Phenyl amide derivative as well as preparation and application thereof

Abstract

The invention relates to a phenylamide derivative as well as preparation and application thereof. Specifically, the invention relates to a compound as shown in a formula (I), or an isotope labeled compound thereof, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture thereof, or an acceptable salt, and application of the compound in preparation of a pesticide for pest control, the invention also relates to the use thereof for the control of insects, arachnids and nematodes in agriculture, and for the control of ectoparasites in non-agriculture. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of medicinal chemistry, and particularly to a phenylamide derivative and its preparation and application. Background Art

[0002] As is well known, specific phenyl-substituted compounds have a variety of bioactive functions. The damage caused by invertebrate pests is widespread in the fields of agriculture, forestry, greenhouse crops, ornamental plants, nursery crops, stored food, livestock, living quarters, turf, wood products, and public health, causing great losses to economic property and life health. Due to the increasing resistance of many current commercial pesticides, higher doses are required to kill pests, imposing a great burden on the environment. Therefore, there is a continuous need for new compounds that are more effective, more economical, less toxic, safer for the environment, or have different action sites to control invertebrate pests.

[0003] Patents CN105873906A and CN106103414A disclose the control effects of compounds similar to those of the present invention on various pests, while the compounds involved in the present invention are not disclosed. Summary of the Invention

[0004] The present invention relates to a phenylamide derivative, which has a novel structure and is applicable to agricultural and non-agricultural uses. It can be used to control invertebrate pests, parasites, and sanitary pests, etc., and particularly has excellent control effects on pests such as insects, arachnids, and nematodes in agriculture, and ectoparasites in non-agriculture.

[0005] Specifically:

[0006] On the one hand, the present invention provides a phenylamide derivative, which is a compound represented by formula (I) or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer, or isomer mixture, or an acceptable salt:

[0007]

[0008] Wherein,

[0009] X1, X2, X3, X4 are each independently selected from hydrogen, halogen, hydroxyl, nitro, amino, cyano, carboxyl, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-12 cycloalkyl, C 1-6 haloalkyl, C 1-6 alkoxy, or C 1-6 haloalkoxy;

[0010] R1 is selected from C 1-6 alkyl, C 2-6 alkenyl, C2-6 Alkynyl, C 3-12 Cycloalkyl, C 3-6 Heterocyclic group, C 6-12 Aryl, C 5-12 Heteroaryl, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, C 1-6 Alkylamino C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, C 3-6 Heterocyclic group C 1-6 Alkyl, C 6-12 Aryl C 1-6 Alkyl, C 5-12 Heteroaryl C 1-6 Alkyl, C 6-12 Aryloxy C 1-6 Alkyl, C 5-12 Heteroaryloxy C 1-6 Alkyl,

[0011] or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 1-6 Alkylamino, C 3-12 Cycloalkyl, C 3-8 Heterocyclic group, C 6-12 Aryl, C 6-12 Aryloxy, C 5-12 Heteroaryl, C 5-12 Heteroaryloxy, C 1-6 Alkoxy C 1-6 Alkyl, C 1-6 Alkylthio C 1-6 Alkyl, C 1-6 Alkylamino C 1-6 Alkyl, C 3-12 Cycloalkyl C 1-6 Alkyl, C 3-6 Heterocyclic group C 1-6 Alkyl, C 6-12 Aryl C 1-6 Alkyl, C 5-12 Heteroaryl C 1-6 Alkyl, C 6-12 Aryloxy C 1-6 Alkyl, C 5-12 Heteroaryloxy C 1-6 Alkyl;

[0012] and R1 and R2 may be mono- or poly-substituted by one or more identical or different substituents selected from: halogen, cyano, nitro, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl, C 1-6 alkoxycarbonyl, C 1-3 alkylamino, C 3-6 cycloalkyl, C 3-6 epoxyalkyl, C 6-12 aryl;

[0013] R3 is selected from hydrogen, halogen, hydroxy, cyano, nitro, amino, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 1-6 haloalkyl, C 2-6 haloalkenyl, C 2-6 haloalkynyl;

[0014] In some embodiments, X1, X2, X3, X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxy, C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy;

[0015] R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-12 aryl, C 5-12 heteroaryl, C 1-3 alkoxyC 1-3 alkyl, C 1-3 alkylthioC 1-3 alkyl, C 1-3 alkylaminoC 1-3 alkyl, C 3-12 cycloalkylC 1-3 alkyl, C 3-6 heterocyclic groupC 1-3 alkyl, C 6-12 arylC 1-3 alkyl, C 5-12 heteroarylC 1-3 alkyl, C 6-12 aryloxyC 1-3 alkyl, C5-12 Heteroaryloxy C 1-3 alkyl,

[0016] or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 6-12 aryloxy, C 5-12 heteroaryl, C 5-12 heteroaryloxy, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, C 1-3 alkylamino C 1-3 alkyl, C 3-8 cycloalkyl C 1-3 alkyl, C 3-6 heterocyclic group C 1-3 alkyl, C 6-12 aryl C 1-3 alkyl, C 5-12 heteroaryl C 1-3 alkyl, C 6-12 aryloxy C 1-3 alkyl, C 5-12 heteroaryloxy C 1-3 alkyl,

[0017] and R1 and R2 may be mono- or poly-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 1-3 alkoxycarbonyl, C 1-3 alkylamino, C 6-12 aryl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl.

[0018] R3 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl, C 3-8 cycloalkyl or C 1-4 haloalkyl.

[0019] In some other embodiments, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, nitro, amino, cyano, carboxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy;

[0020] R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocycloalkyl, C 6-9 aryl, C 5-9 heteroaryl, C 1-3 alkoxyC 1-3 alkyl, C 1-3 alkylthioC 1-3 alkyl, C 1-3 alkylaminoC 1-3 alkyl, C 3-6 cycloalkylC 1-3 alkyl, C 3-6 heterocycloalkylC 1-3 alkyl, C 6-9 arylC 1-3 alkyl, C 5-9 heteroarylC 1-3 alkyl,

[0021] or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocycloalkyl, C 6-12 aryl, C 5-12 heteroaryl, C 1-3 alkoxyC 1-3 alkyl, C 1-3 alkylthioC 1-3 alkyl, C 3-8 cycloalkylC 1-3 alkyl, C 3-6 heterocycloalkylC 1-3 alkyl, C 6-12 arylC 1-3 alkyl, C 5-12 heteroarylC 1-3 alkyl,

[0022] And R1 and R2 may be mono- or poly-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 1-3 alkoxycarbonyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl;

[0023] R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl or halo C 1-4 alkyl.

[0024] In some other embodiments, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, nitro, amino, cyano, carboxyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy;

[0025] R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-9 aryl, C 5-9 heteroaryl, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, C 1-3 alkylamino C 1-3 alkyl, C 3-6 cycloalkyl C 1-3 alkyl, C 3-6 heterocyclic group C 1-3 alkyl, C 6-9 aryl C 1-3 alkyl, C 5-9 heteroaryl C 1-3 alkyl,

[0026] or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C6-12 Aryl, C 5-12 heteroaryl,

[0027] and R1, R2 may be monosubstituted or polysubstituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl;

[0028] R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl or halo C 1-4 alkyl.

