N-substituted phenylpyrazoles and their use

Abstract

This invention relates to the preparation and use of a phenylpyrazole derivative. Specifically, this invention relates to an N-substituted phenylpyrazole derivative of formula (I) or its isotopically labeled compound, or its optical isomers, geometric isomers, tautomers, or mixtures of isomers, or its agronomically acceptable salt, and the use of said compound in the preparation of insecticides for pest control. Such compounds can achieve better pest control effects at lower dosages, particularly against pests of the orders Lepidoptera, Coleoptera, Homoptera, Hemiptera, Thysanoptera, Isoptera, Diptera, Hymenoptera, Trichophyton, Pseudocoptera, Orthoptera, Blattodea, Silicaria, Acari, and Nematodes.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, specifically relating to an N-substituted phenylpyrazole compound and its applications. Background Technology

[0002] With the development of modern green pesticides, pyrazole pesticides, characterized by high activity, low toxicity, and high selectivity, are increasingly widely used in insect control, acaricide, herbicide, and fungicide applications. However, long-term use of a particular pyrazole compound may lead to resistance in pests and mites. Therefore, among the currently developed new pesticide varieties, an increasing number of novel pyrazole insecticides, acaricides, herbicides, and fungicides are emerging, providing new avenues for finding highly effective and low-toxic new invertebrate pest control agents. Summary of the Invention

[0003] The purpose of this invention is to provide a new class of N-substituted phenylpyrazole compounds that can be used to control invertebrate pests, parasites, and sanitary pests, especially insects, arachnids, and nematodes in agronomy. Furthermore, these compounds can achieve better pest control effects with lower dosages.

[0004] To achieve the objective of this invention, the following technical solution is provided:

[0005] An N-substituted phenylpyrazole compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pesticide-acceptable salt thereof:

[0006]

[0007] Among them, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl.

[0008] R is selected from H, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methyl acetate, N,N-dimethylcarbamoyl, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropanecarbonyl, cyclohexyl, and phenyl.

[0009] Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, or adamantyl, provided that R is H, methyl, methyl acetate, N,N-dimethylcarbamoyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyclopropane ethyl, or cyclopropane carbonyl;

[0010] Alternatively, Q may be selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propyl, propynyl, isopropyl, butyl, isobutyl, propenyl, methoxy, ethoxy, propoxy, cyclopropyl, cyclohexyl, pyridyl, furanyl, thiophene, phenyl, phenylmethyl, adamantyl, and naphthyl.

[0011] Alternatively, Q may be selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, or phenyl.

[0012] The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl;

[0013] n is 0 or 1.

[0014] In some implementation schemes, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl.

[0015] R is selected from H, methyl, isopropyl, methoxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methyl acetate, N,N-dimethylcarbamoyl, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropane carbonyl, cyclohexyl, and phenyl.

[0016] When n=0, Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butylketone methyl, tert-butylketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl;

[0017] Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, cyclopropyl, furanyl, cyclohexyl, and phenyl;

[0018] R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: fluorine, chlorine, cyano, and methyl;

[0019] When n=1, Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butylketone methyl, tert-butylketone ethyl, provided that R is H, methyl, cyclopropyl, isopropyl, cyclopropylmethyl, cyclopropaneethyl, or cyclopropanecarbonyl.

[0020] Alternatively, Q may be selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thienyl, and phenyl.

[0021] Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl;

[0022] The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl;

[0023] In other embodiments, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl.

[0024] When n=0, R is selected from methyl, cyclopropylmethyl, and cyclopropane carbonyl;

[0025] Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl;

[0026] Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl;

[0027] R1 may be mono- or poly-substituted by one or more identical or different substituents, wherein the substituents are selected from: chloro, cyano, and methyl;

[0028] When n=1, R is selected from H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, and N,N-dimethylcarbamoyl.

[0029] Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoyl;

[0030] Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thiophene, and phenyl;

[0031] Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl;

[0032] The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl;

[0033] In other embodiments, when n=0, X1 and X5 are selected from chlorine, X2 and X4 are selected from hydrogen, and X3 is selected from heptafluoroisopropyl.

[0034] R is selected from H, methyl, cyclopropylmethyl, and cyclopropanecarbonylmethoxymethyl;

[0035] Q is selected from -C(=O)-R1, where R1 is selected from chlorine, methyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl;

[0036] Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl;

[0037] Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl.

[0038] R1 may be mono- or poly-substituted by one or more identical or different substituents, wherein the substituents are selected from: chloro, cyano, and methyl;

[0039] When n=1, X1 and X5 are selected from chlorine and fluorine, X2 and X4 are selected from hydrogen and fluorine, and X3 is selected from nitrile, trifluoromethyl, and heptafluoroisopropyl.

[0040] R is selected from H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoylmethoxy, cyclopropyl, cyclopropylmethyl, and phenyl.

[0041] Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoyl;

[0042] Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thiophene, and phenyl;

[0043] Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl;

[0044] The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl;

[0045] In other embodiments, the compounds are selected from the following.

[0046]

[0047]

[0048] To avoid ambiguity, the terms used in this article are defined below. Unless otherwise stated, the meanings of the terms used in this article are as follows.

[0049] The term "alkyl," used alone or in compound terms such as "alkathioyl" or "haloalkyl," includes straight-chain or branched alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, or various butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes, such as vinyl, 1-propenyl, 2-propenyl, and various butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and various butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include a moiety consisting of multiple triple bonds, such as 2,5-hexadiynyl. "Alkylene" refers to a straight-chain or branched alkanediyl group. The "alkyl", "alkenyl", and "alkynyl" groups may optionally be replaced by one or more (e.g., 1 to 5) suitable substituents.

[0050] The term "haloalkyl" refers to an alkyl group having one or more halogen substituents (at most fully haloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). For example, the term "C1-C6 haloalkyl" refers to a C1-C6 alkyl group having one or more halogen substituents (at most fully haloalkyl, i.e., each hydrogen atom of the alkyl group is replaced by a halogen atom). The term "C1 haloalkyl" refers to a methyl group having one, two, or three halogen substituents. Examples of haloalkyl groups include: CF3, C2F5, CHF2, CH2F, CH2CF3, CH2Cl, etc.

[0051] The term "alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and various butoxy, pentoxy, and hexoxy isomers. "Alkoxyalkyl" indicates alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2OCH2CH2.

