Substituted arylthio heterocyclic derivative as well as preparation and application thereof

Abstract

The invention relates to a substituted arylthio heterocyclic 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, or an optical isomer, a geometric isomer, a tautomer or an isomer mixture, or an acceptable salt of the compound, which is used as a substituted arylthio heterocyclic derivative, and application of the compound in preparation of insecticides for pest control, the compound can achieve a better pest control effect at a lower dosage, especially for pests such as tetranychidae, microcosaridae, acaridae, tarsonidae, aleuridae and root-knot nematode, and can be used for controlling pests such as tetranychidae, microcosaridae, gall mite, tarsonidae, aleuridae and the like. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of chemistry, and in particular to a heterocyclic derivative substituted with an arylthio group, and a preparation and application thereof. Background Art

[0002] Agricultural pests are recognized worldwide as one of the most difficult groups of organisms to control. In my country, there are over 40 species of agricultural pests, the most common of which are spider mites, gall mites, tarsonemes, and flour mites. These pests are extremely destructive to commercial crops such as fruit trees, vegetables, and flowers. Due to the excessive and irrational long-term use of existing acaricides, many pests have developed severe resistance.

[0003] Trifluoroethyl sulfide (sulfoxide) compounds are a class of novel and highly effective acaricides reported in recent years. For example, patents WO 2013092350, CN108658816A, CN108276358A, WO2017067500, WO2011020567, WO2014202505, WO 2014095979, WO 2015004028, WO2016087371, WO2018051252, WO2019233321, WO2021056922, CN114763330A, and WO2022012483 have reported many similar compounds. However, the results of these studies are still unsatisfactory in terms of efficacy, durability, and toxicity.

[0004] Therefore, there is an urgent need to develop highly efficient green acaricides with novel structures and unique mechanisms of action. Summary of the Invention

[0005] The present invention relates to a heterocyclic derivative substituted with an aromatic thio group, which has a novel structure. Such a compound can achieve better pest control effects at a lower dosage, especially against pests such as Tetranychus, Tenebrionidae, Cyprinidae, Tarsonemidae, Acaridae, and Heterodermidae.

[0006] Specifically:

[0007] In one aspect, the present invention provides a substituted arylthio heterocyclic derivative, which is a compound represented by formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture, or an acceptable salt thereof:

[0008]

[0009] in,

[0010] R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl;

[0011] R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;

[0012] R6, R7 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C6 alkoxycarbonyl, C1-C3 alkyl, C1-C6 alkylthio, C1-C3 alkylcarbonyl, C1-C6 alkylaminocarbonyl, C1-C6 dialkylaminocarbonyl, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 alkyloxalyl or C1-C6 alkoxyoxalyl;

[0013] R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkyl, C 1-6 Alkoxycarbonyl, C 3-6 Cycloalkyl, C 6-12 aryl;

[0014] A is oxygen or sulfur, and n is 0, 1 or 2.

[0015] In some embodiments,

[0016] R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl;

[0017] R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;

[0018] R6, R7 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C6-C 10 Heterocyclic group, C6-C 10Aryl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C6 alkoxycarbonyl, C1-C3 alkyl, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 alkyloxalyl or C1-C6 alkoxyoxalyl;

[0019] R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkyl, C 1-6 Alkoxycarbonyl, C 3-6 Cycloalkyl;

[0020] A is oxygen or sulfur, and n is 0, 1 or 2.

[0021] In other embodiments,

[0022] R1 is selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl;

[0023] R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl;

[0024] R6, R7 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkyl, C1-C3 alkylsulfoxide, C1-C3 alkylsulfone, C1-C3 alkyloxalyl or C1-C3 alkoxyoxalyl;

[0025] R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl;

[0026] A is oxygen or sulfur, and n is 0, 1 or 2.

[0027] In other embodiments,

[0028] R1 is selected from methyl, ethyl, n-propyl, isopropyl, CFH2, CF2H, CF3, CH3CF2, CF2CH 2、 CF3CH2, CF3CF2, CH3CF2CH2, CH3CF2CF2, CF3CH2CH2, CF3CF2CH2, CF3CF2CF2, CH3CH(CF3), CH3CF(CF3), CF3CH(CF3), cyclopropylmethyl, glycidylmethyl;

[0029] R2, R3, R4, R5 are independently selected from hydrogen, cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, CF3, CF3CH2, CF3CF2, CH3CF(CF3), CF3CH(CF3), (CF3)2CF, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

[0030] R6, R7 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkyl, C1-C3 alkylsulfoxide, C1-C3 alkylsulfone, C1-C3 alkyloxalyl or C1-C3 alkoxyoxalyl;

[0031] R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl;

[0032] A is oxygen or sulfur, and n is 0, 1 or 2.