[0029] In other embodiments, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, cyclopropyl, C 1-3 alkyl or C 1-3 haloalkyl;

[0030] R1 is selected from methyl, ethyl, propyl, allyl, propargyl, cyclopropylmethyl, epoxypropylmethyl,

[0031] or R1 is selected from -C(=O)-R2, where R2 is selected from methyl, ethyl, n-propyl, isopropyl, allyl, propargyl, methoxy, ethoxy, n-propoxy, isopropoxy, N,N-dimethylamino, cyclopropyl, epoxypropyl, furyl, phenyl;

[0032] and R1, R2 may be monosubstituted or polysubstituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl;

[0033] R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, C(CH3)3, CH2Cl, CHF2 or CF3.

[0034] In other embodiments, exemplary compound structures are as follows:

[0035]

[0036]

[0037] In other embodiments, R1 = C(=O)R2, and the exemplary compound structures are as follows:

[0038]

[0039] To avoid ambiguity, the terms used herein are defined below. Unless otherwise specified, the meanings of the terms used herein are as follows.

[0040] The term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight-chain or branched-chain alkyl groups, such as methyl, ethyl, n-propyl, isopropyl, or different butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight-chain or branched-chain alkenes, such as vinyl, 1-propenyl, 2-propenyl, and different butenyl, pentenyl, and hexenyl isomers. "Alkenyl" also includes polyenes, such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched-chain alkynes, such as ethynyl, 1-propynyl, 2-propynyl, and different butynyl, pentynyl, and hexynyl isomers. "Alkynyl" may also include moieties composed of multiple triple bonds, such as 2,5-hexadiynyl. "Alkylene" represents a straight-chain or branched-chain alkanediyl. The "alkyl", "alkenyl", and "alkynyl" groups may optionally be substituted with one or more (e.g., 1 to 5) suitable substituents.

[0041] The term "haloalkyl" refers to an alkyl group having one or more halogen substituents (up to a perhaloalkyl group, 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 (up to a perhaloalkyl group, 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 1, 2, or 3 halogen substituents. Examples of haloalkyl groups include: CF3, C2F5, CHF2, CH2F, CH2CF3, CH2Cl, etc.

[0042] The term "alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and different butoxy, pentyloxy, and hexyloxy isomers. "Alkoxyalkyl" represents an alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2OCH2CH2.

[0043] The term "alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the various propylthio, butylthio, pentylthio, and hexylthio isomers. "Alkylthioalkyl" denotes an alkylthio substitution on an alkyl group, and examples include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2, and CH3CH2SCH2CH2.

[0044] The term "alkylcarbonyl" denotes a straight-chain or branched alkyl moiety bonded to a C(=O) moiety. Examples of "alkylcarbonyl" include CH3C(=O)-, CH3CH2CH2C(=O)-, and (CH3)2CHC(=O)-. Examples of "alkoxycarbonyl" include CH3OC(=O)-, CH3CH2OC(=O)-, CH3CH2CH2OC(=O)-, (CH3)2CHOC(=O), and the various butoxycarbonyl, pentyloxycarbonyl, and hexyloxycarbonyl isomers.

[0045] The term "cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "alkylcycloalkyl" denotes an alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl, and 4-methylcyclohexyl. The term "cycloalkylalkyl" denotes a cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, cyclohexylmethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.

[0046] The term "halogen", either alone or in a compound word such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine, or iodine. Further, when used in a compound word such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", the alkyl may be partially or completely substituted by halogen atoms, which may be the same or different. Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O-, and CF3CH2O-. Examples of "haloalkylthio" include CCl3S-, CF3S-, CCl3CH2S-, and ClCH2CH2CH2S-.

[0047] The total number of carbon atoms in a substituent is denoted by the "C i -C j " prefix, where i and j are numbers from 1 to 9. For example, C1-C4 alkyl denotes methyl to butyl.

[0048] The following abbreviations may be used herein: Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Pn is pentyl, cPn is cyclopentyl, cHx is cyclohexyl, cHp is cycloheptyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Thi is thien-2-yl, Pyrr is pyrrol-1-yl, 2-Py is pyridin-2-yl, 3-Py is pyridin-3-yl, 4-Py is pyridin-4-yl. In substituents represented by multiple abbreviations, the substituents are composed of the substituents represented by the abbreviations bonded to each other. For example, 2-Me-Ph represents a 2-methyl-substituted phenyl, and cPr-CH2 represents a cyclopropyl-substituted methyl.

[0049] A variety of synthetic methods are known in the art for preparing aromatic and non-aromatic heterocycles and ring systems; for a comprehensive review, see the eight-volume collection of Comprehensive Heterocyclic Chemistry, edited by A.R. Katritzky and C.W., Pergamon Press, Oxford, 1984, and the twelve-volume collection of Comprehensive Heterocyclic Chemistry II, edited by A.R. Katritzky, C.W. Rees, and E.F.V. Scriven, Pergamon Press, Oxford, 1996.

[0050] The compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers that have the same constitution but differ in the arrangement of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also called geometric isomers), and atropisomers. Atropisomers result from restricted rotation about a single bond, where the rotational barrier is high enough to allow separation of the isomeric 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. Additionally, those skilled in the art know how to separate, enrich, and / or selectively prepare the stereoisomers. For a comprehensive discussion of all aspects of stereochemistry, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

[0051] The present invention provides a method for preparing a compound of formula (I) as a phenylamide derivative:

[0052] Synthesis Scheme 1:

[0053]

[0054] The target compound I can be prepared by Synthesis Scheme 1. The specific steps include: dissolving the raw material II in a suitable solvent, carrying out a substitution reaction with the corresponding halide III under basic conditions, and reacting at a temperature in the range of 0 - 120 °C for 1 - 48 hours to obtain the target compound I. Among them, Y is selected from fluorine, chlorine or bromine. The remaining substituents are as described above.

[0055] Synthesis Scheme 2:

[0056]

[0057] The target compound I can also be prepared by Synthesis Scheme 2. The specific steps include: dissolving the raw material A in a suitable solvent, obtaining a boric acid or borate intermediate under the action of a boron donor and a catalyst, then carrying out a Suzuki coupling with the compound P to obtain the product C, hydrolyzing the product C under basic conditions to obtain the product D, obtaining E through a conventional acylation reaction of the product D, and substituting the product E with the corresponding compound F under basic conditions and reacting at a temperature in the range of 0 - 120 °C for 1 - 24 hours to obtain the target compound I. Among them, Z is selected from bromine or iodine. The remaining substituents are as described above.

[0058] In addition, the present invention also lists multiple synthesized exemplary compounds, and the specific group selections are shown in Table 1 below. It should be understood that the scope of the present invention is not limited to the exemplary compounds listed in the following table, and any combination of the group selections of the compounds in Table 1 below is possible without particular limitation.

[0059] In Table 1 of the general formula I - 1, X1, X2, X3, X4, R1, and R3 are specifically shown in the following table.

[0060]

[0061]

[0062] In Table 2 of the general formula I - 2, R1 = C(O)R2, and X1, X2, X3, X4, R2, and R3 are specifically shown in the following table.

[0063]

[0064]

[0065]

[0066]

[0067] In a second aspect, the present invention provides an insecticide composition comprising a compound of formula (I) 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.

[0068] The acceptable carrier of the composition can be an organic or inorganic inert carrier material. For example, suitable carriers include water, gelatin, gum arabic, magnesium stearate, talc, vegetable oils, polyalkylene glycols, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, brine, glycerol, ethanol, etc. In addition, the insecticide composition may also contain other additives such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, etc.

[0069] The dosage form of the insecticide composition of the present invention can be a liquid dosage form, solid dosage form or semi-solid dosage form, without particular limitation. In some embodiments, the dosage form 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, emulsifiable oil-in-water concentrates, sprayable solutions, dispersible oil suspensions, microcapsule suspensions, water-dispersible granules, water-soluble granules, macrogranules, granules for broadcasting and soil application, aerosols, ultra-low volume agents and wax products.

