -B(OH)2, R 71 It can be further subjected to Suzuki, Negishi or Sonogashira type CC coupling reaction with -B(OR)2.

[0079] a compound of formula (XVII) corresponding to a compound of formula (I), wherein Q is NR 5 ) can be prepared as shown in Process 3 below. Step 3: [ka]

[0080] This type of reaction is described in EP 3257853 A1, WO 2019 / 234160, and WO 2016162318 A1. The reaction is typically carried out in an inert solvent, optionally in the presence of an acid or coupling agent and a base, at elevated temperatures, for example, 60 to 160° C. Suitable solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, or petroleum ether; aromatic hydrocarbons such as benzene, toluene, o-, m-, and p-xylene; halogenated hydrocarbons or halogenated aromatic C6-C6 10 hydrocarbons such as CH2Cl2, CHCl3, CCl4, CH2ClCH2Cl, CCl3CH3, CHCl2CH2Cl, CCl2CCl2 or chlorobenzene; ethers such as CH3CHOCH2CH3, (CH3)2CHOCH(CH3)2, CH3OC(CH3)3(MTBE), CHOCH3(DME), CHOCH2CH2OCH3, CH3OC(CH3)2CH2CH3, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofuran (THF) and diethylene glycol; nitriles such as CH3CN and CH3CH2CN; alcohols such as CH3OH, CH3CH2OH, CH3CH2CH2OH, CH3CH(OH)CH3, CH3(CH2)3OH and C(CH3)3OH, CH2(OH)CH2(OH) and CH3CH(OH)CH2OH. Mixtures of the above solvents are also possible.

[0081] Suitable acids are generally inorganic acids such as HF, HCl, HBr, H2SO4 and HClO4; Lewis acids such as BF3, AlCl3, FeCl3, SnCl4, TiCl4 and ZnCl2, as well as organic acids such as HCOOH, CH3COOH, CH3CH2COOH, oxalic acid, toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, citric acid and CF3COOH.

[0082] Suitable coupling agents are carbodiimides such as DCC (dicyclohexylcarbodiimide) and DIC (diisopropylcarbodiimide), benzotriazole derivatives such as HATU (O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate), HBTU ((O-benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate) and HCTU (1H-benzotriazole). riazolim-1-[bis(dimethylamino)methylene]-5-chlorotetrafluoroborate) and phosphonium-based activators such as BOP ((benzotriazol-1-yloxy)-tris(dimethylamino)phosphonium hexafluorophosphate), PyBOP ((benzotriazol-1-yloxy)-tripyrrolidine phosphonium hexafluorophosphate) and PyBrOP (bromotripyrrolidine phosphonium hexafluorophosphate). Suitable solvents are selected from aliphatic hydrocarbons such as pentane, hexane, cyclohexane or petroleum ether; aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene; halogenated hydrocarbons or halogenated aromatics C6-C6. 10hydrocarbons, such as CH2Cl2, CHCl3, CCl4, CH2ClCH2Cl, CCl3CH3, CHCl2CH2Cl, CCl2CCl2 or chlorobenzene; ethers, such as CH3CHOCH2CH3, (CH3)2CHOCH(CH3)2, CH3OC(CH3)3(MTBE), CHOCH3(DME), CH3OCH2CH2OCH3, CH3OC(CH3)2CH2CH3, dioxane, anisole, 2-methyltetrahydrofuran, tetrahydrofuran (THF) and diethylene glycol; nitriles, such as CH3CN and CH3CH2CN; alcohols, such as CH3OH, CH3CH2OH, CH3CH2CH2OH, CH3CH(OH)CH3, CH3(CH2)3OH and C(CH3)3OH, CH2(OH)CH2(OH) and CH3CH(OH)CH2OH. Mixtures of the above solvents are also possible in the presence of a suitable base, as listed for Process 1 above, to produce compounds of formula XXII, followed by the condensation described in Process 1 to produce compounds of formula XVI.

[0083] Alternatively, the compound of formula (XV) can be replaced by its corresponding carbonic acid halide, such as an acid chloride. In this case, the reaction is typically carried out in the presence of a base. Suitable bases are those listed for Process 1 above.

[0084] The compound of formula (XIV) and the compound of formula (XV) are typically reacted with each other in equimolar amounts. In terms of yield, it may be advantageous to use an excess of the compound of formula (XV).

[0085] The compound of formula (XV) can be prepared as described in WO 2019 / 234160A1. The compound of formula (XIV) can be prepared as described in WO 2017 / 167832A1, Example C-4 or Bashandy et al. Journal of Enzyme Inhibition and Medicinal Chemistry, 29(5), 619-627, 2014.

[0086] Process 4a: [ka] Thus, the compound of formula (XV) can be prepared, for example, as follows: Compound VI can be oxidized to SO (sulfone) by an oxidation reaction involving a reagent such as m-chloroperbenzoic acid, hydrogen peroxide, oxone, sodium periodate, sodium hypochlorite, or tert-butyl hypochlorite. Solvents used in the oxidation include aliphatic halogenated hydrocarbons such as dichloromethane and chloroform; alcohols such as methanol and ethanol; acetic acid; and water. The amount of oxidizing agent used in the reaction is generally 1 to 3 moles, preferably 1 to 1.2 moles, per mole of sulfide compound VI to produce a sulfoxide compound, as described in WO 2015 / 091945 A1, WO 2016107742, and WO 2018095795. Preferably, the amount of oxidizing agent used in the reaction is 2 to 2.2 moles per mole of sulfide compound VI, as described in WO 2015 / 091945 A1, WO 2016107742, and WO 2018095795. For example, XIX was obtained by hydrolysis of a compound of formula (XVIII), as defined in formula I, where X is a leaving group, specifically a compound where X is a halogen (even more preferably chlorine, bromine, or iodine), by heating (XVIII) in a concentrated acid such as concentrated hydrochloric acid (HCl) or sulfuric acid (HS0) optionally in the presence of an inert solvent such as acetic acid or an ether (e.g., tetrahydrofuran, ethylene glycol dimethyl ether, or 1,4-dioxane), preferably in the presence of water. Such hydrolysis conditions and variations thereof are known to those skilled in the art. Suzuki coupling (as described for the synthesis of compound II or X) can be used to generate compound XV, which has the meaning defined for formula (I), which can be reacted with compound XIV via intermediate XVI by direct condensation or amide formation to generate (XVII), followed by a condensation reaction.

[0087] Compounds of formula (XXI) may be prepared by reaction of compounds of formula (XIV) with compounds of formula (XIX), as shown in Process 5. Step 5: [ka]

[0088] The amide formation reaction to produce a compound of formula (XX), followed by condensation to produce a compound of formula XXI and / or direct reaction of compounds XIV with XIX to produce XXI can be carried out as discussed in Process 4.

[0089] Process 5a: [ka] Compounds of formula (XXII) falling within the definition of formula (I) can be prepared by reaction of a compound of formula (XXI) with a compound of formula (IX or XII) under Suzuki-type coupling reaction conditions, as illustrated in Process 1 for the production of compounds XXI or II.

[0090] Step 6: [ka] Compounds of formula (XV) can be prepared by esterifying compounds of formula (XIX) under conditions known to those skilled in the art, such as under acidic conditions by refluxing in ethanol, methanol, or other alcoholic solvents, or under basic conditions by adding an electrophile containing the corresponding alkyl halide Rd-X using potassium carbonate, cesium carbonate, sodium carbonate, sodium hydroxide, or potassium hydroxide, to produce compound XXII, where Rd is a C1-C6 alkyl (Process 6). Compound XXII is then converted to compound XXIII by Suzuki-type C-C coupling with boronic acid XII or boronic ester IX (as described in Process 1) to produce compound XXIII. Compound XXIII is then converted to compound XIV by saponification of compound XXIII under conditions known to those skilled in the art (e.g., using conditions such as aqueous sodium hydroxide, potassium hydroxide, or lithium hydroxide in methanol, ethanol, or dioxane at room temperature, or up to reflux conditions), to give compounds of formula (XV) as defined in Formula I.

[0091] Compounds of formula (XXIV) can be converted to compounds XXV by rearrangement as shown below, where # denotes the linkage to residue G as defined in formula (I). Step 7: [ka]

[0092] This type of reaction is described in Potts KT, Surapaneni CR, 1970, Journal of Heterocyclic Chemistry or Nagamatsu T., Fujita T., 2002, Heterocycles, 57(4), 631-636. The reaction is typically carried out in the presence of a catalyst, usually an acid or base such as NaOH or formic acid, in an inert organic solvent or water at a temperature of 0 to 80°C. When no catalyst is used, the reaction can be carried out at an elevated temperature, for example, 30 to 100°C.

[0093] Compounds of formula (XXIV) can be prepared by reaction of a hydrazine compound of formula (XXVI), as shown in Process 8 below, where # represents the linkage to residue G as defined in formula (I). Step 8: [ka]

[0094] This type of reaction is described in Glushkov VA et al., 1998, Pharmaceutical Chemistry Journal, vol. 32(5), pp. 29-32, or in WO 2012148808, p. 143. The reaction is typically carried out in an inert organic solvent at elevated temperatures of 50-150°C in the presence of a Lewis acid such as FeCl3 or AlCl3. The reaction can also be carried out in the presence of an oxidizing agent, such as H2O2 or CuCl2.

[0095] Compounds of formula (XXVI) are available by reaction of a hydrazine compound of formula (XXVII) with an aldehyde compound of formula (XXVIII), as shown in Process 9 below. Step 9: [ka] # denotes the linkage to residue G as defined in formula (I).

[0096] The reaction is typically carried out in an inert organic solvent in the presence of an acid catalyst such as toluenesulfonic acid. Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane or petroleum ether, or aromatic hydrocarbons such as benzene, toluene, o-, m- and p-xylene. Mixtures of the above solvents are also possible.