[0033] In other embodiments,

[0034] R1 is selected from methyl, ethyl, n-propyl, isopropyl, CF3, CH3CF2, CF3CH2, CF3CF2, CH3CF2CH2, CH3CF2CF2, CF3CH2CH2, CF3CF2CH2, CF3CF2CF2;

[0035] R2, R3, R4, R5 are independently selected from hydrogen, cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, CF3, CF3CH2, CF3CF 2、 (CF3)2CF;

[0036] R6, R7 are independently selected from hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, glycidylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, phenyl, indolyl, benzimidazolyl, quinolyl, aryl, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, isobutylcarbonyl, methoxycarbonyl, ethoxycarbonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, arylcarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methylsulfoxide, methylsulfone, methyloxalyl, ethyloxalyl, methoxyoxalyl, ethoxyoxalyl;

[0037] R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl;

[0038] A is oxygen or sulfur, and n is 0, 1 or 2.

[0039] In a second aspect, the present invention provides an intermediate compound, which is an intermediate 4 for preparing the derivative described in the first aspect, wherein the structure of the intermediate compound is:

[0040]

[0041] wherein R1, R2, R3, R4, R5, R6, R7, A, and n are as defined above.

[0042] In other embodiments, in order to avoid ambiguity, the following definitions are given for the terms used in this article. Unless otherwise specified, the meanings of the terms used in this article are as follows.

[0043] The term "alkyl", used alone or in compound words such as "alkylthio" or "haloalkyl", includes straight or branched chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, or different butyl, pentyl, or hexyl isomers. "Alkenyl" includes straight 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 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. "Alkyne" refers to straight or branched chain alkanediyl. "Alkyl," "alkenyl," and "alkynyl" groups may be optionally substituted by one or more (eg, 1 to 5) suitable substituents.

[0044] 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.

[0045] The term "alkoxy" includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, and the different butoxy, pentoxy, and hexoxy isomers. "Alkoxyalkyl" refers to an alkoxy substitution on an alkyl group. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2OCH2, and CH3CH2OCH2CH2.

[0046] The term "alkylcarbonyl" refers to a straight 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 different butoxycarbonyl, pentoxycarbonyl, and hexoxycarbonyl isomers.

[0047] The term "cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "alkylcycloalkyl" refers to an alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl, and 4-methylcyclohexyl. The term "cycloalkylalkyl" refers to a cycloalkyl substitution on an alkyl moiety. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, cyclohexylmethyl, and other cycloalkyl moieties bonded to a straight or branched chain alkyl group.

[0048] The term "halogen", alone or in compound words such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", includes fluorine, chlorine, bromine or iodine. Furthermore, when used in compound words such as "haloalkyl", or when used in a description such as "alkyl substituted by halogen", the alkyl group may be partially or fully substituted with halogen atoms (which may be the same or different). Examples of "haloalkoxy" include CF3O-, CCl3CH2O-, HCF2CH2CH2O- and CF3CH2O-.

[0049] The total number of carbon atoms in a substituent is represented by "C i -C j " prefix represents, wherein i and j are numbers from 1 to 9. For example, C1-C4 alkyl represents methyl to butyl.

[0050] 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, cBu is cyclobutyl, cPn is cyclopentyl, cHx is cyclohexyl, cHp is cycloheptyl, Oct is octyl, Ph is phenyl, Bn is benzyl, Thi is thiophen-2-yl, Pyrrole-1-yl, 2-Py is pyridin-2-yl, 3-Py is pyridin-3-yl, and 4-Py is pyridin-4-yl. In a substituent represented by a plurality of abbreviations, the substituent consists of the substituents represented by the abbreviations bonded to each other. For example, 2-Me-Ph represents a 2-methyl substituted phenyl group, and cPr-CH2 represents a cyclopropyl substituted methyl group.

[0051] A variety of synthetic methods are known in the art that enable the preparation of aromatic and nonaromatic heterocycles and ring systems; for extensive reviews, see the eight-volume collection Comprehensive Heterocyclic Chemistry, edited by AR Katritzky and CW, Pergamon Press, Oxford, 1984, and the twelve-volume collection Comprehensive Heterocyclic Chemistry II, edited by AR Katritzky, CW Rees, and EF V Scriven, Pergamon Press, Oxford, 1996.

[0052] The compounds of the present invention may exist as one or more stereoisomers. Stereoisomers are isomers that have the same composition but different arrangements of their atoms in space, and include enantiomers, diastereomers, cis-trans isomers (also referred to as geometric isomers) and atropisomers. Atropisomers are caused by restricted rotation around a single bond, where the rotation barrier is high enough to allow separation of isomers. Those skilled in the art will appreciate 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 the stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds [organic compound stereochemistry], John Wiley & Sons [John Wiley & Sons Publishers], 1994.