[0052] The term "alkathioyl" includes branched or straight-chain alkathioyl moieties, such as methylthioyl, ethylthioyl, and various propylthio, butylthio, pentylthio, and hexylthio isomers. "Alkathioalkyl" indicates alkathioyl substitution on an alkyl group, examples of which include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, and CH3CH2SCH2CH2.

[0053] The term "alkyl carbonyl" refers to a straight-chain or branched alkyl moiety bonded to a C(=O) portion. Examples of "alkyl carbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)-, and (CH3)2CHC(=O)-. Examples of "alkoxy carbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O), and various butoxy carbonyl, pentoxy carbonyl, and hexoxy carbonyl isomers.

[0054] The term "cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "alkylcycloalkyl" indicates alkyl substitution on the cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl, and 4-methylcyclohexyl. The term "cycloalkylalkyl" indicates cycloalkyl substitution on the alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, cyclohexylmethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.

[0055] The term "halogen," alone or in compound terms such as "halogenated alkyl," or when used in descriptions such as "halogen-substituted alkyl," includes fluorine, chlorine, bromine, or iodine. Furthermore, when used in compound terms such as "halogenated alkyl," or when used in descriptions such as "halogen-substituted alkyl," the alkyl group may be partially or completely substituted with halogen atoms (which may be the same or different). Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O-, and CF3CH2O-. Examples of "halogenated alkylthio" include CCl3S-, CF3S-, CCl3CH2S-, and ClCH2CH2CH2S-.

[0056] The total number of carbon atoms in a substituent is indicated by the prefix "Ci-Cj", where i and j are numbers from 1 to 9. For example, C1-C4 alkyl represents methyl to butyl.

[0057] Various synthetic methods are known in this art for preparing aromatic and non-aromatic heterocyclic and cyclic systems; for a comprehensive review, see the eight-volume collection *Comprehensive Heterocyclic Chemistry*, edited by A.R. Katritzky and C.W., Pergamon Press, Oxford, 1984, and the twelve-volume collection *Comprehensive Heterocyclic Chemistry II*, edited by A.R. Katritzky, C.W. Rees and E.F. V. Criven, Pergamon Press, Oxford, 1996.

[0058] The compounds of the present invention can exist as one or more stereoisomers. Stereoisomers are isomers that have the same composition but whose atoms are arranged differently in space, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and blocked isomers. Blocked isomers arise from restricted rotation around a single bond, where the rotation barrier is high enough to allow the separation of isomer species. Those skilled in the art will understand that a stereoisomer may be more active and / or may exhibit beneficial effects when enriched relative to one or more other stereoisomers, or when separated from one or more other stereoisomers. In addition, those skilled in the art know how to separate, enrich, and / or selectively prepare said stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0059] The present invention also provides a method for preparing the above-mentioned phenylpyrazole compounds, as follows:

[0060] Synthesis Scheme 1:

[0061]

[0062] The specific steps include: 1) Dissolving raw material A in a suitable solvent and performing amide condensation with the corresponding R2-NH2 to obtain product B; 2) Dissolving raw material B in a suitable solvent and obtaining boric acid intermediate C under the action of boron donor and catalyst; 3) Product C is directly coupled with compound D via Suzuki coupling without further separation and purification to obtain target compound I.

[0063] Synthesis Scheme 2:

[0064]

[0065] The substituents are as described above. The specific steps include: dissolving raw material I in a suitable solvent, adding the corresponding halogenated compound, substituting under alkaline conditions, reacting at 0-120℃ for 1-24 hours to obtain target compound II.

[0066] Synthesis Scheme 3:

[0067]

[0068] The specific steps include: 1) dissolving raw material E in a suitable solvent and substituting it with the corresponding acyl chloride compound to obtain product F; 2) dissolving raw material F in a suitable solvent and substituting it with the corresponding halogen to obtain product G; 3) dissolving raw material G in a suitable solvent and obtaining boric acid intermediate H under the action of a boron donor and a catalyst; 4) without further separation and purification, product H is directly coupled with compound D via Suzuki coupling to obtain target compound III.

[0069] Furthermore, the present invention also lists several exemplary compounds that have been synthesized, the specific selection of which is shown in Tables 1 and 2 below. It should be understood that the scope of the present invention is not limited to the exemplary compounds listed in the tables below, and the selection of the groups in the compounds in Tables 1 and 2 below can be arbitrarily combined without particular limitation.

[0070] Table 1 General Formula (Ⅰ-1), n=0, X1, X2, X3, X4, X5, Q, R are detailed in the table below.

[0071]

[0072]

[0073]

[0074] Table 2 General Formula (Ⅰ-2), n=1, X1, X2, X3, X4, X5, Q, R are detailed in the table below.

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] In a second aspect, the present invention provides an insecticide composition comprising a compound of formula (I-1), formula (I-2) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt, and an acceptable carrier.

[0083] Acceptable carriers for the composition can be organic or inorganic inert carrier materials. Suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oils, polyalkylene glycols, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, brine, glycerin, ethanol, etc. Furthermore, the insecticide composition may also contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, flow aids, etc.

[0084] The formulation of the insecticide composition of the present invention can be a liquid, solid, or semi-solid formulation, without particular limitation. In some embodiments, the formulation of the insecticide composition is selected from powders, granules, liquids, suspensions, or sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, water-emulsions, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, large granules, granules for broadcasting and soil application, aerosols, ultra-low volume formulations, and wax products.

[0085] The content of the compounds of the present invention in their insecticide compositions can be adjusted according to actual needs (e.g., formulation, method of application, target of application, etc.), including but not limited to 0.001 mg / L-50 mg / L, such as 0.001 mg / L, 0.01 mg / L, 0.1 mg / L, 0.5 mg / L, 1 mg / L, 2.5 mg / L, 5 mg / L or 50 mg / L.

[0086] The specific application frequency can be determined by technical personnel in the relevant field, such as once a day, once every two days, once every three days, once every four days, once every five days, once every six days, twice a day, three times a day, etc.

[0087] In a third aspect, the present invention provides the use of compounds of formula (I-1), formula (I-2) or isotopically labeled compounds thereof, or optical isomers, geometric isomers, tautomers or mixtures of isomers thereof, or acceptable salts thereof, in the preparation of insecticides for pest control.