[0097] Hydrazine derivatives of formula (XXVII) are commercially available or can be derived from commercially available compounds. Alternatively, compounds of formula (XXVII) can be prepared by the reaction of hydrazine with compounds of formula (XXIX), as shown in Process 10 below. Step 10: [ka]

[0098] wherein LG is a leaving group, and all other variables have the meanings defined for formula (I). Typical leaving groups are triflate, iodide, and chloride. This type of reaction is described in Mao, Y. et al., 2014, Journal of Heterocyclic Chemistry, 51(3), pp. 594-597. The reaction is typically carried out in a polar solvent such as CH3CH2OH at elevated temperatures, such as 50-100°C. Compounds of formula (XXXV) are commercially available or can be prepared by standard methods of organic chemistry.

[0099] By analogy, compounds IIa falling within the definition of Formula II can be prepared as shown in Process 11 below. Process 11: [ka]

[0100] Compounds of formula (XXX) are commercially available or can be prepared by standard methods of organic chemistry. Condensation of compound XXX with aldehyde XXXI by a method similar to that described in U.S. Patent No. 4,503,050 (March 5, 1985) to Wade et al. gives compound XXXII. Hydrolysis of R (Cl, -OMe) present in compound XXXII under conditions known in the literature gives compound XXVI. Compound XXVI can be prepared from XXXIII by N-alkylation under basic or copper-catalyzed conditions, as described in Bioorganic & Medicinal Chemistry Letters, 25(6), 1310-1317; 2015. Rearrangement of XXIV to give compound IIa, as described in Process 7, gives compound IIa.

[0101] Alternatively, compound IIa can be obtained as shown in Scheme 2 below. Scheme 2 [ka]

[0102] Compound XXXVII, in which PG is a protecting group, can be obtained by reacting commercially available compound XXXIV with compound XXV in the presence of an inert solvent such as DCM, THF, DMF or dioxane and a base such as triethylamine (TEA) at 20-100°C, as described in European Journal of Medicinal Chemistry (1990), 25(8), 653-8.

[0103] Compound XXXVIII can be obtained by reacting compound XXXVII with cyanoacetic acid in the presence of acetic anhydride, followed by reaction under aqueous basic conditions such as (aqueous NaOH, aqueous KOH, aqueous NaCO, aqueous KCO, etc.), as described in CN Patent Publication No. 112125903A and CN Patent No. 111170951.

[0104] Removal of the protecting group from intermediate XXXVIII by using a reaction under basic conditions (aqueous NaOH, aqueous KOH, aqueous NaCO, aqueous KCO), acidic conditions (aqueous HCl, aqueous HSO, AcOH) or under hydrogenation conditions in the presence of H and a metal catalyst such as Rh, Pd, Pt or transfer hydrogenation conditions using ammonium formate, potassium formate or sodium formate results in the formation of compound XXXIX.

[0105] Compound XL can be prepared from compound XXXIX by reaction with POX3 (e.g., POCl3, POBr3) in the presence of a polar aprotic solvent such as THF, dioxane, or DEE, as described in Tetrahedron Letters (2003), 44(13), 2717-2720. Further condensation of compound XL with compound IV or XI using the process described in Process 1 produces compound XLI. Further Suzuki coupling reaction of XLI with IX or XII under standard Suzuki-type conditions described in Process 1 affords compounds XLII and / or IIa.

[0106] Alternatively, compound XXXIX can be condensed with intermediates IV or XI to give intermediate XLIII using processes described in Process 1. The hydroxy group can then be converted to R using processes known to those skilled in the art. 1 where X is a leaving group such as Cl, Br, -OTf, -Onf, -tosyl, mesyl, etc., to prepare compound XLIV. Furthermore, compound IIa and / or compound XLII can be produced by Suzuki coupling of XLIV with IX or XII.

[0107] Compounds of formula (XLV) falling within the definition of formula (I), wherein R 71is the group -C(CN)(CH) or 1-cyanocyclopropyl) can be prepared from compound XLVI by, for example, condensing compound XLVI with compound XLVII (synthesized as described in WO2021204577) following the procedures described in Process 1 and as shown in Process 13 below. Process 13: [ka] # denotes the linkage to residue G as defined in formula (I).

[0108] The reaction mixture is worked up in a conventional manner, for example by mixing with water, separating the phases, and, if appropriate, chromatographically purifying the crude product.Some intermediates and final products are obtained in the form of colorless or slightly brownish viscous oils, which are purified or freed from volatile components under reduced pressure and at moderately elevated temperatures.If the intermediates and final products are obtained as solids, purification can also be carried out by recrystallization or digestion.

[0109] N-oxides can be prepared from compounds of the invention by treating compound I according to conventional oxidation methods, for example with organic peracids such as metachloroperbenzoic acid (see WO 03 / 64572 or J. Med. Chem. 38(11), 1892-903, 1995); or with inorganic oxidizing agents such as hydrogen peroxide (see J. Heterocyc. Chem. 18(7), 1305-8, 1981) or oxone (see J. Am. Chem. Soc. 123(25), 5962-5973, 2001). Oxidation can lead to pure mono-N-oxides or mixtures of different N-oxides, which can be separated by conventional methods, such as chromatography.

[0110] When a mixture of isomers is obtained by synthesis, separation is generally not necessary, since in some cases the individual isomers can be interconverted during workup for use or during application (e.g., under the action of light, acid, or base). Such conversions can also occur after use, for example, in plant treatments or within the harmful fungi being controlled in treated plants.

[0111] Those skilled in the art will readily appreciate that the variable preferences defined herein, and in particular those shown in the table below for each substituent set forth herein in connection with Compound I, also apply accordingly to the intermediates (Compounds II to XLVII), whereby the substituents in each instance, independently of one another or, more preferably, in combination, have the meanings as defined herein.

[0112] The variables, each alone and in combination, have the following preferred meanings:

[0113] In one embodiment of the compound of Formula (I), E is NR 3 and Q is CH. In another embodiment of the compound of formula (I), E is NR 3 and Q is N.

[0114] In one embodiment of the present invention, the compound of formula (I) is a compound of formula (IA) or compound (IB). [ka] wherein all variables have the meanings as defined for formula (I). In one embodiment, the compound of formula (I) is a compound of formula (IA). In another embodiment, the compound of formula (I) is a compound of formula (IB).

[0115] In one embodiment of the present invention, the compound of formula (I) is a compound of formula (IA), wherein: G is phenyl or pyridyl; W is S, S(O), S(O)2, S(O)(NRH); R1 is a halogen; R 3 is unsubstituted or halogenated C1-C6-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl; Each R 7 are independently H, halogen, OH, CN; unsubstituted or halogenated C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl; containing one or more of the same or different heteroatoms O, N or S and being unsubstituted or containing one or more R H a 3- to 12-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with; unsubstituted or one or more R J phenyl substituted with; OR K ; -C(CN)(CH3)2 or 1-cyanocyclopropyl, Each R H are independently halogen, CN; C1-C3-alkyl, C1-C3-haloalkyl; Each R J are independently halogen, CN; unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy; or two adjacent substituents R are C1-C6-alkoxy. J wherein the substituents form an alkyl bridge between two oxygens, which is unsubstituted or halogenated; Each R K is C1-C6-alkyl which is unsubstituted or substituted with one or more halogens; Each R W are independently C1-C4 alkyl; The subscript n is 1 or 2, and the compounds and their N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts.

[0116] In one embodiment of the present invention, the compound of formula (I) is a compound of formula (IA), wherein: G is phenyl or pyridyl; W is S(O)2, S(O)(NRH); R 1 is Cl or Br; R 3 is C1-C2-alkyl, cyclopropyl or cyclopropylmethyl; Each R 7 are independently H, chloro, bromo; Unsubstituted or halogenated C1-C2-alkyl, C3-C6-cycloalkyl; unsubstituted or one or more R H Pyridine substituted with; unsubstituted or one or more R J phenyl substituted with; OR K ; -C(CN)(CH3)2 or 1-cyanocyclopropyl, Each R H are independently halogen, CN; C1-C3-alkyl, C1-C3-haloalkyl; Each R J are independently fluoro, chloro, CN; unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, or two adjacent substituents R are C1-C6-alkoxy. J where the substituents form an alkyl bridge between two oxygens, which is unsubstituted or halogenated; Each R K is C1-C6-alkyl which is unsubstituted or substituted with one or more halogens; R W is ethyl or isopropyl; The subscript n is 1 or 2, as well as N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

[0117] In one embodiment of the present invention, the compound of formula (I) is a compound of formula (IA), wherein: G is pyridyl; W is S(O)2; R 1 , Cl; R 3 is methyl, cyclopropyl or cyclopropylmethyl; Each R 7 are independently H, chloro, bromo; Unsubstituted or halogenated C1-C2-alkyl, C3-C6-cycloalkyl; 1,3-benzodioxol-5-yl, unsubstituted or substituted with halogen; unsubstituted or one or more R H Pyridine substituted with; unsubstituted or one or more R J phenyl substituted with; OR K ; -C(CN)(CH3)2 or 1-cyanocyclopropyl, Each R H are independently halogen, CN; C1-C3-alkyl, C1-C3-haloalkyl; Each R J are independently fluoro, chloro, CN; unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, or two adjacent substituents R are C1-C6-alkoxy. J where the substituents are unsubstituted or halogenated to form an alkyl bridge between the two oxygens; Each R K is C1-C6-alkyl which is unsubstituted or substituted with one or more halogens; R W is ethyl or isopropyl; The subscript n is 1 or 2, as well as N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

[0118] In a preferred embodiment of the present invention, the compound of formula (I) has the formula (IA1) [ka] wherein the variable R 1 , R 3 and R W has the meaning as defined in relation to formula (I) or (IA), and the variable R 71 and R 72 is R in formula (I). 7 The terms "A" and "B" have the meanings as defined with respect to the following:

[0119] In another embodiment of the present invention, the compound of formula (I) has the formula (IA2) [ka] wherein the variable R 1 , R 3 and R W has the meaning as defined in relation to formula (I) or (IA), and the variable R 71 and R 72 is R in formula (I). 7 The terms "A" and "B" have the meanings as defined with respect to the following:

[0120] In another embodiment of the present invention, the compound of formula (I) has the formula (IA3) [ka] wherein the variable R 1 , R 3 and R W has the meaning as defined in relation to formula (I) or (IA), and the variable R 71 and R 72 is R in formula (I). 7 The terms "A" and "B" have the meanings as defined with respect to the following:

[0121] R 1 is halogen, i.e., F, Cl, Br or I, preferably F, Cl or Br, more preferably Cl or Br. In one embodiment, R 1is Cl. In another embodiment, R 1 is Br.