[0070] The content of the compound of the present invention in its insecticide composition can be adjusted according to actual needs (such as dosage form, application method, application object, etc.), including but not limited to 0.001 mg / L - 10 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 10 mg / L.

[0071] The specific application frequency can be determined by those skilled in the relevant art, 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.

[0072] In a third aspect, the present invention provides the use of a compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt in the preparation of an insecticide for pest control.

[0073] The compounds of the present invention are suitable for controlling pests or mites, that is, controlling pests or mites, where the pests or mites refer to harmful or unwanted insects or mites, especially harmful or unwanted insects or mites encountered in the fields of agriculture, forestry, storage protection, material protection, as well as in the fields of hygiene and animal protection. The compounds of the present invention are active against both generally sensitive and resistant species and are effective at all stages of pest or mite development.

[0074] The present invention also relates to a method for controlling pests or mites, which method comprises applying a controlling effective amount of a compound of formula (I) to the location of the insects, the insect habitat, the pest habitat, the area to be protected, or directly to the insects to be controlled. The compounds of the present invention can also be used to control other invertebrate pests or organisms.

[0075] Specifically, the insect habitat, pest habitat or mite habitat refers to the environment where the 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 the active compound to the seeds of the plant (before planting), to the seedlings, or to the planted cuttings, leaves, stems, fruits, grains and / or roots, or to the soil or other growth media (before or after crop planting), insects or mites that feed on, damage or come into contact with edible agricultural products, ornamental plants, turf, forage plants or other economically valuable plants can be controlled. It is also possible to protect these plants against diseases caused by viruses, fungi or bacteria by controlling sap-sucking pests such as whiteflies, planthoppers, aphids, etc. or mites such as Tetranychus urticae, Tetranychus cinnabarinus, etc.; the plants include plants obtained by conventional breeding methods as well as plants with insect or mite resistance, herbicide resistance, high yield / or other beneficial characteristics obtained by genetic modification using modern biotechnology. It is expected that these compounds can be applied to protect articles and / or places such as fabrics, paper, stored grains, seeds and other foods, houses, buildings, etc. by applying the compounds of the present invention to or near these objects.

[0076] The inventors of the present invention have found that even when the compounds of the present invention are applied at a relatively low dose, they are still capable of controlling animal pests encountered in the fields of agronomy and non-agronomy, as well as in the fields of hygiene and animal protection, especially insects, arachnids, worms, nematodes and molluscs. These compounds are preferably used as insecticides. They are effective against both usually sensitive and resistant species and are effective against all or part of the developmental stages. The above pests include:

[0077] Pests from the phylum Arthropoda, especially from the class Arachnida, such as Acari, Metastigmata and Mesostigmata, Tetranychidae, Eupodidae, Eriophyidae, Phytoseiidae, Acaridae, and Acarus spp. (such as Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp., Aculus spp. (such as Aculus fockeui, Aculus schlechtendali), Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp. (such as Brevipalpus phoenicis), Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Ornithodorus spp., Otobius spp., Ixodes spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp. (the original genus of heteroxenous mites), Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Sternostoma spp., Varroa spp., Acarapis spp., etc.;

[0078] Pests from the order Coleoptera, such as Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp. (such as Agriotes linneatus, Agriotes mancus), Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp. (such as Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp. (such as Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (such as Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata, Ceuthorhynchus spp. (such as Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp. (such as Chaetocnema confinis, Chaetocnema denticulata, Chaetocnema ectypa), Cleonus mendicus, Conoderus spp., Cosmopolites spp. (such as Cosmopolites sordidus), etc.;

[0079] Pests from the order Diptera, such as, Aedes spp. (e.g., Aedes aegypti, Aedes albopictus, Aedes sticticus, Aedes vexans), Agromyza spp. (e.g., Agromyza frontella, Agromyza parvicornis), Anastrepha spp., Anopheles spp. (e.g., Anopheles quadrimaculatus, Anopheles gambiae), Asphondylia spp., Bactrocera spp. (e.g., Bactrocera cucurbitae, Bactrocera dorsalis, Bactrocera oleae), Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp. (e.g., Contarinia johnsoni, Contarinia nasturtii, Contarinia pyrivora, etc.;

[0080] Pests from the order Heteroptera, such as, Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (such as Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., etc.;

[0081] Pests from the order Homoptera, such as Acizzia acaciaebaileyanae, Acizziadodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. (such as Acyrthosiphon pisum), Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (such as Amrasca bigutulla, Amrasca devastans), Anuraphis cardui, Aonidiella spp. (such as Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp (such as Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middletoni, Aphis nasturtii, Aphis nerii, etc.);

[0082] Pests from the order Hymenoptera, such as Acromyrmex spp., Athalia spp. (e.g., Athalia rosae), Atta spp., Diprion spp. (e.g., Diprion similis), Hoplocampa spp. (e.g., Hoplocampa cookei, Hoplocampa testudinea), Lasius spp., etc.;

[0083] Pests from the order Isoptera, such as Coptotermes spp. (e.g., Coptotermes formosanus), Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp. (e.g., Reticulitermes flavipes, Reticulitermes hesperus), etc.;

[0084] Pests from the order Lepidoptera, for example, Argyroploce spp., Anarsia spp., Choristoneura spp., Cnephasia spp., Conopomorpha spp., as well as Heliothis spp., Helicoverpa spp., Spodoptera spp., Mythimna unipuncta, Agrotis spp. (such as Agrotis segetum, Agrotis ipsilon), Earias spp., Trichoplusia ni, Anticarsia gemmatalis, Rachiplusia nu, Plutella xylostella, Chilo spp, Scirpophaga incertulas, Sesamia inferens, Cnaphalocrocis medinalis, Ostrinia nubilalis, Cydia pomonella, Carposina niponensis, Cacoecia spp., Adoxophyes orana, Archips argyrospilus, Pandemis heparana, Carpocapsa pomonella, Epinotia aporema, Eupoecilia ambiguella, Lobesia botrana, Polychrosis biteana, Pectinophora gossypiella, Pieris rapae, Phyllonorycter spp., Leucoptera malifoliella, Phyllocnisitis citrella, Podoptera exigua Hübner;

[0085] Pests from the order Orthoptera or Saltatoria, such as Acheta domesticus, Dichroplus spp., Gryllotalpa spp. (such as Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (such as Locusta migratoria, Locusta migratoria manilensis), Melanoplus spp. (such as Melanoplus devastator), Schistocerca gregaria, Gryllotalpidae (mole crickets), etc.;

[0086] Pests from the order Thysanoptera, such as Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp. (such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi), Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp. (such as Thrips palmi, Thrips tabaci), etc.;

[0087] Pests from Phthiraptera, such as Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloxera vastatrix, Ptirus pubis, Trichodectes spp., sucking lice, Pthirus pubis, etc.;

[0088] Pests from Siphonapterida, such as Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.; In particular, representative examples are Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis, etc.;

[0089] Pests from Blattarida, such as cockroaches of Blattarida, Blatta orientalis, Blattella germanica, Periplaneta americana, Supella longipalpa, Periplaneta australasiae, Periplaneta brunnea, Parcoblatta pennsylvanica, Periplaneta fuliginosa, Pycnoscelus surinamensis, Supella spp. (e.g., Suppella longipalpa), etc.;

[0090] Plant pests from the phylum Nematoda, namely plant parasitic nematodes, especially those of the genus Aglenchus spp. (such as Aglenchus agricola), Anguina spp. (such as Anguina tritici), Aphelenchoides spp. (such as Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (such as Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (such as Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus), Dirofilaria immitis, Meloidogyne spp., Heterodera spp., Hoplolaimus columbus, Belonolaimus spp., Pratylenchus spp., Rotylenchus reniformis, Criconemella ornata, Ditylenchus spp., Aphelenchoides besseyi, Hirschmanniella spp., etc.