[0088] The compounds of this invention are suitable for the prevention and control of pests or mites, i.e., pests or mites refer to harmful or unwanted insects or mites, especially those encountered in agriculture, forestry, storage and material protection, as well as in the fields of hygiene and animal protection. The compounds of this invention are active against both generally sensitive and resistant species and are effective at all stages of pest or mite development.

[0089] This invention also relates to a method for controlling pests or mites, comprising applying an effective amount of a compound of formula (I-1) or (I-2) to the location of the insect, the insect habitat, the pest habitat, the area to be protected, or directly to the insect to be controlled. The compounds of this invention can also be used to control other invertebrate pests or organisms.

[0090] Specifically, the insect habitat, pest habitat, or mite habitat refers to the environment in which insects, pests, or mites live or where their eggs are present, including the surrounding air, the food they consume, or the objects they come into contact with. For example, by applying active compounds to the seeds of plants (before planting), to seedlings, or to planted cuttings, leaves, stems, fruits, grains, and / or roots, or to the soil or other growing media (before or after crop planting), it is possible to control insects or mites that consume, damage, or come into contact with edible agricultural products, ornamental plants, turf, forage plants, or other plants of economic value. It is also possible to protect these plants against diseases caused by viruses, fungi, or bacteria by controlling sap-feeding pests such as whiteflies, planthoppers, and aphids, or mites such as two-spotted spider mites and carmine spider mites. The plants include plants propagated through conventional methods, as well as plants genetically modified using modern biotechnology that possess insect or mite resistance, herbicide resistance, high yield, and / or other beneficial characteristics. These compounds are expected to be suitable for protecting fabrics, paper, stored grains, seeds and other foods, houses, buildings and / or places by applying the compounds of the present invention to or near these objects.

[0091] This invention has discovered that even at low doses, the compounds of this invention are effective in controlling animal pests encountered in agricultural and non-agricultural fields, as well as in the fields of hygiene and animal protection, particularly insects, arachnids, worms, nematodes, and mollusks. These compounds are preferably used as insecticides. They are effective against commonly susceptible and resistant species, and are resistant to all or part of the developmental stages. The aforementioned pests include:

[0092] Pests from the phylum Arthropoda, especially from the class Arachnida, such as those from the orders Acari, Metastigmata, and Mesostigmata, families Tetranychidae, Eupodidae, Eriophyiade, Phytoseiidae, and Acaridae, as well as species of mites (e.g., *Acarus siro*, *Aceria kuko*, *Aceriasheldoni*), *Aculops* spp., *Aculus* spp. (e.g., *Aculus fockeui*, *Aculus schlechtendali*), and *Amblyomma*. The following are genera of ticks: *Amphitetranychus viennensis*, *Argas*, *Boophilus*, *Brevipalpus* (e.g., *Brevipalpus phoenicis*), *Bryobia graminum*, *Bryobia praetiosa*, *Centruroides*, *Chorioptes*, *Dermanyssus gallinae*, *Dermatophagoides pteronyssinus*, *Dermatophagoides farinae*, *Dermacentor*, *Eotetranychus*, *Ornithodorus*, *Otobius*, and *Ixodes*. spp.), Haemophysalis spp., Hyalomma spp., Rhipicephalus spp. (the original genus of heteroparasitic mites), Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Varroa spp., Acarapis spp., etc.;

[0093] Pests from the order Coleoptera include, for example, the striped leaf beetle (Acalymma vittatum), the bean weevil (Acanthoscelides obtectus), the beetle (Adoretus spp.), the poplar leaf beetle (Agelasticaalni), the click beetle (Agriotes spp.) (e.g., the straight click beetle (Agriotes linneatus) and the wireworm (Agriotes mancus)), the black fungus beetle (Alphitobius diaperinus), the June beetle (Amphimallon solstitialis), the furniture thieving beetle (Anobium punctatum), the longhorn beetle (Anoplophoras spp.), the flower weevil (Anthonomus spp.) (e.g., the cotton boll weevil (Anthonomus grandis)), the round beetle (Anthrenus spp.), the pear weevil (Apion spp.), and the sugarcane beetle (Apogonia). spp.), genus *Atomaria* (e.g., *Atomaria linearis*), genus *Attagenus*, genus *Baris caerulescens*, genus *Bruchidius obtectus*, genus *Bruchus* (e.g., *Bruchus pisorum*, *Bruchus rufimanus*), genus *Cassida*, genus *Cerotoma trifurcata*, genus *Ceuthorhynchus* (e.g., *Ceutorrhynchus assimilis*, *Ceutorrhynchus quadridens*, *Ceutorrhynchus rapae*), genus *Chaetocnema* (e.g., sweet potato flea beetle (Chaetocnema confinis), Chaetocne madenticulata, corn flea beetle (Chaetocnema ectypa)), Cleonus mendicus, broad-breasted click beetle (Conoderus spp.), root weevil (Cosmopolites spp.) (e.g., banana black weevil (Cosmopolites sordidus)), etc.);

[0094] Pests from the order Diptera, such as those from the genera *Aedes* (e.g., *Aedes aegypti*, *Aedes albopictus*, *Aedes sticticus*, *Aedes vexans*), *Agromyza* (e.g., *Agromyza frontella*, *Agromyza parvicornis*), *Anastrepha* (e.g., *Anopheles quadrimaculatus*, *Anopheles gambiae*), *Asphondylia* (e.g., *Bactrocera* spp.), and *Bactrocera* (e.g., *Bactrocera cucurbitae*, *Bactrocera cucurbitae*). The following species are listed: *Calliphora dorsalis*, *Bactrocera oleae*, *Bibio hortulanus*, *Calliphora erythrocephala*, *Calliphora vicina*, *Ceratitis capitata*, *Chironomus* spp., *Chrysomyia* spp., *Chrysops* spp., *Chrysozona pluvialis*, *Cochliomyia* spp., and *Contarinia* spp. (e.g., *Contarinia johnsoni*, *Contarinia nasturtii*, *Contarinia pyrivora*, etc.).