[0122] R 3 , R 5 are independently unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C4-alkyl. 3 , R 5 is independently unsubstituted or halogenated C1-C3-alkyl or C3-C6 cycloalkyl. 3 , R 5 is independently cyclopropyl. In one embodiment, R 3 is C1-C2-alkyl, cyclopropyl or cyclopropylmethyl. Preferably, R 3 is cyclopropyl.

[0123] Ring G is phenyl or pyridyl. In one embodiment, G is phenyl. In another embodiment, G is pyridyl, more preferably 2-pyridyl.

[0124] Preferred rings G are shown below as formulae A1-A3, where "&" represents the connection to the tricyclic scaffold of the compound of formula (I). For the avoidance of doubt, formulae A1-A3 are preferred embodiments by themselves and in combination for the following groups: [ka] In other words, the substituent R in formulas A1-A3 W -W and (R 7 ) n is merely an illustration and is not part of the ring G. [ka]

[0125] In one embodiment, G is A1. In another embodiment, G is A2. In another embodiment, G is A3.

[0126] The variable W is S, S(O), S(O) or S(O)(NR W ), preferably S(O)2. In one embodiment, the variable W is S(O)(NH). In one embodiment, the variable W is not S(O)NH, while the other variables have the meanings as described in the embodiments herein.

[0127] The subscript n is 1, 2, 3, or 4 when G is phenyl, or 1, 2, or 3 when G is pyridyl. Typically, n is 1 or 2. In another embodiment, n is 1. In another embodiment, n is 2. In another embodiment, n is 3.

[0128] In one embodiment, R 7 are independently H, halogen, OH, CN; unsubstituted or halogenated C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C2-C6-alkynyl; containing one or more of the same or different heteroatoms O, N or S and unsubstituted or containing one or more R H a 3- to 12-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with; J Phenyl substituted with OR K ;-C(CN)(CH3)2 or 1-cyanocyclopropyl.

[0129] In another embodiment, R 7 is halogen; C1-C3-alkyl, cyclopropyl; 6- to 9-membered saturated, partially unsaturated or fully unsaturated heterocyclic rings or ring systems containing one or more identical or different heteroatoms O or N and which are unsubstituted or substituted with one or more substituents selected from halogen, CN, C1-C3-alkyl and C1-C3-haloalkyl; J Phenyl substituted with OR; K(In the formula, R K is C1-C3-alkyl which is unsubstituted or substituted by CN).

[0130] In another embodiment, R 7 is selected from —C(CN)(CH 3 ) 2 and 1-cyanocyclopropyl.

[0131] In another embodiment, R 7 is halogen; CH, cyclopropyl; pyridyl substituted with CN; 1,3-benzodioxol-5-yl substituted with halogen; phenyl substituted with halogen, or C1-C3 alkoxy substituted with CN. In another embodiment, R 7 is selected from —C(CN)(CH 3 ) 2 and 1-cyanocyclopropyl.

[0132] In another embodiment, R 7 is halogen; CH, cyclopropyl; pyridyl substituted with CN; 1,3-benzodioxol-5-yl substituted with halogen; phenyl substituted with halogen, C-C alkoxy substituted with CN, —C(CN)(CH) or 1-cyanocyclopropyl.

[0133] In another embodiment, R 7 is halogen; CH3, cyclopropyl; pyridyl substituted with CN; 1,3-benzodioxol-5-yl substituted with halogen; phenyl substituted with halogen, CN, unsubstituted or halogenated C1-C6-alkyl, C1-C6-alkoxy; -C(CN)(CH3)2 or 1-cyanocyclopropyl.

[0134] In a preferred embodiment, R 7is chloro, bromo, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,6-dichlorophenyl, 4-chlorophenyl, methyl, cyclopropyl or phenyl substituted with C1-C2-alkyl, C1-C2-alkoxy, which are unsubstituted or halogenated.

[0135] Each R H are independently halogen, CN; C1-C3-alkyl or C1-C3-haloalkyl. Preferably, each R H are independently CN or C1-C3-haloalkyl, more preferably CN or CF3.

[0136] Each R J are independently halogen, CN; C1-C3-alkyl or C1-C3-alkoxy, which groups are unsubstituted or halogenated. Preferably, each R J are independently halogen, CN or C1-C3-haloalkoxy, more preferably halogen, CN, CF3O or CHF2O, particularly preferably halogen, CF3O or CHF2O.

[0137] In one embodiment, two adjacent substituents R are C1-C6-alkoxy. J is present, the substituents forming an alkyl bridge between two oxygens that are unsubstituted or halogenated.

[0138] Adjacent substituents R forming an alkylene ether bridge J An example of this is as follows: [ka] Each R K is C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, which groups are unsubstituted or substituted with one or more identical or different substituents selected from halogen and CN. Preferably, each R Kis C1-C3-alkyl substituted with CN, more preferably isopropyl substituted with CN, especially 1-cyanoisopropyl.

[0139] R W is C1-C4-alkyl or cyclopropyl, preferably ethyl or isopropyl.

[0140] Formula IA1 is a preferred embodiment that falls within the definition of formula IA, where n is 2 and the residue R 71 and R 72 is R 7 It has a definition by [ka]

[0141] The following Table A shows the substituents R in lines 1 to 75. 1 and R 71 Each combination individually and all combinations collectively represent preferred embodiments. Each of the groups mentioned for the substituents in the table is also itself a particularly preferred embodiment of the substituent in question, independently of the combination in which it is mentioned. [ka] [ka] [ka] [ka] Table A:R 1 and R 71 Preferred combinations I.1 to I.75

[0142] Particularly preferred embodiments of the present invention are listed in Tables 1-4, which correspond to certain compounds falling within Formula IA.

[0143] Table 1: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is H and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0144] Table 2: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is CH3 and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0145] Table 3: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is CH2CH3 and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0146] Table 4: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is Cl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0147] Table 5: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is Br and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0148] Table 6: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72is cyclopropyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0149] Table 7: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is isopropyl, and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0150] Table 8: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is N-imidazolyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0151] Table 9: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is ethyl, and R 72 is N-triazolyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0152] Table 10: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is H and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0153] Table 11: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is CH3 and R 1 and R 71and combinations are as defined in row 1 of Table A).

[0154] Table 12: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is CH2CH3 and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0155] Table 13: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is Cl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0156] Table 14: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is Br and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0157] Table 15: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is cyclopropyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0158] Table 16: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is isopropyl, and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0159] Table 17: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is N-imidazolyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0160] Table 18: Compounds of formula IA1 (wherein R 3 is cyclopropyl and R W is isopropyl, and R 72 is N-triazolyl and R 1 and R 71 and combinations are as defined in row 1 of Table A).

[0161] In a preferred embodiment, the compound of formula (I) is a compound of formula (IA) wherein G is pyridyl; R 1 is a halogen; R 3 is cyclopropyl; R W is C1-C4-alkyl, cycloalkyl; n is 1 or 2; R 7 teeth, halogen; C1-C3-alkyl, cyclopropyl; 6- to 9-membered saturated, partially unsaturated or fully unsaturated heterocyclic rings or ring systems containing one or more identical or different heteroatoms O or N and which are unsubstituted or substituted with one or more substituents selected from halogen, CN, C1-C3-alkyl and C1-C3-haloalkyl; unsubstituted or one or more R J phenyl substituted with; or OR K (In the formula, R K is C1-C3-alkyl, unsubstituted or substituted with CN; -C(CN)(CH3)2 and 1-cyanocyclopropyl is selected from.

[0162] In another preferred embodiment, the compound of formula (I) is a compound of formula (IA) wherein G is pyridyl; R 1 is a halogen; R 3 is cyclopropyl; R W is C1-C4-alkyl, cycloalkyl; n is 1 or 2; R 7 is two adjacent substituents R which are C1-C6-alkoxy J and phenyl having two R J forms an alkyl bridge between two oxygens, which may be unsubstituted or halogenated.

[0163] In another preferred embodiment, the compound of formula (I) is a compound of formula (IA) wherein G is pyridyl; R 1 is a halogen; R 3 is cyclopropyl; R W is C1-C3-alkyl; n is 1 or 2; R 7 is selected from halogen; CH, cyclopropyl; pyridyl substituted with CN; 1,3-benzodioxol-5-yl substituted with halogen; phenyl substituted with halogen, C-C alkoxy substituted with CN, —C(CN)(CH) or 1-cyanocyclopropyl.

[0164] The term "compounds of the invention" refers to compounds of Formula I or "Compound I," including salts, tautomers, stereoisomers, and N-oxides thereof.

[0165] The present invention also relates to an agrochemical composition comprising an adjuvant and at least one compound I.

[0166] The pesticidal composition comprises Compound I in a pesticidally effective amount.

[0167] Compound I can be converted into conventional types of pesticide compositions, such as solutions, emulsions, suspensions, dusts, powders, pastes, granules, compacts, capsules, and mixtures thereof. Examples of composition types are suspensions (e.g., SC, OD, FS), emulsifiable concentrates (e.g., EC), emulsifiable concentrates (e.g., EW, EO, ES, ME), capsules (e.g., CS, ZC), pastes, pastilles, wettable powders or dusts (e.g., WP, SP, WS, DP, DS), compacts (e.g., BR, TB, DT), granules (e.g., WG, SG, GR, FG, GG, MG), insecticidal articles (e.g., LN), and gel formulations (e.g., GF) for treating plant propagation materials (e.g., seeds). These and other composition types are defined in "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International. The compositions are prepared by known methods, for example those described in 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.

[0168] Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners, moisturizing agents, repellents, attractants, feeding stimulants, compatibilizers, bactericides, antifreeze agents, antifoaming agents, colorants, tackifiers and binders.

[0169] Suitable solvents and liquid carriers are water and organic solvents. Suitable solid carriers or fillers are mineral earths.