[0053] The present invention provides a method for preparing a compound of formula (I) which is a heterocyclic derivative of a substituted arylthio group:

[0054]

[0055] Intermediate 7 is reacted with different electrophilic reagents in an alkaline environment to obtain intermediate 6. Aniline of formula 6 is directly reacted with thiophosgene to obtain isothiocyanate or reacted with carbon disulfide in the presence of a base to form the corresponding dithio salt, and then reacted with the following reagents, such as chloroformate (J.Org.Chem.29(1964)3098), toluenesulfonyl chloride (WO2012 / 129338), phosgene (Chem.Zentralblatt 101(1930)Buch1(3),3431), sodium hypochlorite (LiebigsAnn.Chem.585(1954)230), sodium chlorite (DE 960276), TCT or hydrogen peroxide to prepare isothiocyanate (A=S). At the same time, aniline of formula 6 can be converted into the corresponding isocyanate (A=O) by known methods. Isothiocyanate or isocyanate in formula 5 reacts with different hydrazines to obtain compounds of formula 4. Compounds of Formula 4 and halogenated carbonyl compounds form annulations to yield the corresponding target compounds of Formula 3 (oxazolidinone or thiazolidinone). Compounds of Formula 3 react with various electrophiles in an alkaline environment to yield disubstituted target compounds 2, or compounds of Formula 4-2 directly form annulations to yield target compounds 2. Compounds of Formula 2 are then oxidized to yield target compounds of Formula I.

[0056] In addition, the present invention also lists a number of exemplary compounds that have been synthesized, and their 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 table below, and the various group selections of the compounds in Table 1 below can be arbitrarily combined without particular limitation.

[0057] In the general formula I in Table 1, n=0, A=S, and the specific R1, R2, R3, R4, R5, R6, and R7 are shown in the table below.

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069] R1, R2, R3, R4, R5, R6, and R7 of compounds II-001 to II-374 are as defined in Table 1, except that n=0 and A=O;

[0070] R1, R2, R3, R4, R5, R6, and R7 of compounds III-001 to III-374 are as defined in Table 1, except that n=1 and A=S;

[0071] R1, R2, R3, R4, R5, R6, and R7 of compounds IV-001 to IV-374 are as defined in Table 1, except that n=1 and A=O;

[0072] R1, R2, R3, R4, R5, R6, and R7 of compounds V-001 to V-374 are as defined in Table 1, except that n=2 and A=S;

[0073] R1, R2, R3, R4, R5, R6, and R7 of compounds VI-001 to VI-374 are defined as in Table 1, except that n=2 and A=O.

[0074] In a third aspect, the present invention provides an insecticide composition comprising a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture thereof, or an acceptable salt thereof, and an acceptable carrier.

[0075] 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 oil, polyalkylene glycol, petrolatum, mannitol, cellulose, cellulose derivatives, sodium saccharin, magnesium carbonate, saline, glycerol, ethanol, etc. In addition, the pesticide composition may also contain other additives, such as preservatives, stabilizers, emulsifiers, buffers, diluents, binders, wetting agents, lubricants, glidants, etc.

[0076] The dosage form of the insecticide composition of the present invention can be a liquid dosage form, a solid dosage form or a semisolid 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, aqueous 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.

[0077] 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 target, 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, 1.0 mg / L, 2.5 mg / L, 5.0 mg / L or 10.0 mg / L.

[0078] The specific administration frequency can be determined by technicians in the relevant field, for example, 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.

[0079] In a fourth aspect, the present invention provides use of a compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture, or an acceptable salt thereof in the preparation of an insecticide for pest control.

[0080] The compounds of the present invention are suitable for controlling pests or acarids, that is, controlling pests or acarids, wherein the pests or acarids refer to harmful or unwanted insects or acarids, especially harmful or unwanted insects or acarids encountered in agriculture, forestry, storage product protection and material protection, as well as in the fields of hygiene and animal protection. The compounds of the present invention are active against generally sensitive and resistant species and are effective at all stages of the development of the pests or acarids.

[0081] The present invention also relates to a method for controlling pests or acarids, which comprises applying a control-effective amount of a compound of formula (I) to the locus 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 may also be used to control other invertebrate pests or organisms.

[0082] Specifically, the insect habitat, pest habitat, or mite habitat refers to the environment where insects, pests, or mites live or where their eggs exist, including the surrounding air, food, or objects they come into contact with. For example, by applying the active compound to plant seeds (before planting), seedlings, or planted cuttings, leaves, stems, fruits, grains, and / or roots, or to soil or other growth media (before or after crop planting), it is possible to control insects or mites that eat, destroy, or come into contact with edible agricultural products, ornamental plants, turf, pasture plants, or other economically valuable plants. It is also possible to protect these plants from diseases caused by viruses, fungi, or bacteria by controlling sap-feeding pests such as whiteflies, planthoppers, aphids, or mites such as spider mites and spider mites. The plants include those bred by conventional methods, as well as plants genetically modified through modern biotechnology to impart insect or mite resistance, herbicide resistance, high yield, and / or other beneficial characteristics. It is expected that the compounds will be useful for protecting fabrics, paper, stored grain, seeds and other foodstuffs, homes, buildings and the like, and / or loci, by applying the compounds of the invention to or in the vicinity of such objects.