[0091] In another preferred embodiment of the present invention, the pests that can be prevented and / or controlled by the compounds or compositions described in the present invention can be selected from Mythimna separata, Spodoptera exigua, Plutella xylostella, Chilo suppressalis, Frankliniella occidentalis, Phyllotreta striolata, Agrotis ypsilon, Bradysia odoriphaga, Ctenocephalides felis, Boophilus microplus, Aedes albopictus, Blattodea, Termite.

[0092] Those skilled in the art can understand that the definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. Those skilled in the art can understand that the embodiments of various aspects of the present invention can be combined in various ways without departing from the subject matter and ideas of the present invention, and these combinations are also included within the scope of the present invention. Detailed Description

[0093] As mentioned in this disclosure, the term "invertebrate pest" includes arthropods, gastropods, nematodes, and worms that are of economic importance as pests. The term "arthropod" includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs, and symphylans. The term "gastropod" includes snails, slugs, and other Stylommatophora. The term "nematode" includes members of the phylum Nematoda, such as phytophagous nematodes and parasitic worm nematodes of animals. The term "worm" includes all parasites, such as roundworms (phylum Nematoda), heartworms (phylum Nematoda, class Secernentea), flukes (phylum Platyhelminthes, class Tematoda), acanthocephalans (phylum Acanthocephala), and tapeworms (phylum Platyhelminthes, class Cestoda).

[0094] In the context of this disclosure, "invertebrate pest control" means inhibiting the development of invertebrate pests (including death, reduced feeding, and / or mating disruption), and related expressions are defined similarly.

[0095] The term "agronomy" refers to the production of field crops such as those for food and fiber, and includes the growth of maize or corn, soybeans and other legumes, rice, grains (e.g., wheat, oats, barley, rye, and rice), leafy vegetables (e.g., lettuce, cabbage, and other brassica crops), fruiting vegetables (e.g., tomatoes, peppers, eggplants, crucifers, and cucurbit crops), 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, sunflowers, and olives).

[0096] The term "non-agronomic" refers to applications different from field crops, such as horticultural crops (e.g., greenhouse, nursery, or ornamental plants not grown in the field), residential, agricultural, commercial, and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood 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, non-domestic animals such as wild animals).

[0097] Non-agronomic applications include protecting animals from invertebrate parasitic pests by administering to the animal to be protected a parasiticidally effective (i.e., biologically effective) amount of the compounds of the present disclosure, typically in the form of a composition formulated for veterinary use. As referred to in the present disclosure and the claims, the terms "parasiticidal" and "parasiticidally" refer to the observable effects on invertebrate parasitic pests to protect the animal from the pests. The parasiticidal effect is typically associated with a reduction in the emergence or activity of the target invertebrate parasitic pests. Such effects on the pests include necrosis, death, growth retardation, reduced mobility or ability to remain on or in the host animal, reduced feeding, and reproductive inhibition. These effects on invertebrate parasitic pests prevent (including preventing, reducing, or eliminating) parasitic infestation or infection of the animal.

[0098] The compounds of formula (I) of the present invention can be synthesized by various methods familiar to those skilled in the art of organic synthesis. Some exemplary methods for synthesizing the compounds of formula (I) are given in the following specific examples, which are well-known in the field of synthetic chemistry. Obviously, with reference to the exemplary schemes in this patent, those skilled in the art can easily design other synthetic routes for the compounds of formula (I) by appropriately adjusting the reactants, reaction conditions, and protecting groups.

[0099] The present invention will be further illustrated below in conjunction with examples; however, these examples do not limit the scope of the present invention. Unless otherwise stated, all reactants used in each example are obtained commercially; the instruments and equipment used in synthetic experiments and product analysis and detection are all conventional instruments and equipment commonly used in organic synthesis.

[0100] Example 1: Synthesis of Compound I-21

[0101]

[0102] First step: Synthesis of methyl 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-1H-pyrazol-4-yl)benzoate

[0103] Methyl 5-bromo-2-chlorobenzoate (4.96 g, 20 mmol) and 60 ml of isopropanol were placed in a 250 ml reaction flask. Tetrahydroxy diborane (1.79 g, 20 mmol), N,N-diisopropylethylamine (5.17 g, 40 mmol), and chloro[(n-butylbis(1-adamantyl)phosphine)-2-(2-aminobiphenyl)]palladium(II) (10% mmol) were added successively. Under nitrogen protection, the temperature was controlled at 65 °C and the reaction was carried out for 6 h. After the reaction was monitored by TLC to completion, it was cooled to room temperature.

[0104] To the above reaction flask was added a solution of 1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-4-iodo-1H-pyrazole (10.12 g, 20 mmol), potassium carbonate (8.29 g, 60 mmol), and 30 ml of H2O, and then tetrakis(triphenylphosphine)palladium (10% mmol) was added. Under nitrogen protection, the temperature was controlled at 80 °C and the reaction was carried out overnight. After 12 h, the reaction was terminated, cooled to room temperature, extracted with dichloromethane, dried, filtered, concentrated under reduced pressure, and purified by flash column chromatography to obtain a pale yellow solid (6.38 g, yield: 58%). LC-MS: (M + 1) m / z = 549.1.

[0105] Step 2: Synthesis of 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-1H-pyrazol-4-yl)benzoic acid

[0106] The product of the first step (3.30 g, 6 mmol) and 40 ml of THF were placed in a 100 ml reaction flask. While stirring, LiOH·H2O (0.99 g, 24 mmol) and water (10 ml) were added, and the reaction was stirred at 40 - 50 °C. After the reaction was monitored by TLC to completion, it was cooled to room temperature, diluted with water, and the pH was adjusted to 4 - 5 with 10% hydrochloric acid. It was extracted with ethyl acetate, washed with water, dried, filtered, concentrated under reduced pressure, and dried to obtain a pale yellow solid (2.14 g, yield 67%). LC-MS: (M - 1) m / z = 533.0.

[0107] Step 3: Synthesis of 2-chloro-5-(1-(2,6-dichloro-4-(perfluoropropan-2-yl)phenyl)-1H-pyrazol-4-yl)benzoyl chloride

[0108] The product of the second step (1.60 g, 3 mmol) and 20 ml of dichloromethane were placed in a 100 ml reaction flask. Under ice bath conditions, oxalyl chloride (1.91 g, 15 mmol) was slowly added while stirring, and 2 drops of DMF were added as a catalyst. The temperature was raised to 40 °C and the reaction was carried out for 2 h. After the reaction was completed, it was cooled to room temperature, and the solvent and unreacted substances were removed by rotary evaporation under reduced pressure to obtain the acyl chloride product for use.