[0170] Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic, and amphoteric surfactants, block polymers, and polyelectrolytes. Such surfactants can be used as emulsifiers, dispersants, solubilizers, wetting agents, penetration enhancers, protective colloids, or adjuvants. Surfactants are listed in McCutcheon's, Vol. 1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth, or ammonium salts of sulfonates, sulfates, phosphates, and carboxylates. Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar surfactants, and polymeric surfactants. Suitable cationic surfactants are quaternary surfactants.

[0171] The pesticide composition generally contains 0.01 to 95% by weight, preferably 0.1 to 90% by weight, and most preferably 0.5 to 75% by weight of the active substance. The active substance is used at a purity of 90% to 100%, preferably 95% to 100%.

[0172] Various types of oils, wetting agents, adjuvants or fertilizers can be added to the active substances or compositions containing them as premixes or, if appropriate, added immediately before use (tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1.

[0173] The user typically applies the compositions according to the invention from a pre-metering device, backpack sprayer, spray tank, spray aircraft or irrigation system. The agrochemical composition is typically made up to the desired application concentration with water, buffers and / or further adjuvants, thus providing a ready-to-use spray solution or agrochemical composition according to the invention. Typically, 20 to 2000 liters of ready-to-use spray solution are applied per hectare of agriculturally useful area.

[0174] Compound I is suitable for use in protecting crops, plants, plant propagation material (e.g., seeds), or the soil or water in which plants are growing, from attack or infestation by animal pests. Accordingly, the present invention also relates to a method for protecting plants, which comprises contacting a crop, plant, plant propagation material, such as seeds, or the soil or water in which plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of compound I.

[0175] Compound I is also suitable for use in combating or controlling animal pests. Accordingly, the present invention also relates to a method for combating or controlling animal pests, which comprises contacting an animal pest, its habitat, breeding ground or food source, or a crop, plant, plant propagation material, such as a seed, or soil or area, material or environment in which an animal pest is growing or may grow, with a pesticidally effective amount of compound I.

[0176] Compound I is effective both by contact and ingestion and against any and all developmental stages, such as eggs, larvae, pupae and adults. Compound I can be applied on its own or in the form of a composition containing it.

[0177] Application can be carried out both before and after infestation of the crop, plant or plant propagation material by pests.

[0178] The term "contact" includes both direct contact (applying a compound / composition directly to an animal pest or plant) and indirect contact (applying a compound / composition to a habitat).

[0179] The term "animal pests" includes arthropods, gastropods and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, especially insects.

[0180] The term "plant" includes cereals such as durum and other wheat, rye, barley, triticale, oats, rice or maize (fodder and sugar maize / sweet corn and field corn); beets, such as sugar beet or fodder beet; fruits, such as pome fruits, stone fruits or soft fruits, for example apple, pear, plum, peach, nectarine, almond, cherry, papaya, strawberry, raspberry, blackberry or gooseberry; legumes, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed, oilseed rape, mustard, olive, sunflower, palm, cocoa bean, castor bean, oil palm, groundnut or soybean; cucurbits, such as eggplant, pumpkin, cucumber, cucumber, onion ... cucumbers or melons; fibre plants such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruit or mandarins; vegetables such as eggplant, spinach, lettuce (e.g. head lettuce), chicory, cabbage, asparagus, cabbage, carrots, onions, garlic, leeks, tomatoes, potatoes, melons or sweet peppers; lauraceae plants such as avocado, cinnamon or camphor; energy plants and raw material plants such as maize, soybeans, rapeseed, sugarcane or oil palm; tobacco; nuts such as walnuts; pistachios; coffee; tea; bananas; vines; hops; sweetleaf (stevia); natural rubber plants or ornamental plants and forest plants, shrubs, broad-leaved or evergreen trees, eucalyptus; turf; lawn; grasses. Preferred plants include potato, sugar beet, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rapeseed, legumes, sunflower, coffee or sugarcane; fruits; vines, ornamentals; or vegetables such as cucumber, tomato, bean or pumpkin.

[0181] The term "seed" encompasses seeds and plant propagules, including true seeds, seed fragments, suckers, corms, bulbs, fruits, tubers, grains, cuttings and cut shoots, and preferably means true seeds.

[0182] "Pesticidally effective amount" means the amount of active ingredient required to achieve an observable effect on growth, including necrosis, killing, delay, prevention and elimination, destruction, or otherwise reducing the appearance and activity of the target organism. Pesticidally effective amounts may vary for the various compounds / compositions used in the present invention. The pesticidally effective amount of the composition will also vary depending on the prevailing conditions (e.g., desired pesticidal effect and duration, weather, target species, habitat, mode of application, etc.).

[0183] When used in treating crop plants (for example by foliar application), the rate of application of the active ingredient of the invention may range from 0.0001 g to 4000 g per hectare, for example from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare.

[0184] Compound I is also suitable for use against non-crop insect pests, where it can be used as a bait composition, gel, general insect spray, aerosol, ultra-low volume application and mosquito net (impregnation or surface application).

[0185] The term "non-crop insect pest" refers to pests that are particularly associated with non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitoes, bedbugs, crickets or cockroaches, such as Aedes aegypti, Musca domestica, Tribolium spp.; termites, such as Reticulitermes flavipes, Coptotermes formosanus; cockroaches, such as Blatella germanica, Periplaneta americana; ants, such as Solenopsis invicta, Argentine ant, Linepithema humile and Camponotus pennsylvanicus.

[0186] The bait may be a liquid, solid or semi-solid preparation (e.g., a gel). When used in a bait composition, the typical content of the active ingredient is 0.001% to 15% by weight of the active compound, preferably 0.001% to 5% by weight.

[0187] Compound I and compositions thereof can be used to protect wooden materials (e.g., trees, board fences, sleepers, framing, artistic artifacts, etc.) and buildings, as well as construction materials, furniture, leather, textiles, vinyl products, electrical wires and cables, etc., from ants, termites, and / or wood- or fabric-destroying beetles, and to control ant and termite damage to crops or humans (e.g., when the pests invade homes and public facilities or nest in gardens, orchards, or parks).

[0188] The customary application rate for protecting materials is, for example, 1 m of treated material. 2 The amount of active compound is 0.001 g to 2000 g or 0.01 g to 1000 g per 1 ml, preferably 1 ml 2 Each serving weighs between 0.1g and 50g.

[0189] Insecticidal compositions for use in impregnating materials typically contain from 0.001 to 95% by weight, preferably from 0.1 to 45% by weight, more preferably from 1 to 25% by weight of at least one repellent and / or insecticide.

[0190] pest The compounds of the present invention are particularly suitable for effectively controlling animal pests, such as arthropods and nematodes, including: Insects of the suborder Auchenorrhyncha, such as Amrasca biguttula, Empoasca spp., Nephotettix virescens, Sogatella furcifera, Mahanarva spp., Laodelphax striatellus, Nilaparvata lugens, and Diaphorina citri; Lepidoptera, e.g. Helicoverpa spp., Heliothis virescens, Lobesia botrana, Ostrinia nubilalis, Plutella xylostella, Pseudoplusia includens, Scirpophaga incertulas, Spodoptera spp., Trichoplusia ni, Tuta absoluta, Cnaphalocrocis medialis, Cydia pomonella, Chilo suppressalis, Anticarsia gemataris gemmatalis), Agrotis ipsilon, Chrysodeixis includens; Hemipteran insects, such as Lygus spp., stink bugs, such as Euschistus spp., Halyomorpha halys, Nezara viridula, Piezodorus guildinii, Dichelops furcatus; Thrips, e.g. Frankliniella spp., Thrips spp., Dichromothrips corbettii; Aphids, such as Acyrthosiphon pisum, Aphis spp., Myzus persicae, Rhopalosiphum spp., Schizaphis graminum, Megoura viciae; Whiteflies, such as Trialeurodes vaporariorum, Bemisia spp.; Coleoptera, for example Phyllotreta spp., Melanotus spp., Meligethes aeneus, Leptinotarsa ​​decimlineata, Ceutorhynchus spp., Diabrotica spp., Anthonomus grandis, Atomaria linearia, Agriotes spp., Epilachna spp.; Flies, such as Delia spp., Ceratitis capitate, Bactrocera spp., Liriomyza spp.; Coccoidea, e.g., Aonidiella aurantia, Ferrisia virgate; Arthropods (mites) of the Arachnida family, such as Penthaleus major, Tetranychus spp.; Nematodes, such as Heterodera glycines, Meloidogyne spp., Pratylenchus spp., Caenorhabditis elegans.

[0191] In one embodiment, the pest is selected from Phyllophaga spp., Limonius spp., Popillia japonica.

[0192] Animal Health Compound I is suitable for use in treating or protecting animals against parasitic infestation or infection. Accordingly, the present invention also relates to the use of the compounds of the present invention for the manufacture of a medicament for treating or protecting animals against parasitic infestation or infection. Furthermore, the present invention relates to a method for treating or protecting animals against parasitic infestation and infection, which comprises orally, topically or parenterally administering or applying to an animal a parasiticidally effective amount of Compound I.

[0193] The present invention also relates to the non-therapeutic use of the compounds of the present invention for treating or protecting animals against parasitic infestation and infection. Furthermore, the present invention relates to a non-therapeutic method for treating or protecting animals against parasitic infestation and infection, which comprises applying to a locus a parasiticidally effective amount of Compound I.

[0194] The compounds of the present invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the present invention relates to a method for combating or controlling parasites in and on animals, which method comprises contacting the parasites with a parasiticidally effective amount of compound I.

[0195] The present invention also relates to the non-therapeutic use of compound I for combating or eliminating parasites. Furthermore, the present invention relates to a non-therapeutic method for combating or controlling parasites, which method comprises applying a parasiticidally effective amount of compound I to a locus.

[0196] Compound I can be effective by both contact (via soil, glass, walls, bed nets, carpets, blankets, or animal parts) and ingestion (e.g., bait). Furthermore, Compound I can be applied to any and all stages of development.

[0197] The compounds I can be applied on their own or in the form of compositions containing them.

[0198] The term "habitat" means the habitat, food source, breeding ground, area, material or environment in which the parasite lives or can live outside of an animal.