[0083] The inventors have discovered that the compounds of the present invention are effective against animal pests encountered in agronomic and non-agronomic fields, as well as in the health and animal protection sectors, even when applied at relatively low doses, particularly insects, arachnids, worms, nematodes and molluscs. These compounds are preferably used as insecticides. They are effective against normally sensitive and resistant species and against all or some developmental stages. These pests include:

[0084] Pests from the phylum Arthropoda, in particular from the class Arachnida, for example from the orders Acari, Metastigmata and Mesostigmata, the families Tetranychidae, Eupodidae, Eriophyiade, Phytoseiidae, Tarsonemidae, Acaridae, and also Acarus spp. (for example Acarus siro, Aceria kuko, Aceria sheldoni), Aculops spp., Aculus spp. (for example Aculus fockeui, Aculus spp. schlechtendali), Amblyomma spp., Amphitetranychus viennensis, Eotetranychus spp., Tetranychus, Panonychus, Oligonychus, Schizotetranychus, Argas spp., Boophilus spp., Brevipalpus spp. (e.g., Brevipalpus phoenicis), Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus), Dermatophagoides farinae, Dermacentor spp., Ornithodorus spp., Otobius spp., 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.

[0085] Pests from the order of the Coleoptera, for example, Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp. (e.g. Agriotes linneatus, Agriotes mancus), Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp. (e.g. Anthonomus grandis), Anthrenus spp., Apion spp., Apogonia spp.), Atomaria spp. (e.g., Atomaria linearis), Attagenus spp., Baris caerulescens, Bruchidius obtectus, Bruchus spp. (e.g., Bruchus pisorum, Bruchus rufimanus), Cassida spp., Cerotoma trifurcata, Ceuthorhynchus spp. (e.g., Ceutorrhynchus assimilis, Ceutorrhynchus quadridens, Ceutorrhynchus rapae), Chaetocnema spp.) (e.g., sweet potato flea beetle (Chaetocnema confinis), Chaetocnemadenticulata, corn flea beetle (Chaetocnema ectypa)), Cleonus mendicus, broad-breasted click beetle (Conoderus spp.), root-necked weevil (Cosmopolites spp.) (e.g., banana black weevil (Cosmopolites sordidus));

[0086] Pests from the order of Diptera, for example, 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 orientalis), dorsalis, olive fruit fly (Bactrocera oleae), garden midge (Bibio hortulanus), glass fly (Calliphora erythrocephala), red-headed blowfly (Calliphora vicina), Mediterranean fruit fly (Ceratitis capitata), Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp. (e.g., grape gall midge (Contarinia johnsoni), cabbage gall midge (Contarinia nasturtii), pear gall midge (Contarinia pyrivora);

[0087] Pests from the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp. (e.g., Cimex adjunctus, Cimex hemipterus, Cimex lectularius, Cimex pilosellus), Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti), Dysdercus spp., and Euschistus spp.;

[0088] Pests from the order of the Homoptera, for example, Acizzia acaciae baileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp. (e.g., Acyrthosiphon pisum), Acrogonia spp., Aeneolamia spp., Agonascena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. (e.g., Amrasca bigutulla, Amrasca devastans), Anuraphis cardui, Aonidiella spp. (e.g. Aonidiella aurantii, Aonidiella citrina, Aonidiella inornata), Aphanostigma piri, Aphis spp. (e.g. Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis glycines, Aphis gossypii, Aphis hederae, Aphis illinoisensis, Aphis middlingtoni, Aphis nasturtii, Aphis nerii);

[0089] Pests from the order of the Hymenoptera, for example, Acromyrmex spp., Athalia spp. (for example Athalia rosae), Atta spp., Diprion spp. (for example Diprion similis), Hoplocampa spp. (for example Hoplocampa cookei, Hoplocampa testudinea), Lasius spp.;

[0090] Pests from the order of the Isoptera, for example, Coptotermes spp. (e.g. Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp.), Reticulitermes spp. (e.g. Reticulitermes flavipes, Reticulitermes hesperus);

[0091] Pests from the order of the Lepidoptera, for example, Achroia grisella, Acronicta major, Adoxophyes spp. (e.g., Adoxophyesorana), Aedia leucomelas, Agrotis spp. (e.g., Agrotissegetum, Agrotis ipsilon), Alabama spp. (e.g., Alabama argillacea), Amyelois transitella, Anarsia spp., Anticarsia spp. (e.g., Anticarsia gemmatalis), Argyroploce spp., Barathra brassicae), Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capuareticulana, Carpocapsa pomonella, Carposinaniponensis, Cheimatobia brumata, Chilo spp. (e.g., Chiloplejadellus, Chilo suppressalis), Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocism medinalis, Cnephasia spp.), Conopomorpha spp.;