[0109] Step 4: Synthesis of 2-chloro-N-(cyclopropylmethyl)-N-cyclopropyl-5-(1-(2,6-dichloro-4-(2,2,2-trifluoropropyl)phenyl)-1H-pyrazol-4-yl)benzamide

[0110] Place N-(cyclopropylmethyl)cyclopropylamine (0.40 g, 3.6 mmol) and 30 ml of THF in a 100 ml reaction flask. Under ice bath conditions, add 60% NaH (0.22 g, 5.4 mmol) with stirring, and then slowly dropwise add the acyl chloride product obtained in the above step. Stir and react at 50 °C overnight. After the reaction is completed, cool to room temperature, quench with water, extract the aqueous layer, combine the organic phases, and concentrate under reduced pressure. Column chromatography gives a white solid (1.35 g, yield: 72%). LC-MS: (M + 1) m / z = 628.1.

[0111] 1 1H NMR (400 MHz, DMSO-d6) δ 8.74 (d, J = 0.7 Hz, 1H), 8.45 (s, 1H), 8.10 (s, 2H), 7.71 (dd, J = 4.5, 2.2 Hz, 2H), 7.54 (d, J = 9.0 Hz, 1H), 3.54 (d, J = 21.5 Hz, 1H), 3.18 (s, 1H), 2.79 (d, J = 5.8 Hz, 1H), 1.16 (dd, J = 9.6, 5.0 Hz, 1H), 0.90–0.73 (m, 2H), 0.53 (d, J = 7.8 Hz, 4H), 0.33 (s, 2H).

[0112] LC-MS: (M + 1) m / z = 628.1.

[0113] Example 2: Synthesis of Compound I-24

[0114]

[0115] Referring to the synthesis method of Reference Example 1, replace the starting material in Step 1 with methyl 5-bromo-2-methylbenzoate, and the remaining synthesis methods are the same to prepare the target compound.

[0116] 1 1H NMR (400 MHz, Chloroform-d) δ 8.09 (s, 1H), 7.86 (s, 1H), 7.82 (s, 1H), 7.73 (s, 2H), 7.45 (d, J = 8.0 Hz, 1H), 7.38 (s, 1H), 3.99 (dd, J = 8.3, 4.5 Hz, 2H), 3.51–3.43 (m, 1H), 1.56 (s, 3H), 1.36 (d, J = 6.2 Hz, 1H), 0.96–0.76 (m, 2H), 0.65–0.45 (m, 6H).

[0117] LC-MS: (M+1) m / z = 608.2.

[0118] Example 3: Synthesis of Compound I-25

[0119]

[0120] Referring to the synthesis method of Reference Example 1, replace the starting material in Step 1 with methyl 3-bromobenzoate, and keep the rest of the synthesis method the same to prepare the target compound.

[0121] 1 H NMR (400 MHz, DMSO-d6) δ 8.71 (s, 1H), 8.42 (s, 1H), 8.10 (s, 2H), 7.79–7.69 (m, 2H), 7.45 (d, J = 7.9 Hz, 1H), 7.35 (s, 1H), 3.33 (s, 2H), 2.97 (s, 1H), 1.16 (d, J = 8.5 Hz, 1H), 0.69–0.39 (m, 6H), 0.27 (s, 2H).

[0122] LC-MS: (M+1) m / z = 594.1.

[0123] Example 4: Synthesis of Compound II-1

[0124]

[0125] Referring to the synthesis method of Reference Example 1, replace the amine corresponding to Step 4 with N-cyclopropylethanamide, and keep the rest of the synthesis method the same to prepare the target compound

[0126] 1 H NMR (400 MHz, DMSO-d6) δ 8.74 (d, J = 0.7 Hz, 1H), 8.47–8.42 (m, 1H), 8.10 (s, 2H), 7.81 (d, J = 2.2 Hz, 1H), 7.74 (d, J = 2.2 Hz, 1H), 7.54 (d, J = 8.4 Hz, 1H), 2.79 (dt, J = 6.9, 3.2 Hz, 1H), 2.41 (s, 3H), 0.95–0.83 (m, 2H), 0.70 (dd, J = 4.6, 2.4 Hz, 2H).

[0127] LC-MS: (M+1) m / z = 616.1.

[0128] Example 5: Synthesis of Compound II-4

[0129]

[0130] Referring to the synthesis method of Reference Example 2, replace the amine corresponding to Step 4 with cyclopropylacetamide, and keep the rest of the synthesis method the same to prepare the target compound.

[0131] 1 H NMR(400MHz,DMSO-d6)δ8.68(d,J=0.7Hz,1H),8.40(d,J=0.7Hz,1H),8.09(s,2H),7.65(s,2H),7.33(d,J=8.2Hz,1H),2.78(dt,J=7.0,3.1Hz,1H),2.36(s,3H),2.31(s,3H),0.87–0.71(m,2H),0.64–0.51(m,2H).

[0132] LC-MS:(M+1)m / z=596.1.

[0133] Example 6: Synthesis of Compound II-5

[0134]

[0135] Referring to the synthesis method of Reference Example 3, replace the corresponding amine in Step 4 with cyclopropylacetamide, and keep the rest of the synthesis method the same to prepare the target compound.

[0136] 1 H NMR(400MHz,DMSO-d6)δ8.77(s,1H),8.46(s,1H),8.11(s,2H),7.93(d,J=1.7Hz,1H),7.88(d,J=7.4Hz,1H),7.61–7.47(m,2H),2.96(tt,J=7.1,3.8Hz,1H),2.34(s,3H),0.85(t,J=3.9Hz,2H),0.65–0.47(m,2H).

[0137] LC-MS:(M+1)m / z=582.0.

[0138] Example 7: Synthesis of Compound II-25

[0139]

[0140] 2-Chloro-N-cyclopropyl-5-(1-(2,6-dichloro-4-(2,2,2-trifluoro-1,1,1-trimethyl-ethyl)phenyl)-1H-pyrazol-4-yl)benzamide (0.57 g, 1 mmol) and 20 ml of THF were placed in a 50 ml reaction flask. Under ice bath conditions, 60% NaH (0.06 g, 2 mmol) was added with stirring, and then methyl chloroformate was added slowly. After completion, the reaction was stirred at 50 °C overnight. After the reaction was completed, it was cooled to room temperature, quenched with water, and the aqueous layer was extracted with ethyl acetate. The organic phases were combined, concentrated under reduced pressure, and purified by column chromatography to obtain a white solid (0.27 g, yield: 43%).

[0141] 1 H NMR (400 MHz, DMSO-d6) δ 8.74 (d, J = 0.7 Hz, 1H), 8.45 (s, 1H), 8.10 (s, 2H), 7.71 (dd, J = 4.5, 2.2 Hz, 2H), 7.54 (d, J = 9.0 Hz, 1H), 3.54 (s, 3H), 2.79 (d, J = 5.8 Hz, 1H), 0.90–0.73 (m, 2H), 0.83–0.79 (m, 2H).

[0142] LC-MS: (M+1) m / z = 632.1.

[0143] Example 8: Synthesis of Compound II-70

[0144]

[0145] Using a method similar to that of Example 7, the corresponding halide was replaced with N,N-dimethylcarbamoyl chloride, and the remaining synthetic methods were the same to prepare the target compound.

[0146] 1 H NMR (400 MHz, Chloroform-d) δ 8.63 (d, J = 2.4 Hz, 1H), 8.20–8.09 (m, 1H), 7.92 (d, J = 0.7 Hz, 1H), 7.81 (d, J = 2.4 Hz, 1H), 7.75 (s, 2H), 7.01 (dd, J = 16.8, 10.3 Hz, 1H), 3.06 (s, 6H), 2.93 (t, J = 3.7 Hz, 1H), 1.24–1.09 (m, 2H), 0.97–0.69 (m, 2H).

[0147] LC-MS: (M+1) m / z = 645.1.