[0199] As used herein, the term "parasite" includes endoparasites and ectoparasites. In some embodiments of the present invention, endoparasites may be preferred. In other embodiments, ectoparasites may be preferred. Infestations of warm-blooded animals and fish include lice, biting lice, ticks, bot flies, pediculid flies, stable flies, blowflies, flies, myiasis fly larvae, chiggers, black flies, mosquitoes, and fleas.

[0200] The compounds of the present invention are particularly useful for combating the following parasites: bed bugs (Cimex lectularius), brown dog ticks (Rhipicephalus sanguineus) and cat fleas (Ctenocephalides felis).

[0201] As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferred are mammals such as cattle, sheep, pigs, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, buffalo, donkeys, fallow deer and reindeer, as well as fur animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks, and fish, including freshwater and saltwater fish such as trout, carp and eels. Domestic animals such as dogs or cats are particularly preferred.

[0202] Compound I may be applied in a total amount of 0.5 mg / kg to 100 mg / kg per day, preferably 1 mg / kg to 50 mg / kg per day.

[0203] For oral administration to warm-blooded animals, Compound I can be formulated as animal feed, animal feed premix, animal feed concentrate, pill, liquid, paste, suspension, drench, gel, tablet, bolus, and capsule. For oral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of Compound I per kg of animal body weight per day, preferably 0.5 mg to 100 mg per kg of animal body weight per day.

[0204] Alternatively, Compound I can be administered to animals parenterally (e.g., by intraruminal, intramuscular, intravenous, or subcutaneous injection). Compound I can be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, Compound I can be formulated into an implant for subcutaneous administration. In addition, Compound I can be administered transdermally to animals. For parenteral administration, the selected dosage form should provide the animal with 0.01 mg to 100 mg of Compound I per kg of animal body weight per day.

[0205] Compound I can be topically applied to animals in the form of dips, powders, dusts, collars, medallions, sprays, shampoos, spot-on formulations, and pour-on formulations, as well as ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays typically contain 0.5 ppm to 5,000 ppm, preferably 1 ppm to 3,000 ppm, of Compound I. In addition, Compound I can be formulated as an ear tag for animals, particularly quadrupeds (e.g., cattle and sheep).

[0206] Oral solutions are administered directly.

[0207] Solutions applied to the skin may be dripped, spread, rubbed, sprinkled or sprayed.

[0208] The gel is applied or spread on the skin or introduced into a body cavity.

[0209] Pour-on formulations are applied or sprayed onto a limited area of ​​the skin, allowing the active compound to penetrate the skin and act systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in a suitable skin-compatible solvent or solvent mixture.

[0210] The emulsion can be administered orally, transdermally or as an injection.

[0211] Suspensions may be administered orally or topically / dermally.

[0212] Semi-solid preparations can be administered orally or topically / transdermally.

[0213] For the production of solid preparations, the active compound is mixed with suitable excipients and, if appropriate with the addition of auxiliaries, brought into the desired form.

[0214] The compositions that can be used in the present invention can generally contain Compound I in an amount of about 0.001 to 95%.

[0215] The ready-to-use preparations contain compounds acting against parasites (preferably ectoparasites) in a concentration of 10 ppm to 80% by weight, preferably 0.1 to 65% by weight, more preferably 1 to 50% by weight, most preferably 5 to 40% by weight.

[0216] The preparations, which are diluted before use, contain the compound acting against ectoparasites in a concentration of 0.5 to 90% by weight, preferably 1 to 50% by weight.

[0217] Furthermore, the preparation contains a compound of the formula I acting against endoparasites in a concentration of 10 ppm to 2% by weight, preferably 0.05 to 0.9% by weight, very particularly preferably 0.005 to 0.25% by weight.

[0218] The solid formulations releasing the compounds of the present invention may be applied in a total amount of 10 mg to 300 mg, preferably 20 mg to 200 mg, most preferably 25 mg to 160 mg per kg of body weight of the animal to be treated for a period of 3 weeks.

[0219] The following examples illustrate the invention. [Example]

[0220] A. Compound Preparation Materials: Unless otherwise stated, reagents and solvents were purchased of the highest commercial quality and used without further purification. All reactions were monitored by thin-layer chromatography (TLC) using Merck silica gel 60F254 precoated plates (0.25 mm). Flash chromatography was performed using Agela technologies silica gel (Agela techno, silica irregular 40–60 μm, 60A, Cat. No. C-CS1400).

[0221] 1 H NMR spectra were recorded on a Bruker (500 MHz). Chemical shifts were determined using DMSO-d6 ( 1H;δ=2.50 ppm)( 1 H; δ = 2.50 ppm) and CD3OD ( 1 The NMR spectra were measured on a JEOL JMS-T100LP. ... The NMR spectra were measured on a JEOL JMS-T100LP. The NMR spectra were measured on a JEOL JMS-T100LP. The NMR spectra were measured on a JEOL JMS-T100LP. The NMR spectra were measured on a JEOL JMS-T100LP. The NMR spectra were measured on a JEOL J

[0222] Characterization: The compounds were characterized by high performance liquid chromatography coupled with mass spectrometry (HPLC / MS).

[0223] Method A: UHPLC-MS on a Shimadzu LCMS 2020 ESI. Analytical UHPLC column: C-18, 50 mm, 4.6 mm, 5 micron; mobile phase: 100 mM ammonium formate, B: acetonitrile; flow rate: 1.2 mL / min; injection volume: 1 μL at 1.50 min; gradient: 10% B to 100% B at 1.5 min, hold at 100% B for 1 min, 10% B at 2.51 min. Run time: 3 min at 400 °C. MS-method: ESI positive; mass range (m / z): 100-800.

[0224] Method B: Waters (ACQUITY-H Class UPLC. Analytical UHPLC Column), Mass Detector 3100: BEH-C-18, 50 mm, 2.1 mm, 1.7 micron; Mobile Phase: A: 0.1% formic acid in water, 10% IPA; B: 0.1% formic acid in acetonitrile; C: 20 mM ammonium formate in water. Flow rate: 1.2 mL / min; Injection volume: 1 μL at 1.50 min; Gradient: 10% A to 100% B in 1.5 min, hold at 100% B for 1 min, 10% B at 2.51 min. Run time: 3 min at 400 °C. MS-Method: ESI positive; Mass Range (m / z): 100-800.

[0225] Abbreviations used: min is minute; ACN is acetonitrile; DCM is dichloromethane; DMF is dimethylformamide; THF is tetrahydrofuran; mL is milliliter; min is minute; h is hour.

[0226] Synthesis Example 1: Preparation of 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one (compound I.1) Step 1: Preparation of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile To a stirred solution of 5-bromo-3-nitro-pyridine-2-carbonitrile (20 g, 0.087 mol) in DMF (200 mL) at -40 °C under a N2 atmosphere was added sodium ethanethiolate (11 g, 0.105 mol) in small portions over 30 minutes at -40 to -50 °C. The resulting reaction mixture was stirred at the same temperature for 10 minutes and then allowed to gradually reach a temperature of 20 to 25 °C with continued stirring for an additional hour. After completion of the reaction, the reaction mixture was quenched, extracted, and the organic layer was washed. The combined organic layers were dried and concentrated under reduced pressure to give a crude mass, which was purified by column chromatography to give 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile as a yellow solid (17 g; 82% yield). 1 NMR(500MHz,CDCl3):δ 8.52(s,1H),7.85(s,1H),3.07(q,2H,J=10Hz),1.43(t,3H,J=7.3Hz).LC-MS:[M+H] + Calculated mass: 243, measured mass: 244.

[0227] Step 2: Preparation of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone To a stirred solution of 5-bromo-3-ethylsulfanyl-pyridine-2-carbonitrile (17 g, 0.069 mol) in THF (170 mL) at 0°C under N2 atmosphere at 0°C to -5°C, methylmagnesium bromide (2 equiv.) was added dropwise over 30 minutes. The resulting reaction mixture was stirred at 0°C for 2 hours. After completion of the reaction, the above reaction mixture was quenched with a 1N aqueous solution of HCl (250 mL) and extracted with ethyl acetate. The organic layer was washed, dried, and concentrated under reduced pressure to give a crude mass, which was purified by crystallization. The resulting solid was filtered and dried under reduced pressure to give 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone as a yellow solid (14 g, 82% yield). 1 NMR(500MHz,DMSO):δ 8.57(s,1H),8.05(s,1H),3.01(q,2H,J=10Hz),2.59(s,3H),1.26(t,3H,J=7.3Hz).LC-MS:[M+H] + Calculated mass: 260, measured mass: 261.

[0228] Step 3: Preparation of 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone To a stirred solution of 1-(5-bromo-3-ethylsulfanyl-2-pyridyl)ethanone (3.9 g, 0.018 mol) in DCM (40 mL) at 0 °C, m-chloroperoxybenzoic acid (9.7 g, 0.039 mol) was added. The resulting reaction mixture was stirred at 20-25 °C for 3-4 hours. After completion of the reaction, the above reaction mixture was quenched and extracted. The organic layer was washed, dried, and concentrated under reduced pressure to give 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethanone (3.2 g, 82% yield) as an off-white solid. 1 NMR(500MHz,CDCl3):δ 9.12(s,1H),8.55(s,1H),3.55(q,2H J=12Hz),2.5(s,3H),1.20(t,3H,J=7Hz).LC-MS:M+H] + Calculated mass: 291, measured mass: 292.

[0229] Step 4: Preparation of 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]ethanone To a stirred solution of 1-(5-bromo-3-ethylsulfonyl-2-pyridyl)ethenone (10 gm, 0.342 mol) in dioxane (95 ml), 4-fluorophenylboronic acid (4.7 gm, 0.342 mol) was added and stirred for several minutes until a clear solution was obtained. 5 ml of HO was added to the reaction mass, followed by KCO (14.919 gm, 1.026 mol) and stirred for 5 minutes under continuous N purging via gas injection. Finally, Pd(PPh) (1.977 gm, 0.0171 mol) was added to the reaction mass. The reaction was then stirred at 100°C for 2 hours. After completion of the reaction, the reaction mass was cooled, quenched, and extracted. The organic layer was washed, dried and concentrated under reduced pressure to give a crude mass, which was purified by column to give 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]ethanone as an off-white solid (8 g, 82% yield). 1 H NMR(300MHz,DMSO-d6)δ 9.25(d,J=2.1Hz,1H),8.52(d,J=2.1Hz,1H),8.02-7.89(m,2H),7.49-7.35 (m,2H),3.60(q,J=7.4Hz,2H),2.54(s,3H),1.25(t,J=7.4Hz,3H).LC-MS:C 15 H 14 FNO3S[M] + Calculated mass: 307, measured mass: 308.