[0092] Pests from the order of Orthoptera or Saltatoria, for example, house crickets (Acheta domesticus), Dichroplus spp., Gryllotalpa spp. (for example Gryllotalpa gryllotalpa), Hieroglyphus spp., Locusta spp. (for example Locusta migratoria), Melanoplus spp. (for example Melanoplus devastator), desert locust (Schistocerca gregaria);

[0093] Pests from the order of the Thysanoptera, for example, Anaphothrips obscurus, Baliothrips biformis, Drepanothris reuteri, Enneothrips flavens, Frankliniella spp. (e.g. Frankliniella fusca, Frankliniella occidentalis, Frankliniella schultzei, Frankliniella tritici, Frankliniella vaccinii, Frankliniella williamsi), Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp.), Taeniothrips cardamoni, Thrips spp. (e.g. Thrips palmi, Thrips tabaci);

[0094] Plant pests from the phylum Nematoda, i.e. plant-parasitic nematodes, in particular Aglenchus spp. (e.g. Aglenchus agricola), Anguinas spp. (e.g. Anguina tritici), Aphelenchoides spp. (e.g. Aphelenchoides arachidis, Aphelenchoides fragariae), Belonolaimus spp. (e.g. Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni), Bursaphelenchus spp. (e.g. Bursaphelenchus spp. cocophilus), Bursaphelenchus eremus, Bursaphelenchus xylophilus); Meloidogyne spp.) (e.g., Meloidogyne chitwoodi, Meloidogyne fallax, Meloidogyne acronea, Meloidogyne africana, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyneartiella, Meloidogyne chitwoodi, Meloidogyne coffeicola, Meloidogyne ethiopica, Meloidogyne exigua, Meloidogyne fallax, Meloidogyne graminicola ... graminis), Meloidogyne hapla, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne kikuyensis, Meloidogyne minor, Meloidogyne naasi, Meloidogyne paranaensis, Meloidogyne thamesi, and non-migratory parasitic Meloidogyne spp.; Tylenchulus spp. (e.g., Tylenchulus semipenetrans), Xiphinema species spp.) (e.g. marking Xiphinema index).

[0095] In another preferred embodiment of the present invention, the pests prevented and / or controlled by the compound or composition of the present invention can be selected from the family Tetranychus urticae, preferably Tetranychus urticae and Tetranychus cinnabarinus.

[0096] The beneficial effects of the present invention are:

[0097] By chemically modifying and molecularly designing compounds with thiazolidinone structures and changing the substituents on the thiazole ring, a series of more efficient compounds with excellent activity that can be used for insecticides or acaricides in agriculture or forestry have been obtained, especially with high insecticidal or acaricidal activity at low doses. DETAILED DESCRIPTION

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

[0099] Those skilled in the art will appreciate that the definitions and preferences described in one aspect of the present invention are equally applicable to other aspects. Those skilled in the art will appreciate that the embodiments of the various aspects of the present invention may 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.

[0100] The present invention is further illustrated below with reference to examples; however, these examples are not intended to limit the scope of the present invention. Unless otherwise stated, all reactants used in the examples were obtained from commercial sources; and the instruments and equipment used in the synthesis experiments and product analysis and testing were conventional instruments and equipment commonly used in organic synthesis.

[0101] Example 1 Synthesis of 2-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)imino)-3-((2,2,2-trifluoroethylamino)thiazolidin-4-one (Compound I-053)

[0102]

[0103] 1.0 g (3.56 mmol) of 1-fluoro-2-isothiocyanato-5-methyl-4-[(2,2,2-trifluoroethyl)thio]benzene was added to a reaction flask and dissolved in 40 mL of toluene. 0.49 g (4.27 mmol) of 2,2,2-trifluoroethylhydrazine and 0.59 g (4.27 mmol) of potassium carbonate were then added in sequence. The reaction was stirred at room temperature and monitored by TLC. After the complete disappearance of 1-fluoro-2-isothiocyanato-5-methyl-4-[(2,2,2-trifluoroethyl)thio]benzene, 0.65 g (4.27 mmol) of methyl bromoacetate was added to the reaction system. The reaction was heated to 45°C and, after complete reaction, poured into a saturated aqueous solution of common salt, the organic phase was collected, dried, filtered, and the solvent was removed by rotary evaporation. Purification by silica gel column chromatography gave 0.53 g of the product with a yield of 34.24%.