[0148] Example 9: Synthesis of Compound II-80

[0149]

[0150] Using a method similar to that in Step 4 of Example 1, replace the corresponding amine with cyclopropylcyclopropanecarboxamide, and keep the rest of the synthesis method the same to prepare the target compound.

[0151] 1 H NMR(400MHz,Chloroform-d)δ8.59(d,J=2.4Hz,1H),8.12(s,2H),7.90(s,1H),7.80(d,J=2.4Hz,1H),7.74(s,2H),3.01(dt,J=6.9,3.2Hz,1H),2.48(ddd,J=7.7,5.2,3.0Hz,1H),1.23(d,J=6.9Hz,2H),1.10(dt,J=5.5,3.0Hz,2H),1.06(dt,J=7.8,2.7Hz,2H),1.01–0.93(m,2H).

[0152] LC-MS:(M+1)m / z=642.0.

[0153] Example 10: Synthesis of Compound II-107

[0154]

[0155] Using a method similar to that in Example 7, replace the corresponding halide with 2-furoyl chloride, and keep the rest of the synthesis method the same to prepare the target compound.

[0156] 1 H NMR(400MHz,Chloroform-d)δ8.59(s,1H),8.07(s,2H),7.88(s,1H),7.80(s,1H),7.68(d,J=2.4Hz,2H),7.61(s,1H),6.93-6.87(m,2H),2.10(d,J=1.2Hz,1H),1.07(d,J=6.7Hz,2H),0.86–0.66(m,2H).

[0157] LC-MS:(M+1)m / z=668.0.

[0158] The structural formulas, physical and chemical properties, NMR, and mass spectrometry data of the exemplary compounds of the present invention are as follows:

[0159]

[0160]

[0161]

[0162] Indoor Activity Determination Method

[0163] 2.1 Determination of Activity against Mythimna separata

[0164] Soak an appropriate amount of corn leaves in the prepared liquid medicine for 30 s, then place them in a plastic petri dish lined with filter paper and air-dry naturally. Place 10 middle-instar larvae of Mythimna separata in each dish, and culture them in an observation room at 24 - 27 °C. After 48 h, investigate the results. Touch the insect body with a writing brush, and those without response are regarded as dead insects. Each treatment is repeated 3 times, and a solvent control is set. The test concentration is 20 mg / L.

[0165] Test Results: Among some of the tested compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of over 95% at a dose of 20 mg / L.

[0166] 2.2 Determination of Activity against Plutella xylostella

[0167] Soak an appropriate amount of Chinese cabbage and kale leaves in the prepared liquid medicine for 30 s, then place them in a plastic petri dish lined with filter paper and air-dry naturally. Place 8 Plutella xylostella larvae at the 2nd - 3rd instar in each dish, and place them in an observation room with light (16 / 8 h) at 22 °C. Observe after 48 h. Gently touch the insect body with a writing brush, and those without response are regarded as dead insects. Each treatment is repeated 3 times, and a solvent control is set. The test concentration is 20 mg / L.

[0168] Test Results: Among some of the tested compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed significant control effects against Plutella xylostella at a dose of 20 mg / L, and the mortality rates were all 100%.

[0169] 2.3 Determination of Activity against Spodoptera exigua

[0170] Pour the prepared artificial feed into a 12-well plate while it is still hot, adding 2.5 ml of artificial feed to each well. Wait for the feed to cool completely before use. For each chemical agent and each concentration gradient, prepare 3 12-well plates. Each 12-well plate is one replicate, with a total of 3 replicates. Add 50 μL of the chemical agent at the corresponding concentration gradient to each well and let it dry. Place 1 Spodoptera litura larva in each well. For the 3 control 12-well plates, with a total of 3 replicates, add 50 μL of the solvent control to each well. Place them in an insect rearing room at a temperature of 26 ± 2 °C, a light cycle of 16 h∶8 h (L∶D), and a humidity of 50 - 70%. Investigate the mortality of the test insects 48 h after the experiment and calculate the mortality rate of the test insects. The test concentration is 10 mg / L.

[0171] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed significant control effects against Spodoptera exigua at a dose of 10 mg / L, and the mortality rates were all 100%.

[0172] 2.4 Determination of the activity against Chilo suppressalis

[0173] Fully soak the thin slices of water bamboo in the prepared liquid medicine for 30 s, then place them in a plastic petri dish lined with filter paper to dry naturally in the shade. Place 10 third-instar Chilo suppressalis larvae in each dish and observe in an observation room at 26 - 28 °C with a light cycle of (16 / 8 h). After 96 h, observe and gently touch the insect body with a writing brush. If there is no response, it is considered a dead insect. Repeat each treatment 3 times and set a solvent control. The test concentration is 20 mg / L.

[0174] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed significant control effects against Chilo suppressalis at a dose of 20 mg / L, and the mortality rates were all 100%.

[0175] 2.5 Determination of the activity against Frankliniella occidentalis

[0176] Dilute the test agents into 4 concentrations. Fill 1.5 mL centrifuge tubes with the liquid medicine of each concentration, place them for 4 h, then pour out the liquid medicine, and let the centrifuge tubes dry on the experimental bench for later use. Heat the tip of the fine needle with an alcohol lamp and burn a small hole with a diameter of about 2 - 3 mm at the bottom of the dried centrifuge tube. Each tube is one replicate, and each concentration has 4 replicates. A solvent control is also set. The test concentration is 20 mg / L.

[0177] Leaf dipping: Use a hole punch to punch fresh cabbage leaves into circles with a diameter of 0.5 cm, and dip them in the liquid medicine of each concentration for 10 s. Place the treated leaves on absorbent paper to dry, and then use small forceps to clamp them into the centrifuge tubes with the corresponding liquid medicine concentration, one leaf per tube, and place them flat. Indoor test insects: Seal the interface of the suction device with gauze, put it on the mouth of the treated centrifuge tube, align the burned hole at the bottom of the centrifuge tube with the test insects, and let the test insects be sucked into the centrifuge tube along the air flow. First do the control and then the treatment. Suck about 40 test insects for each replicate, then cover the tube cap and seal the burned hole with sealing film. After marking the relevant information, record the number of live insects and dead insects 48 h later.

[0178] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed significant control effects against Frankliniella occidentalis at a dose of 20 mg / L, and the mortality rates were all 100%.

[0179] 2.6 Determination of the activity against Phyllotreta striolata

[0180] Fill about half of the volume of the tissue culture bottle (350 ml) with seedling raising soil, plant radish seeds in the tissue culture bottle, 10 radish seeds per bottle, water thoroughly and then place them in the test material culture room for cultivation. The temperature of the test material culture room is 26 ± 2 °C, the light cycle D:L = 16 h:8 h, and the indoor relative humidity is 50% - 70%. Conduct the experiment when the radish seedlings grow to the two-leaf and one-heart stage. Spray each tissue culture bottle with a constant pressure sprayer first. Each concentration of each agent is repeated 3 times, one bottle of radish seedlings for each replicate, and spray 2 ml of the liquid medicine per bottle. The control treatment is sprayed with a solvent without the agent. After the liquid medicine dries, inoculate 8 adult Phyllotreta striolata into each bottle of radish seedlings and seal the bottle mouth. Place them in the insect rearing room for feeding. The temperature of the insect rearing room is 24 ± 2 °C, the light cycle D:L = 16 h:8 h, and the indoor relative humidity is 50% - 70%. Check the number of live insects, dead insects and the damage of radish seedlings caused by feeding 48 h later. The test concentration is 20 mg / L.