[0230] Step 5: Preparation of 2-bromo-1-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]ethanone To a stirred solution of 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]ethanone (3 g, 0.010 mol) in chloroform (30 mL) at 0° C., CH3COOH (30 mL) and HBr in acetic acid (30 mL) were added and stirred for several minutes. Subsequently, bromine (2 g, 0.012 mol) in CHCl3 was added. The resulting reaction mixture was heated to 60° C. for 1 hour. After completion of the reaction, the reaction mixture was quenched, extracted, and the organic layer was washed. The combined organic layers were dried and concentrated under reduced pressure to give a crude mass, which was purified by column chromatography to give 2-bromo-1-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]ethanone as an off-white solid (2.2 g, 82% yield). 1 H NMR(300MHz,DMSO-d6)δ 9.23(d,J=2.1Hz,1H),8.61(m,1H),7.92(ddd,J=8.7,5.3,2.7Hz,2H),7.43-7 .29(m,2H),4.90(s,2H),3.57(q,J=7.4Hz,2H),1.18(t,J=7.4Hz,3H).LC-MS:C 15 H 13 BrFNO3S[M] + The calculated mass is 386, and the measured mass is 386.1.

[0231] Step 6: Preparation of 1-benzyl-3-cyclopropyl-urea To a solution of cyclopropylamine (16 g, 0.281 mol, 1.5 eq.) and triethylamine (51 mL, 0.375 mol, 2 eq.) in DCM (dichloromethane) (1 L) was added a solution of benzyl isocyanate (25 g, 0.187 mol, 1 eq.) in DCM (dichloromethane) (100 mL) at 0 °C. The reaction mixture was gradually warmed to 20-25 °C and stirred for 1 h. After completion of the reaction, it was diluted with DCM until a clear solution was observed. The organic layer was treated with 1 M aqueous HCl (500 ml), followed by saturated aqueous NaHCO (500 mL). The combined organic extracts were washed with water and brine. It was then dried and concentrated to give 1-benzyl-3-cyclopropyl-urea (35 g, 97%) as a white solid. 1H NMR(300MHz,DMSO-d6)δ 7.37-7.16(m,5H),6.39(t,J=6.1Hz,1H),6.21(d,J=2.6Hz,1H),4.22(d,J=6.1Hz ,2H),2.43(tq,J=6.8,3.4Hz,1H),0.67-0.49(m,2H),0.40-0.29(m,2H).LC-MS:C 11 H 14 N2 O [M] + Calculated mass: 190, measured mass: 191.

[0232] Step 7: Preparation of 6-amino-1-benzyl-3-cyclopropyl-pyrimidine-2,4-dione To a stirred solution of 1-benzyl-3-cyclopropyl-urea (65 g, 0.3684 moles, 1 equiv.) and cyanoacetic acid (37.57 g, 0.4421 moles, 1.2 equiv.) at 0°C, acetic anhydride was added slowly. The resulting reaction mixture was stirred at 100°C for 3-4 hours. After completion of the reaction, the above reaction mixture was quenched and extracted. The organic layer was washed with water, dried, and concentrated under reduced pressure to give the intermediate, which was purified by column chromatography to give the desired intermediate (45 gm, 51%). The intermediate was then taken up in 10 volumes of water followed by treatment with an aqueous solution of 2N NaOH (4 volumes) at 20-25°C. The resulting reaction mixture was stirred at 20-25°C for 30 minutes, the precipitated white solid was separated and filtered through a Buckner funnel, and the resulting solid cake was washed with water and dried under reduced pressure to give 6-amino-1-benzyl-3-cyclopropyl-pyrimidine-2,4-dione as a white solid (42 g, 47%). 1 H NMR(500MHz,Chloroform-d)δ 7.45-7.31(m,4H),7.31-7.25(m,1H),5.19(s,2H),5.01(s,1H),2.74(tt,J=7.1,4.0Hz,1H),1.22-1.10(m,2H),0.94-0.83(m,2H).LC-MS:C 14 H 15 N3O2[M] + Calculated mass: 257, measured mass: 258.

[0233] Step 8: Preparation of 6-amino-3-cyclopropyl-1H-pyrimidine-2,4-dione To a stirred solution of 6-amino-1-benzyl-3-cyclopropyl-pyrimidine-2,4-dione (7 g, 0.0272 mol, 1 eq.) in CHOH (350 mL) at 25 °C, potassium formate (22.87 g, 0.2723 mol, 10 eq.) was added to obtain a clear solution, followed by the addition of 10% Pd / C (1.44 g, 0.05 eq.) at 20-25 °C while maintaining an inert atmosphere. The resulting reaction mixture was heated to 70 °C for 1.5 hours. After TLC confirmed the consumption of the starting material, the reaction mass was warmed to 50 °C, at which point the reaction mixture was filtered through a Celite bed. The Celite bed was then washed with hot CHOH (50 °C), and the filtrate containing the reaction mass was concentrated to dryness. 10 volumes of water were added to the concentrate. The pH was then adjusted to 5-6 using 6 N HCl at 0 °C. The resulting solid was filtered and washed with water to give 6-amino-3-cyclopropyl-1H-pyrimidine-2,4-dione as a white solid (yield 80-90%). 1 H NMR(500MHz,DMSO-d6)δ 10.10(s,1H),6.03(s,1H),4.42(d,J=1.7Hz,1H),2.33(td,J=7.1,3.6Hz,1H),0.79(t,J=6.9Hz,2H),0.55(p,J=5.2Hz,2H).LC-MS:C7H9N3O2[M] + Calculated mass: 167, measured mass: 168.

[0234] Step 9: Preparation of 6-amino-4-chloro-3-cyclopropyl-1,6-dihydropyrimidin-2-one To 6-amino-3-cyclopropyl-1H-pyrimidine-2,4-dione (0.5 gm) was slowly added POCl (1 mL) at 20-25°C, and the reaction mixture was then gradually heated to 130°C and stirred for 12 hours. The reaction was concentrated under reduced pressure to remove POCl. The reaction mixture was then slowly added to 4 volumes of ice water and adjusted to pH 10 with a 6N aqueous solution of NaOH to precipitate a solid. The solid was separated, filtered through a Buckner funnel, washed with water, and evaporated to dryness to give 6-amino-4-chloro-3-cyclopropyl-1,6-dihydropyrimidin-2-one as a yellow solid (60% yield). 1 H NMR(500MHz,DMSO-d6)δ 10.45(s,1H),7.13(d,J=2.1Hz,1H),3.57(d,J=2.1Hz,1H),2.92(s,1H),0.84(s,2H),0.64(s,2H).LC-MS:C7H8ClN3O[M] + Calculated mass: 185, measured mass: 186.

[0235] Step 10: Preparation of 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one (compound I.1) To a stirred solution of 6-amino-4-chloro-3-cyclopropyl-1,6-dihydropyrimidin-2-one (1 g, 5.34 mmol) in tert-butanol (10 mL) was added 2-bromo-1-[2-ethylsulfonyl-4-(4-fluorophenyl)phenyl]ethanone (2.04 g, 5.34 mmol). Molecular sieves were added to the above reaction mixture (1 g), and the resulting reaction mixture was heated to 95 °C for 16 hours. After completion of the reaction, the reaction mixture was filtered through a Celite bed, and the filtrate was collected and concentrated under reduced pressure to obtain a crude mass. The crude mass was purified by column chromatography to obtain 7-chloro-6-cyclopropyl-2-[2-ethylsulfonyl-4-(4-fluorophenyl)phenyl]imidazo[1,2-c]pyrimidin-5-one (0.75 g, 30.08% yield) as a yellow solid. 1 H NMR (300 MHz, DMSO-d6)1 H NMR(300MHz,DMSO-d6)δ 9.25(d,J=2.2Hz,1H),8.54(d,J=2.2Hz,1H),8.15(s,1H),7.99-7.89(m,2H),7.42(t,J=8.8 Hz,2H),7.12(s,1H),4.08(q,J=7.4Hz,2H),3.09(s,1H),1.25(m,5H),1.06(m,2H).LC-MS:C 22 H 18 ClFN4O3S[M] + Calculated mass: 472, measured mass: 473.

[0236] Synthesis Example 2: Preparation of 7-bromo-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one (compound I.4) To a stirred solution of 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one (compound I.1, 0.6 g, 1.2 mmol) in CH3COOH (6 mL), HBr (0.6 mL, 1.9 mmol) in CH3COOH was added, and the resulting reaction mixture was heated to 120 °C for 16 h. After the starting material was completed, the reaction mixture was poured into water (100 mL) and extracted with ethyl acetate. The organic layer was separated, dried, and concentrated to obtain a crude mass. The crude mass was then purified by column chromatography to obtain 7-bromo-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one as a beige solid (0.5 g, 75% yield). 1H NMR(500MHz,DMSO-d6)δ 9.26-9.22(m,1H),8.54(t,J=1.9Hz,1H),8.15(s,1H),7.97-7.91(m,2H),7.42(td,J=8.0,7.3,1.8Hz ,2H),7.26(s,1H),4.08(q,J=7.4Hz,2H),3.25(s,1H),1.25(m,3H),1.21(m,2H),1.06(m,2H).LC-MS:C 22 H 18 BrFN4O3S[M]+ The calculated mass is 517.3, and the measured mass is 519.2 [M+2].