[0104] 1 H NMR(400MHz, DMSO-d6)δ:7.80(dd,J=7.8,1.5Hz,1H),7.24(d,J=11.0Hz,1H),5.25(d,J=76.8Hz, 3H),4.99(q,J=9.2Hz,2H),4.01-3.75(m,2H),2.39(d,J=1.5Hz,3H).LC-MS(m / z,ESI):436[M+H] + ;

[0105] Example 2 Synthesis of N-(2-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)imino)-4-oxothiazolidin-3-yl)-N-(2,2,2-trifluoroethyl)acetamide (Compound I-092)

[0106]

[0107] 0.3 g (0.69 mmol) of compound I-053 obtained in Example 1 was added to the reaction flask and dissolved in 15 ml of DMF. Subsequently, 0.084 g (0.83 mmol) of triethylamine was added to the reaction system, and then the reaction system was cooled to 0°C. At this temperature, 0.065 g (0.83 mmol) of acetyl chloride was slowly added dropwise to the reaction system. After the addition was complete, the reaction was stirred at room temperature. After the reaction was completed, the reaction was quenched and poured into saturated brine. The mixture was extracted, and the organic phases were combined, dried, and separated by column chromatography to obtain 0.033 g of the product with a yield of 10.03%.

[0108] 1 H NMR(400MHz, DMSO-d6)δ:7.37(d,J=8.3Hz,1H),7.14(d,J=11.5Hz,1H),4.67(q,J=9.0Hz,2H ),3.87(q,J=10.4Hz,2H),3.31(s,2H),2.33(s,3H),2.25(s,3H).LC-MS(m / z,ESI):478[M+H] + ;

[0109] Example 3 Synthesis of 1,1,1-trifluoro-N-(2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)sulfanyl)phenyl)imino)-4-oxothiazolidin-3-yl)-N-(2,2,2-trifluoroethyl)methanesulfonamide (Compound I-168)

[0110]

[0111] 0.3 g (0.69 mmol) of compound I-053 obtained in Example 1 was added to the reaction flask and dissolved in 15 ml of dichloromethane. Subsequently, 0.084 g (0.83 mmol) of triethylamine was added to the reaction system, and then the reaction system was cooled to 0°C. At this temperature, 0.293 g (1.04 mmol) of trifluorosulfonic anhydride was slowly added dropwise to the reaction system. After the addition was complete, the reaction was stirred at room temperature. After the reaction was completed, the reaction was quenched with sodium bicarbonate, and then the reaction system was poured into saturated brine and extracted with dichloromethane. The organic phases were combined, dried, and separated by column chromatography to obtain 0.053 g of compound I-168 with a yield of 13.56%.

[0112] 1 H NMR(400MHz, DMSO-d6)δ:7.24(d,J=11.3Hz,1H),7.12(d,J=8.2Hz,1H),4.87(q,J=9.0 Hz,2H),4.31(s,2H),3.88(q,J=10.3Hz,2H),2.37(s,3H).LC-MS(m / z,ESI):568[M+H] + ;

[0113] Example 4

[0114] Synthesis of Intermediate 2-(tert-butyl)-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)hydrazine-1-thiocarboxamide (Intermediate 1)

[0115]

[0116] 1.0 g (3.56 mmol) of 1-fluoro-2-isothiocyanato-5-methyl-4-[(2,2,2-trifluoroethyl)thio]benzene was added to the reaction flask and dissolved in 40 mL of toluene. 0.38 g (4.27 mmol) of tert-butylhydrazine hydrochloride and 0.59 g (4.27 mmol) of potassium carbonate were added in sequence, and the reaction was stirred at room temperature. The reaction was monitored by TLC. The reaction was stopped after the complete disappearance of the starting material. The reaction system was poured into water and extracted. The organic phase was collected, dried, filtered, and the solvent was removed by rotary evaporation to obtain 1.30 g of intermediate 1 with a yield of 98.98%. No purification was required and the next step of the reaction was continued.

[0117] The single crystal structure of intermediate 1 is as follows:

[0118]

[0119] Example 5

[0120] 3-(tert-Butylamino)-2-((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)imino)thiazolidin-4-one (Synthesis of Compound I-227)

[0121]

[0122] 0.5 g (1.78 mmol) of 1-fluoro-2-isothiocyanato-5-methyl-4-[(2,2,2-trifluoroethyl)thio]benzene was added to the reaction flask and dissolved in 40 mL of toluene. Then, 0.24 g (1.96 mmol) of tert-butylhydrazine hydrochloride and 0.29 g (2.13 mmol) of potassium carbonate were added in sequence, and the reaction was stirred at room temperature. The reaction was monitored by TLC. After the complete disappearance of 1-fluoro-2-isothiocyanato-5-methyl-4-[(2,2,2-trifluoroethyl)thio]benzene, 0.33 g (2.13 mmol) of methyl bromoacetate was added to the reaction system, and the mixture was heated to 45° C. to react. After the reaction was complete, the mixture was poured into a saturated saline solution, the organic phase was collected, dried, filtered, and the solvent was removed by rotary evaporation. The product was purified by silica gel column chromatography to obtain 0.66 g of the product with a yield of 90.68%.