[0095] Pests from the order Heteroptera, such as the pumpkin stink bug (Anasa tristis), *Antestiopsis* spp., *Boisea* spp., *Blissus* spp., *Calocoris* spp., *Campylomma livida*, *Cavelerius* spp., *Cimex* spp. (e.g., *Cimex adjunctus*, *Cimex hemipterus*, *Cimexlectularius*, *Cimex pilosellus*), *Collaria* spp., *Creontiades dilutus*, *Dasynus piperis*, *Diconocorishewetti*, and *Dysdercus*. spp.), Euschistus spp., etc.;

[0096] Pests from the order Homoptera, such as *Acizzia acaciaebaileyanae*, *Acizzia dodonaeae*, psyllids (*Acizzia uncatoides*), long-headed grasshoppers (*Acrida turrita*), aphids of the genus *Acyrthosipon* (e.g., pea aphid *Acyrthosiphon pisum*), *Acrogonia* spp., *Aeneolamia* spp., *Agonoscena* spp., European cabbage whitefly (*Aleyrodes proletella*), sugarcane whitefly (*Aleurolobus barodensis*), cotton whitefly (*Aleurothrixus floccosus*), malaynsis (*Allocaridara malayensis*), and mango leafhoppers of the genus *Amrascaspp.* (e.g., small green leafhopper *Amrasca bigutulla*, small leafhopper *Amrasca*). The genera *Aphis devastans*, *Aphis cardui*, *Aonidiella* spp. (e.g., *Aonidiella aurantii*, *Aonidiella citrina*, *Aonidiella inornata*), *Aphanostigma piri*, and *Aphis* spp. (e.g., *Aphis craccivora*, *Aphis fabae*, *Aphis forbesi*, *Aphis glycines*, *Aphis gossypii*, *Aphis hederae*, *Aphis illinoisensis*, *Aphismiddletoni*, *Aphis nasturtii*, *Aphis nerii*, etc.);

[0097] Pests from the order Hymenoptera, such as the genera *Acromyrmex* spp., *Athalia* spp. (e.g., *Athalia rosae*), *Atta* spp., *Diprion* spp. (e.g., *Diprion similis*), *Hoplocampa* spp. (e.g., *Hoplocampa cookei*, *Hoplocampa testudinea*), and *Lasius* spp., etc.;

[0098] Pests from the order Isoptera, such as the genera *Coptotermes* (e.g., *Coptotermes formosanus* in China), *Cornitermes cumulans*, *Cryptotermes*, *Incisitermes*, *Microtermesobesi*, *Odontotermes*, and *Reticulitermes* (e.g., *Reticulitermes flavipes*, *Reticulitermes hesperus*).

[0099] Pests from the order Lepidoptera, such as *Argyroploce* spp., *Anarsia* spp., *Choristoneura* spp., *Cnephasia* spp., *Conopomorpha* spp., as well as cotton bollworms (*Heliothis* spp.), cotton bollworms (*Helicoverpa* spp.), cutworms (*Spodoptera* spp.), armyworms (*Mythimna unipuncta*), cutworms (*Agrotis* spp.) (e.g., yellow cutworm *Agrotissegetum*, small cutworm *Agrotis ipsilon*), diamondback moth (*Earias* spp.), white-spotted cutworm (*Trichoplusia ni*), bean cutworm (*Anticarsia gemmatalis*), mint leafminer moth (*Rachiplusia nu*), diamondback moth (*Plutella xylostella*), and rice stem borer (*Chiloa* var. *japonica*). spp.), Rice stem borer (Scirpophaga incertulas), Chinese stem borer (Sesamia inferens), Rice leaf roller (Cnaphalocrocismedinalis), Corn borer (Ostrinia nubilalis), Cotton codling moth (Cydiapomonella), Peach fruit moth (Carposina niponensis), Leaf roller (Cacoecia spp.), Cotton brown leaf roller (Adoxophyes orana), Fruit tree yellow leaf roller (Archipsargyrospilus), Apple brown leaf roller (Pandemisheparana), Apple small leaf roller (Carpocapsa pomonella), Night leaf roller (Epinotia aporema), Grape and apple leaf roller (Eupoecilia ambiguella), Grape flower winged leaf roller (Lobesia botrana), Polychrosisbiteana, Cotton red bollworm (Pectinophora) The following are listed: cabbage caterpillar (Phierisrapae), cabbage looper (Phyllonorycterspp.), leaf miner (Leucoptera malifoliella), citrus leaf miner (Phyllocnisitis citrella), beet armyworm (Podoptera exigua Hübner), etc.

[0100] Pests from the orders Orthoptera or Saltatoria, such as house crickets (Achetadomesticus), Dichroplus spp., mole crickets (Gryllotalpa spp., e.g., European mole cricket (Gryllotalpa gryllotalpa)), cane grasshoppers (Hieroglyphus spp.), migratory locusts (Locusta spp., e.g., migratory locust (Locusta tamigratoria) and East Asian migratory locust (Locusta migratoria)), black locusts (Melanoplus spp., e.g., Melanoplus devastator), desert locusts (Schistocerca gregaria), mole crickets (Gryllotalpidae), etc.;

[0101] Pests from the order Phthiraptera, such as the genera *Damalinia* spp., *Haematopinus* spp., *Linognathus* spp., *Pediculus* spp., phylloxera vastatrix, pubic lice (*Ptirus pubis*), hairy lice (*Trichodectes* spp.), blood-sucking lice (*S. lice*), and pubic lice (*Pthirus pubis*).

[0102] Pests from the order Siphonapterida, such as those from the genera *Pulex*, *Ctenocephalides*, *Tunga*, *Xenopsylla*, and *Ceratophyllus*; particularly representative examples include *Ctenoce phalides canis*, *Ctenocephalides felis*, *Pulex irritans*, *Tungapenetrans*, and *Xenopsylla cheopis*.