[0237] Synthesis Example 3: Preparation of 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one (compound I.5) Step 1: Preparation of 5-fluoro-2-methyl-pyridin-3-amine A stirred solution of 2-bromo-5-fluoro-pyridin-3-amine (15 g, 78.53 mmol), trimethylboroxine 50% in THF (39.4 mL, 157.1 mmol), and KCO (27.13 g, 196.734 mmol) in 1,4-dioxane (120 mL) and HO (20 mL) was degassed under a N atmosphere for 15 minutes, followed by the addition of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (3.02 g, 3.92 mmol) complexed with CHCl. ​​The resulting reaction mixture was heated to 120 °C for 6–7 hours. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was separated, dried, and concentrated to give a crude mass. The crude mass was purified by column chromatography to give 5-fluoro-2-methyl-pyridin-3-amine (7 g, 60% yield). 1 H NMR(500MHz,DMSO-d6)δ:8.15(dd,J=8.1,1.9Hz,1H),8.11(dd,J=8.1,1.9Hz,1H),3.61(q,J=7.3Hz,2H),2.37(s,3H).LC-MS:C6H7FN2[M] + The calculated mass is 126.1, and the measured mass is 127.5 [M+1].

[0238] Step 2: Preparation of 6-bromo-5-fluoro-2-methyl-pyridin-3-amine To a stirred solution of 5-fluoro-2-methyl-pyridin-3-amine (9 g, 71.35 mmol) in CHCl (120 mL) was added N-bromosuccinimide (12.7 g, 71.35 mmol) at 0° C. The resulting reaction mixture was stirred at the same temperature for 10 minutes. After completion of the reaction, the reaction mixture was poured into water and extracted with CHCl. ​​The organic layer was washed with a saturated aqueous solution of sodium thiosulfate, and the separated organic layer was dried and concentrated to obtain a crude mass. The crude mass was purified by column chromatography to obtain 6-bromo-5-fluoro-2-methyl-pyridin-3-amine (9 g, 60% yield). 1 H NMR(500MHz,DMSO-d6)δ:8.11(dd,J=8.1,1.9Hz,1H),3.61(q,J=7.3Hz,2H),2.37(s,3H).LC-MS:C6H6BrFN2[M] + The calculated mass is 205, and the measured mass is 207 [M+2].

[0239] Step 3: Preparation of 1-(5-amino-3-fluoro-6-methyl-2-pyridyl)ethanone A stirred solution of 6-bromo-5-fluoro-2-methyl-pyridin-3-amine (9 g, 2.03 mmol) and tributyl(1-ethoxyvinyl)tin (23.78 mL, 2.03 mmol) in toluene (10 V, 100 mL) was degassed under N2 atmosphere for 10 minutes, followed by the addition of tetrakis-triphenylphosphine-palladium (2.53 g, 32.19 mmol). The resulting reaction mixture was heated to 120 °C for 6-7 hours. After completion of the reaction mixture, the reaction mixture was quenched with water and extracted with ethyl acetate. The organic layer was separated, dried, and concentrated to give a crude mass. The crude mass was purified by column chromatography to give 1-(5-amino-3-fluoro-6-methyl-2-pyridyl)ethanone (5 g, 50% yield). 1 H NMR(500MHz,DMSO-d6)δ:8.11(dd,J=8.1,1.9Hz,1H),3.61(q,J=7.3Hz,2H),2.37(s,3H),1.15-1.08(m,3H).LC-MS:C8H9FN2O[M] + The calculated mass is 168, and the measured mass is 168.1.

[0240] Step 4: Preparation of 1-(5-bromo-3-fluoro-6-methyl-2-pyridyl)ethanone To a stirred solution of 1-(5-amino-3-fluoro-6-methyl-2-pyridyl)ethanone (4.2 g, 24.97 mmol) in ACN (50 mL) was added Cu(I)Br (3.58 g, 24.97 mmol) and isopentyl nitrite (4.38 g, 37.46 mmol) at 0 °C. The resulting reaction mixture was stirred at the same temperature for 10 min, followed by stirring at 20-25 °C for 1 h. After completion of the reaction, the reaction mixture was filtered through a Celite pad, and the filtrate was poured into HO for extraction. The organic layer was separated, dried, and concentrated to give a crude mass. The crude mass was purified by column chromatography to give 1-(5-bromo-3-fluoro-6-methyl-2-pyridyl)ethanone (2.5 g, 40% yield). 1 H NMR(500MHz,DMSO-d6)δ:8.11(dd,J=8.1,1.9Hz,1H),2.37(s,3H),1.15-1.08(m,3H).LC-MS:C8H7BrFNO[M] + The calculated mass is 232, and the measured mass is 234 [M+2].

[0241] Step 5: Preparation of 1-[3-fluoro-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone A stirred solution of 1-(5-bromo-3-fluoro-6-methyl-2-pyridyl)ethanone (1.5 g, 6.46 mmol), (4-fluorophenyl)boronic acid (1.35 g, 9.69 mmol), and K2CO3 (1.78 g, 12.92 mmol) in 1,4-dioxane (10 mL) and water (2 mL) was degassed under a N2 atmosphere for 15 minutes, followed by the addition of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) (0.373 g, 0.323 mmol) complexed with DCM. The resulting reaction mixture was heated to 120 °C for 6 hours. After completion of the reaction, the reaction mixture was poured into water and extracted. The organic layer was separated, dried, and concentrated to give a crude mass. The crude mass was purified by column chromatography to give 1-[3-fluoro-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone (0.9 g, 66% yield). 1 H NMR(300MHz,Chloroform-d)δ 8.15(s,1H),7.46-7.05(m,4H),2.63(s,3H),1.53(s,3H).LC-MS:C 14 H 11 F2NO[M] + The calculated mass is 247.2, and the measured mass is 248.1 [M+1].

[0242] Step 6: Preparation of 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone To a stirred solution of 1-[3-fluoro-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone (0.8 g, 3.39 mmol) and sodium ethanesulfonate (0.898 g, 6.79 mmol) in dimethylacetamide (10 mL). The resulting reaction mixture was heated to 120° C. for 2 hours. After completion of the reaction, the reaction mixture was diluted with water and extracted. The organic layer was separated, dried, and concentrated to obtain a crude mass. The crude mass was purified by column chromatography to obtain 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone (0.88 g, 95% yield) as a pale yellow solid. 1H NMR(300MHz,Chloroform-d)δ 8.15(s,1H),7.46-7.05(m,4H),3.59(q,J=7.5Hz,2H),2.63(s,3H),1.53(s,3H),1.36(t,J=7.5Hz,3H).LC-MS:C 16 H 16 FNO3S[M] + The calculated mass is 321.3, and the measured mass is 322.1 [M+1].

[0243] Step 7: Preparation of 2-bromo-1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone To a stirred solution of 1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone (0.9 g, 3.39 mmol) and pyridinium bromide perbromide (0.94 g, 6.79 mmol) in dioxane (10 mL). The resulting reaction mixture was heated to 90° C. for 1.5 hours. After completion of the reaction, the reaction mixture was diluted with ice-cold water (100 mL) and extracted. The organic layer was separated, dried, and concentrated to obtain a crude mass. The crude mass was purified by column chromatography to obtain 2-bromo-1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone as a pale yellow solid (0.74 g, 60% yield). 1 H NMR(300MHz,Chloroform-d)δ 8.15(s,1H),7.46-7.05(m,4H),4.96(s,2H),3.59(q,J=7.5Hz,2H),2.63(s,3H),1.36(t,J=7.5Hz,3H).LC-MS:C 16 H 15 BrFNO3S[M] + The calculated mass is 400.2, and the measured mass is 402.0 [M+2].

[0244] Step 8: Preparation of 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one To a stirred solution of 4-amino-6-chloro-1-cyclopropyl-pyrimidin-2-one (0.4 g, 2.155 mmol) in tert-butanol (2 mL) was added 2-bromo-1-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]ethanone (1.03 g, 2.58 mmol). Molecular sieves were added to the above reaction mixture (0.1 g), and the resulting reaction mixture was heated to 100 °C for 24 hours. After completion of the reaction, the reaction mixture was filtered through a Celite bed, and the filtrate was collected and concentrated under reduced pressure to obtain a crude mass, which was purified by column chromatography to obtain 7-chloro-6-cyclopropyl-2-[3-ethylsulfonyl-5-(4-fluorophenyl)-6-methyl-2-pyridyl]imidazo[1,2-c]pyrimidin-5-one as a yellow solid (0.15 g, 30% yield). 1 H NMR(300MHz,DMSO-d6)δ 8.11(d,J=8.9Hz,2H),7.61(dd,J=8.5,5.5Hz,2H),7.39(t,J=8.8Hz,2H),7.12 (s,1H),4.01(q,J=7.4Hz,2H),2.58(s,3H),1.22(m,6H),1.06(s,2H).LC-MS:C 23 H 20 ClFN4O3S[M] + The calculated mass is 486.9, and the measured mass is 487.1.

[0245] By appropriately modifying the starting materials or intermediates thereto, and using the procedures described in the preparative examples above, further compounds of formula IA1, listed with physical data in Table B, were obtained. [ka]

[0246] [Table 1]

[0247] [Table 2]

[0248] Table 3

[0249] Table 4

[0250] Table 5

[0251] Table 6

[0252] Table 7

[0253] Table 8

[0254] Table 9

[0255] Table 10

[0256] Table 11

[0257] Table 12

[0258] [Table 13]

[0259] The wavy line represents the bond to the rest of the molecule.

[0260] Similarly, by appropriate modification of the starting materials or intermediates thereto, and using the procedures described in the preparative examples above, further compounds of formula IA2, listed with physical data in Table C, were obtained. [ka]

[0261] [Table 14]

[0262] Similarly, by appropriate modification of the starting materials or intermediates thereto, and using the procedures described in the preparative examples above, further compounds of formula IA3, listed with physical data in Table D, were obtained. [ka]

[0263] [Table 15]

[0264] B. Biological Examples The activity of the compounds of formula (I) of the present invention can be demonstrated and evaluated in the biological tests described below. Unless otherwise specified, test solutions are prepared as follows: the active compound is dissolved at the desired concentration in a mixture of distilled water:acetone 1:1 (vol:vol). Test solutions are prepared on the day of use. Test solutions are generally prepared at concentrations of 2500 ppm, 800 ppm, and 300 ppm (wt / vol).