[0181] Test results: Among some of the tested compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of over 90% at a dose of 20 mg / L.

[0182] 2.7 Determination of Activity against Agrotis ypsilon

[0183] First, pour the prepared artificial diet for Agrotis ypsilon into a 12-well plate while it is still hot, adding 3 ml of artificial diet to each well. Wait for the diet to cool completely before use. For each concentration of each agent, make 3 12-well plates, with each 12-well plate being one replicate, for a total of 3 replicates. Add 50 μL of the corresponding concentration gradient agent to each well. One 12-well plate for the control is one replicate, for a total of 3 replicates, and add 50 μL of the solvent control to each well. After all the 12-well plates for all test treatments are air-dried, they are ready for use. Place 1 third-instar Agrotis ypsilon larva in each well. Put them in an insect rearing room at a temperature of 26 ± 2 °C, a light cycle of 16 h∶8 h (L∶D), and a humidity of 50 - 70%. Investigate the death of the test insects 72 h after the experiment and count the mortality rate of the test insects. The test concentration is 10 mg / L.

[0184] Test results: Among some of the tested compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of over 90% at a dose of 10 mg / L.

[0185] 2.8 Determination of Activity against Bradysia odoriphaga

[0186] Lay a clean filter paper flat in a petri dish with a diameter of 8 cm and agar at the bottom. Drop 1 mL of the prepared liquid medicine on the filter paper. Cut the false stem part of Chinese chives into small sections about 2 cm long, soak them in the liquid medicine at doses of 50 mg / L and 5 mg / L for 30 s respectively. After taking them out, use absorbent paper to absorb the excess liquid medicine and place them on the filter paper with the same concentration of liquid medicine dropped. Put 5 sections in each petri dish. Then use a brush to pick 30 third-instar Bradysia odoriphaga larvae of the same size and place them in the petri dish, with 3 replicates for each dish. At the same time, set a blank control. Investigate the results 48 hours later. Gently touch the insect body with a brush, and those with no response are regarded as dead. The test concentration is 10 mg / L.

[0187] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of over 90% at a dose of 10 mg / L.

[0188] 2.9 Determination of Activity against Cat Fleas

[0189] Dissolve 4 mg of the test compound in 40 mL of acetone to obtain an acetone solution with a concentration of 100 mg / L. Coat 400 μL of the liquid medicine on the bottom and side surfaces of a petri dish with an inner diameter of 5.3 cm, and then wait for the acetone to evaporate to form a thin film of the compound of the present invention on the inner wall of the petri dish. The inner wall of the used petri dish is 40 cm 2 , and the dosage of the treatment is 1 μg / cm 2 ; Put 10 adult cat fleas (mixed male and female) into it, cover it and store it in a constant temperature room at 25°C. Each treatment is repeated 3 times, and the death situation of the test insects is investigated 72 h after the test, and the mortality rate of the test insects is counted.

[0190] Test results: The compounds of Example I-11, I-21, I-24, I-25, II-4, II-5, II-25, II-80, II-115, II-118 showed a dead insect rate of over 70%.

[0191] 2.10 Determination of Activity against Boophilus microplus

[0192] Dissolve 4 mg of the test compound in 40 mL of acetone to obtain an acetone solution with a concentration of 100 mg / L. Coat 400 μL of the liquid medicine on the bottom and side surfaces of two petri dishes with an inner diameter of 5.3 cm, and then wait for the acetone to evaporate to form a thin film of the compound of the present invention on the inner wall of the petri dish. The inner wall of the used petri dish is 40 cm 2 , and the dosage of the treatment is 1 μg / cm 2 . Put 10 first instar nymphs of Boophilus microplus (mixed male and female) into it, combine the two petri dishes, and use tape to seal the joint to prevent escape, and store it in a constant temperature room at 25°C. Each treatment is repeated 3 times, and the death situation of the test insects is investigated 72 h after the test, and the mortality rate of the test insects is counted.

[0193] Test results: The compounds of Examples I-11, I-21, I-24, I-25, II-4, II-5, II-25, II-80, II-115, and II-118 showed a dead bug rate of over 70%.

[0194] 2.11 Determination of Activity against Aedes albopictus

[0195] Aedes albopictus, a sensitive strain introduced from the Center for Disease Control and Prevention and not exposed to any pesticides, was reared in an insectarium for sanitary pests. The rearing conditions were: temperature 26 ± 1°C, relative humidity 65% ± 10%, and light cycle L / D: 12h / 12h. For the mosquito larva killing test, uniformly sized and healthy 4th instar larvae were selected for testing. The toxicity test of the test samples against Aedes albopictus larvae was carried out according to the immersion method of the WHO (1981) standard. Each treatment was repeated 3 times, and the death of the test insects was investigated 24h after the test to count the mortality rate of the test insects. The test concentration was 50mg / L.

[0196] Test results: Among some of the test compounds, the compounds of Examples I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, and II-119 showed a dead bug rate of over 90% at a dose of 50mg / L.

[0197] 2.12 Determination of Activity against Cockroaches

[0198] During the test, uniformly sized and healthy 4th instar male nymphs of Periplaneta americana were selected. After anesthetizing the test insects with carbon dioxide, they were arranged supine in a petri dish. 10 insects were dropped for each concentration treatment of each agent. From low to high concentration, 1ul of the liquid medicine was dropped on the ventral plate between the second and third pairs of coxae of the test insects with a micro-drop pipette. The control treatment used a solvent without the agent. Each treatment was repeated 3 times. After dropping, they were fed normally, and the number of live and dead insects was checked 48h later. The test concentration was 200mg / L.

[0199] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of more than 70% at a dose of 200 mg / L.

[0200] 2.13 Determination of termite activity

[0201] Dilute the test agents into a series of gradients. Place a qualitative filter paper with a diameter of 7 cm in a 9 cm disposable petri dish. Use a pipette to take 1 ml of the liquid medicine and evenly drip it from the outer edge to the inside of the petri dish. Place it on the experimental table to dry in the shade for later use. Introduce 30 worker termites of Reticulitermes flaviceps into each petri dish, seal the petri dish to prevent termites from escaping. The control treatment uses a solvent without the agent, and each treatment is repeated 3 times. Check the number of live insects and dead insects 48 hours after treatment. The test concentration is 20 mg / L.

[0202] Test results: Among some of the test compounds, the compounds of Example I-1, I-2, I-3, I-11, I-21, I-22, I-23, II-1, II-2, II-7, II-13, II-15, II-20, II-25, II-30, II-49, II-56, II-70, II-71, II-80, II-107, II-108, II-109, II-115, II-116, II-117, II-119 showed a dead insect rate of more than 90% at a dose of 20 mg / L.

[0203] In addition to the pest control characteristics, compared with the compounds of the prior art, the compounds according to the present invention also unexpectedly show improved degradation characteristics. Additionally, compared with the prior art compounds, the compounds according to the present invention also unexpectedly show lower toxicity to bees (or aquatic animals).