[0103] Pests from the order Blattarida, such as: cockroaches, oriental cockroaches (Blatta orientalis), German cockroaches (Blattella germanica), American cockroaches (Periplaneta americana), long-bearded cockroaches (Supella longipalpa), Australian cockroaches (Periplaneta australasiae), brown-spotted cockroaches (Periplaneta brunnea), Pennsylvania wood cockroaches (Parcoblatta pennsylvanica), black-breasted cockroaches (Periplaneta fuliginosa), sugarcane cockroaches (Pycnoscelus surinamensis), and cockroaches of the genus Supella (e.g., Suppella longipalpa);

[0104] Pests from the order Thysanoptera, such as the corn thrips (Anaphothrips obscurus), rice thrips (Baliothrips biformis), grape thrips (Drepanothrisreuteri), Enneothrips flavens, thrips genus (Frankliniella spp.) (e.g., smoky brown thrips (Frankliniella fusca), western flower thrips (Frankliniella occidentalis), jasmine thrips (Frankliniella schultzei), wheat thrips (Frankliniella tritici), blueberry thrips (Frankliniella vaccinii), William's thrips (Frankliniella williamsi), sun thrips genus (Heliothrips spp.), greenhouse hedge thrips (Hercinothrips femoralis), grape thrips (Rhipiphorothrips cruentatus), and hard thrips genus (Scirtothrips). spp.), Taeniothrips cardamoni, Thrips spp. (e.g., Thrips palmi, Thrips tabaci), etc.;

[0105] Plant pests from the phylum Nematoda, i.e., plant-parasitic nematodes, especially those from the genera *Aglenchus* (e.g., *Aglenchus agricola*), *Anguinas* (e.g., wheat nematode *Anguina tritici*), *Aphelenchoides* (e.g., peanut nematode *Aphelenchoides arachidis*, strawberry nematode *Aphelenchoides fragariae*), *Belonolaimus* (e.g., small nematode *Belonolaimus gracilis*, long-tailed nematode *Belonolaimus longicaudatus*, Norton nematode *Belonolaimus nortoni*), and *Bursaphelenchus* (e.g., coconut red ring nematode *Bursaphelenchus*). The following nematodes are mentioned: *Cocophilus*, *Bursaphelenchus eremus*, *Bursaphelenchus xylophilus*, *Dirofilaria immitis*, *Meloidogynes pp.*, *Heterodera spp.*, *Hoplolaimus columbus*, *Belonolaimus spp.*, *Pratylenchus spp.*, *Rotylenchus reniformis*, *Criconemella ornata*, *Ditylenchus spp.*, *Aphelenchoides besseyi*, and *Hirschmanniella spp.*.

[0106] In another preferred embodiment of the present invention, the pests prevented and / or controlled by the compounds or compositions described in the present invention may be selected from diamondback moth, beet armyworm, rice stem borer, stem borer, western flower thrips, yellow-striped flea beetle, weevil, cutworm, leek gnat mosquito, Aedes albopictus, small cattle tick, cat flea, termite, red imported fire ant, etc.

[0107] Those skilled in the art will understand that the definitions and preferences described in one aspect of the invention also apply to other aspects. It will be apparent to those skilled in the art that embodiments of various aspects of the invention can be combined in various ways without departing from the subject matter and spirit of the invention, and these combinations are also included within the scope of the invention. Detailed Implementation

[0108] As mentioned in this disclosure, the term "invertebrate pests" includes arthropods, gastropods, nematodes, and worms that are of economic importance as pests. The term "arthropods" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and symphylans. The term "gastropods" includes snails, slugs, and other stylomatophores. The term "nematodes" includes members of the phylum Nematoda, such as herbivorous nematodes and animal-parasitic nematodes. The term "worm" includes all parasites, such as roundworms (Nematoda), heartworms (Nematoda, Secernentea), flukes (Platyhelminthes, Tematoda), acanthocephala, and tapeworms (Platyhelminthes, Cestoda).

[0109] In the context of this disclosure, “invertebrate pest control” means the suppression of the development of invertebrate pests (including death, reduced feeding and / or mating disturbance), and related expressions are similarly defined.

[0110] The term "agronomy" refers to the production of field crops such as those used for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, cereals (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other rapeseed crops), fruit vegetables (e.g., tomatoes, peppers, eggplants, cruciferous vegetables, and cucurbits), potatoes, other tuberous vegetables, onions, garlic, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone, and citrus), small fruits (e.g., berries and cherries), and other specialty crops (e.g., canola, sunflower, and olives).

[0111] The term “non-agricultural” refers to applications other than field crops, such as horticultural crops (e.g., greenhouses, nurseries, or ornamental plants not grown in fields), residential, agricultural, commercial, and industrial structures, turf (e.g., sod farms, pastures, golf courses, lawns, sports fields, etc.), timber products, stored products, agroforestry and vegetation management, public health (i.e., human) and animal health (e.g., domestic animals such as pets, livestock, and poultry, and non-domestic animals such as wild animals).

[0112] Non-agricultural applications include protecting animals from invertebrate parasitic pests by administering to the animals the disclosed compound (typically in the form of a composition formulated for veterinary use) in an effective (i.e., biologically effective) amount of the compound. As mentioned in this disclosure and the claims, the terms "parasitic" and "parasitic" refer to observable effects on invertebrate parasitic pests to protect animals from the pests. Parasitic effects are typically associated with reducing the presence or activity of the target invertebrate parasitic pest. Such effects on the pest include necrosis, death, stunted growth, reduced mobility or ability to remain on or within the host animal, reduced feeding, and reproductive inhibition. These effects on invertebrate parasitic pests control (including prevent, reduce, or eliminate) parasitic infestation or infection in animals.

[0113] The compounds of formula (I-1) and (I-2) of this invention can be synthesized using a variety of methods familiar to those skilled in the art of organic synthesis. The following specific examples provide exemplary methods for synthesizing compounds of formula (I-1) and (I-2), methods well-known in the field of synthetic chemistry. Clearly, by referring to the exemplary schemes in this patent, those skilled in the art can readily design synthetic routes for other compounds of formula (I-1) and (I-2) by appropriately adjusting the reactants, reaction conditions, and protecting groups.

[0114] The invention is further illustrated below with reference to specific embodiments; however, these embodiments do not limit the scope of the invention. Unless otherwise stated, all reactants used in the embodiments were obtained commercially; the instruments and equipment used in the synthesis experiments and product analysis were conventional instruments and equipment commonly used in organic synthesis.

[0115] Example 1: Synthesis of compounds 1-46

[0116]

[0117] Step 1: Synthesis of N-(5-bromo-2-chloropyridin-3-yl)acetamide

[0118] 5-Bromo-2-chloropyridin-3-amine (2.06 g, 10 mmol) and 30 mL of dichloromethane were placed in a reaction flask. Triethylamine (2.1 g, 20 mmol) was added at 0 °C, followed by the slow addition of acetyl chloride (1.17 g, 15 mmol). The mixture was stirred at room temperature for 5 h. After the reaction was completed, the mixture was quenched with water, extracted with dichloromethane, and the organic phases were combined. The organic phases were then rotary evaporated to give 2.43 g of a white solid product, with a yield of 98%. LC-MS: (M+1)m / z = 249.1.