[0265] B.1 Boll weevil (Anthonomus grandis) To evaluate control of boll weevil (Anthonomus grandis), test units consisted of 96-well microtiter plates containing insect bait and 5-10 A. grandis eggs. Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Five microliters of various concentrations of formulated compound were sprayed onto the insect bait in duplicate using a custom-made microatomizer. After application, the microtiter plates were incubated at approximately 25 ± 1°C and approximately 75 ± 5% relative humidity for 5 days. Egg and larval mortality (mortality) was then assessed visually. In this study, compounds I.1, I.2, I.3, I.4, I.5, I.6, I.8, I9, 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.25, I.26, I.27, I.28, I.29, I.32, I.33, I.46, I.47, I.48, I.49, and I.50 each at 800 ppm caused greater than 75% mortality compared to untreated controls.

[0266] B.2 Tobacco budworm (Heliothis virescens) To evaluate control of the false tobacco budworm (Heliothis virescens), test units consisted of 96-well microtiter plates containing insect bait and 15-25 H. virescens eggs. Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Various concentrations of formulated compounds were sprayed onto the insect bait in duplicate using a custom-made microatomizer in 10 μl volumes. After application, the microtiter plates were incubated at approximately 28 ± 1°C and approximately 80 ± 5% relative humidity for 5 days. Egg and larval mortality (mortality) was then assessed visually. In this study, compounds I.1, 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.25, I.26, I.27, I.28, I.29, I.30, I.32, I.36, I.37, I.47, I.48, I.49, and I.50 each at 800 ppm caused greater than 75% mortality compared to untreated controls.

[0267] B.3 Green Peach Aphid (Myzus persicae) To evaluate the control of green peach aphids (Myzus persicae) through systemic means, test units were constructed from 96-well microtiter plates containing a liquid artificial diet under an artificial membrane. Compounds were formulated using a solution containing 75% v / v water and 25% v / v DMSO. Various concentrations of the formulated compounds were transferred into the aphid diet in duplicate using a custom-made pipettor. After application, 5 to 8 adult aphids were placed on the artificial membrane within the microtiter plate wells. The treated aphid diet was then allowed to feed on and incubated for 3 days at approximately 23 ± 1°C and approximately 50 ± 5% relative humidity. Aphid mortality and reproduction were then assessed visually. In this study, compounds I.1, I.2, I.3, I.4, I.5, I.6, I.7, I.8, I.10, I.11, I.12, I.13, I.14, I.16, I.17, I.18, I.19, I.20, I.21, I.25, I.26, I.27, I.28, I.29, I.31, I.32, I.33, I.36, I.37, I.46, I.47, I.48, and I.49 each at 800 ppm caused greater than 75% mortality compared to untreated controls.

[0268] B.4 Diamond back moth (Plutella xylostella) The active compound is dissolved at the desired concentration in a 1:1 (vol:vol) mixture of distilled water:acetone. A surfactant (Kinetic) is added at a rate of 0.01% (vol / vol). Test solutions are prepared on the day of use. Cabbage leaf disks (60 mm diameter) are immersed in the test solution and allowed to air dry. Treated leaves are placed side-by-side with moistened filter paper in a Petri dish and inoculated with 10 third-instar larvae. Mortality is recorded 72 hours after treatment. Feeding damage is also recorded using a 0-100% scale. In this study, compounds I.1, I.2, I.3, I.4, I.5, I.6, I.7, I.8, I9, 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.25, I.26, I.27, I.28, I.29, I.30, I.31, I.32, I.33, I.36, I.37, I.45, I.46, I.47, I.48, I.49, and I.50 each at 800 ppm caused greater than 75% mortality compared to untreated controls.

[0269] B.5 Southern armyworm (Spodoptera eridania), 2nd instar larvae The active compounds were formulated in 100% cyclohexanone as 10,000 ppm solutions delivered via tube using a Tecan liquid handler. The 10,000 ppm solutions were serially diluted with 100% cyclohexanone to create intermediate solutions. These served as stock solutions, with final dilutions of 50% acetone:50% water (v / v) made by the Tecan and placed in 10- or 20-ml glass vials. A 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 an atomizing nozzle for plant / insect application. Two lima bean plants (Cieva cultivar) were grown per pot and selected for treatment at the first-true-leaf stage. The test solutions were sprayed onto the foliage using an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were allowed to dry in the sprayer's fume hood and then removed from the sprayer. Each pot was placed in a perforated plastic zip-top bag. 10-11 armyworm larvae were placed in the bag, and the bag was then resealed. Test plants were maintained in a growth chamber at approximately 25°C and 20-40% relative humidity for 4 days, avoiding direct exposure to fluorescent light (14:10 light:dark photoperiod) to prevent heat from being trapped inside the bag. Four days after treatment, mortality and feeding reduction were assessed compared to untreated control plants. In this study, compounds I.1, I.2, I.3, I.4, I.5, I.6, I.7, I.8, I9, 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.25, I.26, I.27, I.28, I.29, I.30, I.31, I.32, I.34, I.35, I.36, I.37, I.38, I.39, I.40, I.41, I-44, I.45, I.46, I.47, I.48, I.49, and I.50 each at 300 ppm caused greater than 75% mortality compared to untreated controls.

[0270] Comparison data:

[0271] [Table 16]

[0272] The comparative data show that despite the slight structural difference (in this case Cl / CF3), the compounds of the present application have significantly better activity.

Claims

1. Formula (I) 【Chemistry 1】 (In the formula, Rings A and B are fully unsaturated; Y is C=X, where X is O; E is N(R ３ ) and Q is N, N(R ５ ) or CH; G is phenyl or pyridyl; W is S, S(O), S(O) ２ , S(O)(NR Ｗ ), S(O)(NH); R １ is a halogen; R ３ , R ５ is independently an unsubstituted or halogenated C １ ~C ６ -Alkyl, C １ ~C ６ -alkoxy, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl, C ３ ~C ６ -cycloalkyl, C ３ ~C ６ -cycloalkyl-C １ ~C ４ - alkyl; Each R ７ are independently H, halogen, OH, CN; Unsubstituted or halogenated C １ ~C ６ -Alkyl, C ３ ~C ６ -cycloalkyl, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl; containing one or more of the same or different heteroatoms O, N or S and being unsubstituted or containing one or more R Ｈ a 3- to 12-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with unsubstituted or one or more R Ｊ phenyl substituted with; OR Ｋ ; -C(CN)(CH ３ ) ２ or 1-cyanocyclopropyl, Each R Ｈ are independently halogen, CN; １ ~C ３ -Alkyl, C １ ~C ３ -haloalkyl; Each R Ｊ are independently halogen, CN; unsubstituted or halogenated C １ ~C ６ -Alkyl, C １ ~C ６ -alkoxy or C １ ~C ６ - two adjacent substituents R Ｊ wherein the substituents form an alkyl bridge between two oxygens, which is unsubstituted or halogenated; Each R Ｋ is C １ ~C ６ -Alkyl, C ２ ~C ６ -alkenyl, C ２ ~C ６ -alkynyl, C ３ ~C ６ -cycloalkyl, which groups are unsubstituted or substituted with one or more identical or different substituents selected from halogen and CN; Each R Ｗ are independently １ ~C ４ alkyl or cyclopropyl; The subscript n is 1, 2, 3, or 4 when G is phenyl, or 1, 2, or 3 when G is pyridyl. and N-oxides, stereoisomers, tautomers and agriculturally or veterinarily acceptable salts thereof.

2. Formula (I.A) 【Chemistry 2】 wherein all variables have the meanings defined in relation to formula (I).

2. The compound of formula (I) according to claim 1, which is a compound of formula (I):

3. R ３ is unsubstituted or halogenated C １ ~C ３ -Alkyl or C ３ ~C ６ 3. The compound of formula (IA) according to claim 2, wherein: -cycloalkyl.

4. A compound of formula (I) according to any one of claims 1 to 3, wherein G is 2-pyridyl.

5. R Ｗ is C １ ~C ３ 5. The compound of formula (I) according to any one of claims 1 to 4, wherein - is alkyl.

6. A compound of formula (I) according to any one of claims 1 to 5, wherein the index n is 1 or 2.

7. R ７ teeth, halogen; C １ ~C ３ - alkyl, cyclopropyl; containing one or more of the same or different heteroatoms O or N and are unsubstituted or １ ~C ３ -Alkyl and C １ ~C ３ - a 6- to 9-membered saturated, partially unsaturated or fully unsaturated heterocyclic ring or ring system substituted with one or more substituents selected from haloalkyl; unsubstituted or one or more R Ｊ phenyl substituted with; or OR Ｋ (In the formula, R Ｋ is unsubstituted or substituted with CN １ ~C ３ -alkyl) A compound of formula (I) according to any one of claims 1 to 6, wherein

8. R ７ is -C(CN)(CH ３ ) ２ A compound of formula (I) according to any one of claims 1 to 7, selected from: and 1-cyanocyclopropyl.

9. A pesticidal composition comprising a compound of formula (I) according to any one of claims 1 to 8, an N-oxide or an agriculturally acceptable salt thereof and a further pesticidal component.

10. Use of a compound of formula (I) according to any one of claims 1 to 8 as an agrochemical pesticide.

11. 10. A method for combating or controlling invertebrate pests, comprising contacting the pests or their food sources, habitats or breeding sites with a pesticidally effective amount of at least one compound of formula (I) as defined in any one of claims 1 to 8 or a composition as defined in claim 9.

12. 10. A method for protecting growing plants from attack or infestation by invertebrate pests, comprising contacting the plants or the soil or water in which the plants are growing with a pesticidally effective amount of at least one compound of formula (I) as defined in any one of claims 1 to 8 or a composition as defined in claim 9.

13. Seeds comprising a compound of formula (I) according to any one of claims 1 to 8 or a composition according to claim 9 in an amount of 0.1 g to 10 kg per 100 kg of seeds.

14. Use of a compound of formula (I) as defined in any one of claims 1 to 8 or a composition as defined in claim 9 for protecting growing plants from attack or infestation by invertebrate pests.

15. 10. A method of treating or protecting an animal from infestation or infection by an invertebrate pest, comprising contacting the animal with a pesticidally effective amount of a compound of formula (I) as defined in any one of claims 1 to 8 or a composition as defined in claim 9.

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