[0123] 1 H NMR(400MHz,Chloroform-d)δ:7.14(d,J=7.9Hz,1H),6.99(d,J=10.8Hz,1H),4.98(s,1H) ,3.83(s,2H),3.30(q,J=9.6Hz,2H),2.43(s,3H),1.21(s,9H).LC-MS(m / z,ESI):410[M+H] + ; Its single crystal structure is as follows:

[0124]

[0125] Table 2 The structural formula, physicochemical properties, NMR and mass spectrometry data of the exemplary compounds of the present invention are as follows:

[0126]

[0127]

[0128] Test example: Biological indoor activity test

[0129] Test method: Refer to the agricultural industry standard NY / T1154.13-2008 and use the leaf disc spray method to determine.

[0130] Material Preparation: Select female adult mites raised indoors and in a consistent physiological state. Select leaves of a host plant with consistent growth (e.g., broad bean leaves, kidney bean leaves, etc.). Use a hole punch to create leaf discs. Place a damp sponge in a petri dish, topped with filter paper, and the leaf disc on top of the filter paper. Inoculate the leaf discs with 30-40 mites or nymphs raised indoors.

[0131] Dose Preparation: Test compound (2 mg) was dissolved in 2 mL of DMSO to form a 1000 mg / L stock solution. This stock solution was diluted 10-fold with 0.1% Tween-80 in HO to obtain a 100 mg / L test solution, and 20-fold to obtain a 50 mg / L test solution. The same dilution method was repeated to obtain further test concentrations.

[0132] Calculation method:

[0133] Corrected mortality (%) = [(treatment mortality - control mortality) / (1 - control mortality)] × 100%

[0134] Each treatment was repeated 3 times, and a solvent control was set. If the control mortality rate was greater than 10%, the test was repeated. If the control mortality rate was less than 10%, the acaricidal activity was measured using Abbott's correction formula, and the toxicity regression equation was calculated using the DPS data processing system to calculate the LC 50 The values, 95% confidence limits and statistical analysis were performed.

[0135] Test Example 1: Biological activity test against adults of Tetranychus urticae Koch

[0136] Test method: Use leaf disc spray method to determine, select clean, flat, appropriately sized, and uniformly aged kidney bean leaves, spread them flat on a culture dish with clean filter paper, with the reverse side facing up, and add water to the filter paper to keep it moist. Inoculate 30-40 adult spider mites of basically the same physiological state into each dish.

[0137] Place the petri dish under a Potter spray tower and spray with a fixed amount (2.5 mL) of spray until the leaf surface and the mite body are just covered with spray droplets. Incubate the test target in a climatic chamber (24-26°C, L:D = 16:8, RH 60%). After 72 hours, examine and record the mortality of adult mites. Mites are considered dead if their legs do not move or respond when touched with tweezers. Each treatment is replicated four times, with a solvent control. The test concentration is 100 mg / L.

[0138] Test results: Among some exemplary compounds, compounds I-053, I-074, I-092, I-126, I-168, I-227, I-312, II-053, II-227, and II-312 showed a 100% insect mortality rate at a dosage of 100 mg / L.

[0139] Furthermore, in the following test examples, the insecticidal compound Ib71 disclosed in patents WO2013092350A1, CN108658816A, CN108276358A, etc., with the common name sulfiflumin (represented as CK1 in the text); the insecticidal compound Ia-175 (represented as CK2 in the text) was used as a positive control.

[0140]

[0141] According to the above method, compound 8 was selected and tested in parallel with the known compounds CK1 (sulfiflumin), CK2, and spirodiclofen for their activity against adult spider mites. The experimental results are shown in Table 3. CK2 is known to have an efficacy of more than 90% against spider mites at a dose of 500 g / ha.

[0142] Table 3 Activity assay against Tetranychus urticae adults (72h)

[0143]

[0144] From the above biological activity results, it can be seen that the compounds in this study still have excellent control effects on two-spotted spider mites at low concentrations (0.5 ppm), which is better than the control agent. This type of compound is expected to be used to control agricultural pest mites and solve the current problems of high resistance and severe homogenization.

[0145] Test Example 2: Biological activity test against Tetranychus cinnabarinus nymphs

[0146] Experimental method: Use leaf disc spray method, take fresh broad bean potted plants, inoculate several adult cinnabarinus spider mites on the leaves, remove the adult mites after laying eggs for 1 day, wait for the eggs to hatch into nymphs and set them aside, select clean, flat, appropriately sized, and uniform leaf age broad bean leaves, beat the broad bean leaves into leaf discs, moisturize with cotton, and place them in plastic culture dishes, inoculating 30-40 nymphs of cinnabarinus spider mites in each dish.