[0119] Step 2: Synthesis of N-(5-bromo-2-chloropyridin-3-yl)-N-methylacetamide

[0120] N-(5-bromo-2-chloropyridin-3-yl)acetamide (1.98 g, 8 mmol) and 30 mL of tetrahydrofuran were placed in a reaction flask. 60% NaH (0.48 g, 12 mmol) was added in portions under ice bath conditions. After 30 min, iodomethane (1.7 g, 12 mmol) was slowly added. The mixture was stirred overnight at room temperature. The reaction was quenched with water to stop the reaction. The combined organic phases were extracted, and the solvent was removed by rotary evaporation to give 1.89 g of a white solid product, with a yield of 90%. LC-MS: (M+1) m / z = 263.1.

[0121] Step 3: Synthesis of compounds 1-46

[0122] N-(5-bromo-2-chloropyridin-3-yl)-N-methylacetamide (1.24 g, 5 mmol) and 30 mL of isopropanol were placed in a reaction flask, and tetrahydroxydiborane (0.45 g, 5 mmol), N,N-diisopropylethylamine (1.3 g, 10 mmol), and chloro[(n-butyldi(1-adamantyl)phosphine)-2-(2-aminobiphenyl)]palladium(II) (10 mmol) were added sequentially. The mixture was evacuated to nitrogen and reacted at 65 °C for 6 h. The reaction was monitored by TLC until it was complete, and then cooled to room temperature.

[0123] A solution of 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-iodo-1H-pyrazole (2.53 g, 5 mmol), potassium carbonate (2.08 g, 15 mmol), and 15 mL of H2O was added to the above reaction flask. Then, tetra(triphenylphosphine)palladium (10% mmol) was added. The mixture was evacuated and replaced with nitrogen. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was cooled to room temperature, extracted, dried, filtered, concentrated under reduced pressure, and purified by rapid column chromatography [petroleum ether / ethyl acetate (v / v) = 3 / 1] to give a pale yellow solid (2.03 g, yield: 72%).

[0124] 1H NMR (400MHz, DMSO-d6) δ8.84(s,1H),8.82(s,1H),8.55(s,1H),8.44(d,J=2.3Hz,1H),8.12(s,2H),3.13(s,3H),1.79(s,3H).

[0125] LC-MS: (M+1)m / z=563.1.

[0126] Example 2: Synthesis of Compound 2-1

[0127]

[0128] Step 1: Synthesis of 5-bromo-2-chloro-N-(2-cyanopropane-2-yl)nicotinamide

[0129] 5-Bromo-2-chloronicotinic acid (4.7 g, 20 mmol) and 50 mL of dichloromethane were placed in a reaction flask. Under ice bath conditions, oxalyl chloride (5.08 g, 40 mmol) was slowly added with stirring, followed by 0.1 mL of DMF as a catalyst. The mixture was heated to 40 °C and reacted for 2 h. After the reaction was complete, the mixture was cooled to room temperature, and the solvent and unreacted substances were removed by rotary evaporation under reduced pressure to obtain the acyl chloride for later use.

[0130] 1.85 g (22 mmol) of 2-amino-2-methylpropionitrile and 100 mL of dichloromethane were placed in a reaction flask. Triethylamine (3.03 g, 30 mmol) was added under ice bath conditions, followed by the slow dropwise addition of the acyl chloride obtained in the previous step. After completion, the reaction was stirred overnight at room temperature. 500 mL of water was added and stirred to stop the reaction. The mixture was allowed to stand and separate into layers. The aqueous layer was extracted with ethyl acetate. The organic phases were combined, and the solvent was removed by rotary evaporation to give 5.84 g of white solid. Yield: 97%. LC-MS: (M+1) m / z = 302.1.

[0131] Step 2: Synthesis of Compound 2-1

[0132] 5-Bromo-2-chloro-N-(2-cyanopropane-2-yl)nicotinamide (1.51 g, 5 mmol) and 30 mL of isopropanol were placed in a reaction flask, and tetrahydroxydiborane (0.90 g, 10 mmol), N,N-diisopropylethylamine (1.29 g, 10 mmol), and chloro[(n-butyldi(1-adamantyl)phosphine)-2-(2-aminobiphenyl)]palladium(II) (10 mmol) were added sequentially. The mixture was evacuated to nitrogen and reacted at 65 °C for 6 h. The reaction was monitored by TLC until it was complete, and then cooled to room temperature.

[0133] A solution of 1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-4-iodo-1H-pyrazole (2.53 g, 5 mmol), potassium carbonate (2.07 g, 15 mmol), and 15 mL of H2O was added to the above reaction flask. Then, tetra(triphenylphosphine)palladium (10% mmol) was added. The mixture was evacuated and replaced with nitrogen. The reaction was carried out overnight at 80 °C. After the reaction was completed, the mixture was cooled to room temperature, extracted, dried, filtered, concentrated under reduced pressure, and purified by rapid column chromatography [petroleum ether / ethyl acetate (v / v) = 3 / 1] to give a pale yellow solid (1.83 g, yield: 61%).

[0134] 1 H NMR(400MHz,Chloroform-d)δ8.73(d,J=2.5Hz,1H),8.45(d,J=2.5Hz,1H),8.20 (d,J=0.7Hz,1H),8.00(d,J=0.7Hz,1H),7.78(s,2H),6.93(s,1H),1.89(s,6H).

[0135] LC-MS: (M+1)m / z = 602.1.

[0136] Example 3: Synthesis of compounds 2-6

[0137]

[0138] 2-Chloro-N-(2-cyano-2-yl)-5-(1-(2,6-dichloro-4-(perfluoropropane-2-yl)phenyl)-1H-pyrazol-4-yl)nicotinamide (0.60 g, 1 mmol) and 30 mL of THF were placed in a single-necked flask. Under ice bath conditions, 60% NaH (0.06 g, 2 mmol) was added in portions. After 30 min, iodomethane (0.28 g, 2 mmol) was slowly added to the reaction system, and the reaction was stirred overnight at room temperature. The reaction was stopped by adding water (30 mL). The aqueous phase was extracted with ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was separated by silica gel column chromatography [petroleum ether / ethyl acetate (v / v) = 10 / 1] to give a white solid (0.62 g, yield: 90%).