[0204] It should be further noted that among the various specific technical features described in the above specific embodiments, without conflict, they can be combined in any suitable manner. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0205] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A compound of formula (I) which is a phenylamide derivative or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt, wherein, X1, X2, X3, X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxy, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-12 cycloalkyl, C 1-6 haloalkyl, C 1-6 alkoxy or C 1-6 haloalkoxy; R1 is selected from C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-12 cycloalkyl, C 3-6 heterocyclic group, C 6-12 aryl, C 5-12 heteroaryl, C 1-6 alkoxy C 1-6 alkyl, C 1-6 alkylthio C 1-6 alkyl, C 1-6 alkylamino C 1-6 alkyl, C 3-12 cycloalkyl C 1-6 alkyl, C 3-6 heterocyclic group C 1-6 alkyl, C 6-12 aryl C 1-6 alkyl, C 5-12 heteroaryl C 1-6 alkyl, C 6-12 aryloxy C 1-6 alkyl, C 5-12 heteroaryloxy C 1-6 alkyl, or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1-6 alkoxy, C 1-6 alkylthio, C 1-6 alkylamino, C 3-12 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 6-12 aryloxy, C 5-12 heteroaryl, C 5-12 heteroaryloxy, C 1-6 alkoxyC 1-6 alkyl, C 1-6 alkylthioC 1-6 alkyl, C 1-6 alkylaminoC 1-6 alkyl, C 3-12 cycloalkylC 1-6 alkyl, C 3-6 heterocyclic groupC 1-6 alkyl, C 6-12 arylC 1-6 alkyl, C 5-12 heteroarylC 1-6 alkyl, C 6-12 aryloxyC 1-6 alkyl, C 5-12 heteroaryloxyC 1-6 alkyl; and R1 and R2 may be mono - substituted or poly - substituted by one or more identical or different substituents selected from: halogen, cyano, nitro, C 1-6 alkyl, C 1-6 alkoxy, C 1-6 haloalkyl, C 1-6 alkoxycarbonyl, C 1-6 alkylamino, ,, C 3-6 cycloalkyl, C 3-6 epoxyalkyl, C 6-12 aryl; R3 is selected from hydrogen, halogen, hydroxyl, cyano, nitro, amino, carboxyl, C 1-6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 3-8 cycloalkyl, C 1-6 haloalkyl, C 2-6 haloalkenyl, C 2-6 haloalkynyl.

2. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt according to claim 1, wherein, X1, X2, X3, X4 are each independently selected from hydrogen, halogen, hydroxy, nitro, amino, cyano, carboxy, C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy; R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-12 aryl, C 5-12 heteroaryl, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, C 1-3 alkylamino C 1-3 alkyl, C 3-12 cycloalkyl C 1-3 alkyl, C 3-6 heterocyclic group C 1-3 alkyl, C 6-12 aryl C 1-3 alkyl, C 5-12 heteroaryl C 1-3 alkyl, C 6-12 aryloxy C 1-3 alkyl, C 5-12 heteroaryloxy C 1-3 alkyl, or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 6-12 aryloxy, C 5-12 heteroaryl, C 5-12 heteroaryloxy, C 1-3 alkoxyC 1-3 alkyl, C 1-3 alkylthioC 1-3 alkyl, C 1-3 alkylaminoC 1-3 alkyl, C 3-8 cycloalkylC 1-3 alkyl, C 3-6 heterocyclic groupC 1-3 alkyl, C 6-12 arylC 1-3 alkyl, C 5-12 heteroarylC 1-3 alkyl, C 6-12 aryloxyC 1-3 alkyl, C 5-12 heteroaryloxyC 1-3 alkyl, and R1 and R2 may be mono-substituted or multi-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 1-3 alkoxycarbonyl, C 1-3 alkylamino, ,, C 3-6 cycloalkyl, C 3-6 epoxyalkyl, C 6-12 aryl; R3 is selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl, C 3-8 cycloalkyl or C 1-4 haloalkyl.

3. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt according to claim 2, wherein, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, nitro, amino, cyano, carboxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy; R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-9 aryl, C 5-9 heteroaryl, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, C 1-3 alkylamino C 1-3 alkyl, C 3-6 cycloalkyl C 1-3 alkyl, C 3-6 heterocyclic group C 1-3 alkyl, C 6-9 aryl C 1-3 alkyl, C 5-9 heteroaryl C 1-3 alkyl, or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 5-12 heteroaryl, C 1-3 alkoxyC 1-3 alkyl, C 1-3 alkylthioC 1-3 alkyl, C 3-8 cycloalkylC 1-3 alkyl, C 3-6 heterocyclic groupC 1-3 alkyl, C 6-12 arylC 1-3 alkyl, C 5-12 heteroarylC 1-3 alkyl, And R1 and R2 may be mono- or poly-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 1-3 alkoxycarbonyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl; R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxyl, cyano, nitro, amino, carboxyl, C 1-4 alkyl or halo-C 1-4 alkyl.

4. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt according to claim 3, wherein, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, nitro, amino, cyano, carboxy, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, C 1-3 alkyl, C 1-3 haloalkyl, C 1-3 alkoxy or C 1-3 haloalkoxy; R1 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-6 cycloalkyl, C 3-6 heterocyclic group, C 6-9 aryl, C 5-9 heteroaryl, C 1-3 alkoxy C 1-3 alkyl, C 1-3 alkylthio C 1-3 alkyl, C 1-3 alkylamino C 1-3 alkyl, C 3-6 cycloalkyl C 1-3 alkyl, C 3-6 heterocyclic group C 1-3 alkyl, C 6-9 aryl C 1-3 alkyl, C 5-9 heteroaryl C 1-3 alkyl, or R1 is selected from -C(=O)-R2, where R2 is selected from C 1-3 alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 1-3 alkoxy, C 1-3 alkylthio, C 1-3 alkylamino, C 3-8 cycloalkyl, C 3-8 heterocyclic group, C 6-12 aryl, C 5-12 heteroaryl, and R1, R2 may be mono-substituted or multi-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl; R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxy, C 1-4 alkyl or halo-C 1-4 alkyl.

5. The compound of formula (I) or an isotopically labeled compound thereof, or an optical isomer, geometric isomer, tautomer or mixture of isomers thereof, or an acceptable salt according to claim 4, wherein, X1, X2, X3, X4 are each independently selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, cyclopropyl, C 1-3 alkyl or C 1-3 haloalkyl; R1 is selected from methyl, ethyl, propyl, allyl, propargyl, cyclopropylmethyl, glycidylmethyl, or R1 is selected from -C(=O)-R2, wherein R2 is selected from methyl, ethyl, n-propyl, isopropyl, allyl, propargyl, methoxy, ethoxy, n-propoxy, isopropoxy, N,N-dimethylamino, cyclopropyl, glycidyl, furyl, phenyl, and R1, R2 may be mono- or poly-substituted by one or more identical or different substituents selected from: fluorine, chlorine, bromine, cyano, nitro, C 1-3 alkyl, C 1-3 alkoxy, C 1-3 haloalkyl, C 3-6 cycloalkyl, C 3-6 epoxyalkyl; R3 is hydrogen, fluorine, chlorine, bromine, iodine, hydroxy, cyano, nitro, amino, carboxyl, CH3, CH2CH3, CH2CH2CH3, CH(CH3)2, C(CH3)3, CH2Cl, CHF2 or CF3.

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

7. The active composition according to claim 6, wherein the dosage form is selected from powder, bait, granule, 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 granule, water soluble granule, macrogranule, granule for broadcasting and soil application, aerosol, ultra-low volume agent and wax product.

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

9. The use according to claim 8, wherein the pests are selected from pests belonging to Arthropoda, Coleoptera, Diptera, Heteroptera, Homoptera, Hymenoptera, Isoptera, Lepidoptera, Orthoptera, Phthiraptera, Thysanoptera, Nematoda.

10. Use of the compound of formula (I) or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or acceptable salt according to any one of claims 1-5 in the preparation of an agent for controlling animal parasites or a sanitizing and disinfecting agent.

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