[0139] 1 H NMR(400MHz,Chloroform-d)δ8.69(d,J=2.4Hz,1H),8.17(d,J=0.7Hz,1H),7.97 (d,J=0.7Hz,1H),7.89(d,J=2.5Hz,1H),7.78(s,2H),3.02(s,3H),1.93(s,6H).

[0140] LC-MS: (M+1)m / z = 616.0.

[0141] By combining the synthesis methods of Reference Examples 1, 2 or 3, and the synthesis schemes of the present invention 1, 2 or 3, using the corresponding raw materials and conditions, or by referring to the preparation methods in the prior art, the target compounds in Table 3 can be obtained.

[0142] Table 3. Structural and characterization data of exemplary compounds.

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151]

[0152]

[0153]

[0154]

[0155]

[0156] Bioactivity assay

[0157] This embodiment tested the insecticidal activity of some compounds against diamondback moth, beet armyworm, and western flower thrips.

[0158] The specific implementation process is as follows:

[0159] 1) Compound preparation: Weigh a certain mass of the active ingredient using an analytical balance (0.0001g), dissolve it in N,N-dimethylformamide containing 1‰ Tween-80 emulsifier to prepare a 1% stock solution, and then dilute it with distilled water for later use.

[0160] 2) Test methods

[0161] 2.1 Determination of activity against diamondback moth

[0162] Leaf immersion method: Soak an appropriate amount of radish / corn leaves thoroughly in the prepared solution for 30 seconds, then place them in a plastic petri dish lined with filter paper to air dry naturally. Inoculate each dish with 8 2nd-3rd instar diamondback moths and place it in an observation room at 22℃ under 16 / 8h light. Observe after 48 hours; gently touch the insects with a brush; no reaction indicates dead insects. Each treatment was repeated 3 times, with a solvent control included. The experimental concentration was 20 mg / L.

[0163] Among the tested compounds, compounds 1-5, 1-6, 1-19, 1-23, 1-24, 1-25, 1-46, 1-62, 2-1, 2-2, 2-6, 2-7, 2-8, 2-9, 2-13, 2-19, 2-20, 2-25, 2-26, 2-41, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-78, 2-82, 2-83, 2-90, and 2-115 showed significant control efficacy against diamondback moth at a concentration of 20 mg / L, with a mortality rate of 100%.

[0164] 2.2 Determination of activity against beet armyworm

[0165] Artificial feed film method: While still hot, pour 2.5 ml of the prepared artificial feed into each well of a 12-well plate. Allow the feed to cool completely before use. Prepare three 12-well plates for each concentration gradient of each agent, with each 12-well plate representing one replicate, for a total of three replicates. Add 50 μL of the corresponding concentration gradient agent to each well and allow to dry. Inoculate one beet armyworm larva into each well. For the control, prepare three 12-well plates (three replicates), adding 50 μL of solvent to each well as a control. Place the plates in a rearing room at 26±2℃, with a light intensity of 16h:8h (L:D) and humidity of 50-70%. Insect mortality is assessed 48 hours after the experiment, and the mortality rate is recorded. The experimental concentration is 50 mg / L.

[0166] Among the tested compounds, compounds 1-5, 1-6, 1-19, 1-23, 1-24, 1-25, 1-46, 1-62, 2-1, 2-2, 2-6, 2-7, 2-8, 2-9, 2-13, 2-19, 2-20, 2-25, 2-26, 2-41, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-78, 2-82, 2-83, 2-90, and 2-115 showed significant control efficacy against the beet armyworm at a concentration of 50 mg / L, with a mortality rate of 100%.

[0167] 2.3 Determination of activity against western flower thrips

[0168] Leaf immersion method: Select rice seedlings that have grown for 3 weeks and are about 25cm tall in 5cm diameter flowerpots, about 30 seedlings per pot. Remove old and dead leaves. Pour a small amount of agar onto the surface soil of the flowerpot for fixation. After the agar solidifies, set aside. Immerse the rice seedlings in the solution for 10 seconds, then remove and air dry until no water remains. Cut the rice stems at the base, remove the upper leaves, leaving 5.5-6cm of stem. Place the stems in pre-prepared 6.5cm diameter petri dishes, with 4 layers of filter paper at the bottom of each dish and 3mL of sterile water added to maintain humidity. Each dish contains 15 stems. Use a brush to pick 10 mid-second instar larvae of the rice stem borer into each dish, cover with two layers of black cotton cloth, and then cover the petri dish to prevent the larvae from escaping. Each experiment has 5-6 treatments, and each treatment is repeated 3 times. The treated rice stem borer larvae were placed in an incubator at 25℃, RH=70%, and a photoperiod of L:D=16:8. After 48 hours, the mortality rate of the larvae was checked; death was defined as the inability to move coordinately when the larvae were lightly touched with a brush. The experimental concentration was 50 mg / L.

[0169] Among the tested compounds, compounds 1-5, 1-6, 1-19, 1-23, 1-24, 1-25, 1-46, 1-62, 2-1, 2-2, 2-6, 2-7, 2-8, 2-9, 2-13, 2-19, 2-20, 2-25, 2-26, 2-41, 2-56, 2-57, 2-58, 2-59, 2-60, 2-61, 2-62, 2-63, 2-64, 2-65, 2-66, 2-78, 2-82, 2-83, 2-90, and 2-115 showed significant control efficacy against western flower thrips at a concentration of 50 mg / L, with a mortality rate of 100% in all cases.

[0170] Experimental results show that the compounds of this invention exhibit high mortality rates against diamondback moth, beet armyworm, and western flower thrips at different dosages and using different testing methods. Other compounds of general formula (I-1) and formula (I-2) obtained through the preparation process described above also possess the corresponding properties, achieving unexpected effects.

[0171] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

[0172] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An N-substituted phenylpyrazole compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer, or mixture of isomers thereof, or a pesticide-acceptable salt thereof: in, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl. R is selected from H, methyl, ethyl, propyl, isopropyl, methoxy, ethoxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methyl acetate, N,N-dimethylcarbamoyl, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropanecarbonyl, cyclohexyl, and phenyl. Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, or adamantyl, provided that R is H, methyl, methyl acetate, N,N-dimethylcarbamoyl, isopropyl, cyclopropyl, cyclopropylmethyl, cyclopropane ethyl, or cyclopropane carbonyl; Alternatively, Q may be selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propyl, propynyl, isopropyl, butyl, isobutyl, propenyl, methoxy, ethoxy, propoxy, cyclopropyl, cyclohexyl, pyridyl, furanyl, thiophene, phenyl, phenylmethyl, adamantyl, and naphthyl. Alternatively, Q may be selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, or phenyl. The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl; n is 0 or 1.

2. The compound of formula (I) according to claim 1, or its isotopically labeled compound, or its optical isomer, geometric isomer, tautomer, or mixture of isomers, or its pesticide-acceptable salt, wherein, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl. R is selected from H, methyl, isopropyl, methoxy, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, methyl acetate, N,N-dimethylcarbamoyl, cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropane carbonyl, cyclohexyl, and phenyl. When n=0, Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butylketone methyl, tert-butylketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl; Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, cyclopropyl, furanyl, cyclohexyl, and phenyl; R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: fluorine, chlorine, cyano, and methyl; When n=1, Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butylketone methyl, tert-butylketone ethyl, provided that R is H, methyl, cyclopropyl, isopropyl, cyclopropylmethyl, cyclopropaneethyl, or cyclopropanecarbonyl. Alternatively, Q may be selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thienyl, and phenyl. Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl; The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl.

3. The compound of formula (I) according to claim 1, or its isotopically labeled compound, or its optical isomer, geometric isomer, tautomer, or mixture of isomers, or its pesticide-acceptable salt, wherein, X1, X2, X3, X4, and X5 are each independently selected from hydrogen, fluorine, chlorine, cyano, trifluoromethyl, and heptafluoroisopropyl. When n=0, R is selected from methyl, cyclopropylmethyl, and cyclopropane carbonyl; Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl; Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl; R1 may be mono- or poly-substituted by one or more identical or different substituents, wherein the substituents are selected from: chloro, cyano, and methyl; When n=1, R is selected from H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, and N,N-dimethylcarbamoyl. Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoyl; Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thiophene, and phenyl; Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl; The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl.

4. The compound of formula (I) according to claim 1, or its isotopically labeled compound, or its optical isomer, geometric isomer, tautomer, or mixture of isomers, or its pesticide-acceptable salt, wherein, When n=0, X1 and X5 are selected from chlorine, X2 and X4 are selected from hydrogen, and X3 is selected from heptafluoroisopropyl. R is selected from H, methyl, cyclopropylmethyl, and cyclopropanecarbonylmethoxymethyl; Q is selected from -C(=O)-R1, where R1 is selected from chlorine, methyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl; Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is methyl, cyclopropylmethyl, or cyclopropanecarbonyl; Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, vinyl, propynyl, isopropyl, vinyl, cyclopropyl, furanyl, cyclohexyl, and phenyl. R1 may be mono- or poly-substituted by one or more identical or different substituents, wherein the substituents are selected from: chloro, cyano, and methyl; When n=1, X1 and X5 are selected from chlorine and fluorine, X2 and X4 are selected from hydrogen and fluorine, and X3 is selected from nitrile, trifluoromethyl, and heptafluoroisopropyl. R is selected from H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoylmethoxy, cyclopropyl, cyclopropylmethyl, and phenyl. Q is selected from R1, where R1 is selected from H, methyl, methoxy, propoxy, ethyl, ethoxy, methoxyethyl, ethoxymethyl, ethoxyethyl, acetyl, isopropyl, propoxy, propionyl, acryloyl, butyl, isobutyl, isobutylenyl, isobutyryl, butoxy, butynyl, cyclohexanecarbonyl, phenyl, cyclohexylmethoxy, phenylmethoxy, tert-butyl ketone methyl, tert-butyl ketone ethyl, provided that R is H, methyl, methoxy, cyclopropyl, isopropyl, cyclopropanemethyl, cyclopropaneethyl, cyclopropanecarbonyl, methyl acetate, N,N-dimethylcarbamoyl; Or Q is selected from -C(=O)-R1, where R1 is selected from methyl, ethyl, propyl, propenyl, propoxy, cyclopropyl, pyridyl, furanyl, thiophene, and phenyl; Or Q is selected from -SO2-R1, where R1 is selected from methyl, ethyl, propyl, butyl, cyclopropyl, pyridyl, and phenyl; The R1 may be mono- or poly-substituted by one or more of the same or different substituents, wherein the substituents are selected from: halogen, cyano, methyl, methoxy, trifluoromethyl, trifluoromethoxy, N,N-dimethylamino, cyclopropyl, tert-butyl.

5. The compound of formula (I) according to claim 1, or an isotopically-labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer, or a mixture of isomers thereof, or a pesticidal ly-acceptable salt thereof, wherein, The following compounds can be selected:

6. An active composition comprising a compound of formula (I) according to any one of claims 1-5, or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt, and an acceptable support.

7. The active composition according to claim 6, wherein the dosage form is selected from powder, bait, granules, liquid, suspension or spray, preferably wettable powder, wettable liquid, soluble powder, dispersible liquid, aqueous solution, microemulsion, emulsifiable concentrate, water emulsion, sprayable solution, dispersible oil suspension, microcapsule suspension, water-dispersible granules, water-soluble granules, large granules, granules for broadcasting and soil application, aerosols, ultra-low volume formulations and wax products.

8. Use of the compound of formula (I) according to any one of claims 1-5, or its isotopically labeled compound, or its optical isomer, geometric isomer, tautomer or mixture of isomers, or an acceptable salt thereof, in the preparation of an insecticide for pest control.

9. The use according to claim 8, wherein the pest is selected from pests belonging to the phylum Arthropoda, order Coleoptera, order Diptera, order Heteroptera, order Homoptera, order Hymenoptera, order Isoptera, order Lepidoptera, order Orthoptera, order Pseudocoptera, order Thysanoptera, and phylum Nematoda.

10. The use according to claim 9, wherein the pest is selected from diamondback moth, beet armyworm, and western flower thrips.

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