[0147] Place the Petri dish under a Potter spray tower and spray a fixed amount (2.5 mL) of the solution. After air drying, incubate the test specimen in a climatic chamber (24-26°C, L:D = 16:8, RH 60%). Insects were assessed after 48 hours. No response was detected by prodding the insects with forceps; the insects were considered dead. Each treatment was repeated four times, with a solvent control. The test concentration was 100 mg / L.

[0148] Test results: Among some exemplary compounds, compounds I-032, I-053, I-092, I-161, I-168, I-227, I-312, II-053, II-227, and II-312 showed a 100% insect mortality rate at a dosage of 100 mg / L.

[0149] Test Example 3: Biological activity test against adults of Tetranychus cinnabarinus

[0150] Experimental method: Use leaf disc spray method, select clean, flat, appropriate size, and uniform age broad bean leaves, beat the broad bean leaves into leaf discs, moisturize with cotton, place them in plastic culture dishes, and inoculate 30-40 adult cinnabarin spider mites in each dish.

[0151] Place the Petri dish under a Potter spray tower and spray a fixed amount (2.5 mL) of the solution. After air drying, incubate the test specimen in a climatic chamber (24-26°C, L:D = 16:8, RH 60%). Insects were assessed after 72 hours. No response was detected by prodding the insect with forceps; the insect was considered dead. Each treatment was repeated four times, with a solvent control. The test concentration was 100 mg / L.

[0152] Test results: Among some exemplary compounds, compounds I-032, I-053, I-092, I-161, I-168, I-227, I-312, II-053, II-227, and II-312 showed a 100% insect mortality rate at a dosage of 100 mg / L.

[0153] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

[0154] 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 in the scope of protection of the present invention.

Claims

1. A compound of formula (I) or an isotope-labeled compound thereof, or an optical isomer, geometric isomer, tautomer or isomer mixture, or an acceptable salt thereof, which is a heterocyclic derivative of a substituted arylthio group. in, R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl; R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; R6, R7 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C6 alkoxycarbonyl, C1-C3 alkyl, C1-C6 alkylthio, C1-C3 alkylcarbonyl, C1-C6 alkylaminocarbonyl, C1-C6 dialkylaminocarbonyl, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 alkyloxalyl or C1-C6 alkoxyoxalyl; R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, nitro, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkyl, C 1-6 Alkoxycarbonyl, C 3-6 Cycloalkyl, C 6-12 aryl; A is oxygen or sulfur, and n is 0, 1 or 2.

2. The compound of formula (I) according to claim 1 or its isotope-labeled compound, or its optical isomers, geometric isomers, tautomers or isomer mixtures, or acceptable salts thereof, wherein: R1 is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl; R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl; R6, R7 are independently selected from hydrogen, C1-C6 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl C1-C6 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C6 alkoxycarbonyl, C1-C3 alkyl, C1-C6 alkylsulfoxide, C1-C6 alkylsulfone, C1-C6 alkyloxalyl or C1-C6 alkoxyoxalyl; R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, C 1-6 Alkyl, C 1-6 Alkoxy, C 1-6 Halogenated alkyl, C 1-6 Alkoxycarbonyl, C 3-6 Cycloalkyl; A is oxygen or sulfur, and n is 0, 1 or 2.

3. The compound of formula (I) according to claim 2 or its isotope-labeled compound, or its optical isomers, geometric isomers, tautomers or isomer mixtures, or acceptable salts thereof, wherein: R1 is selected from C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C3-C6 cycloalkyl, C1-C3 alkyl or C3-C6 epoxyalkyl, C1-C3 alkyl; R2, R3, R4, R5 are independently selected from hydrogen, cyano, halogen, C1-C3 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl; R6, R7 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkyl, C1-C3 alkylsulfoxide, C1-C3 alkylsulfone, C1-C3 alkyloxalyl or C1-C3 alkoxyoxalyl; R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of halogen, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl; A is oxygen or sulfur, and n is 0, 1 or 2.

4. The compound of formula (I) according to claim 3 or its isotope-labeled compound, or its optical isomers, geometric isomers, tautomers or isomer mixtures, or acceptable salts thereof, wherein: R1 is selected from methyl, ethyl, n-propyl, isopropyl, CFH2, CF2H, CF3, CH3CF2, CF2CH 2、 CF3CH2, CF3CF2, CH3CF2CH2, CH3CF2CF2, CF3CH2CH2, CF3CF2CH2, CF3CF2CF2, CH3CH(CF3), CH3CF(CF3), CF3CH(CF3), cyclopropylmethyl, glycidylmethyl; R2, R3, R4, R5 are independently selected from hydrogen, cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, CF3, CF3CH2, CF3CF2, CH3CF(CF3), CF3CH(CF3), (CF3)2CF, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; R6, R7 are independently selected from hydrogen, C1-C4 alkyl, C3-C6 cycloalkyl, C3-C6 cycloalkyl, C1-C3 alkyl, C6-C 10 Heterocyclic group, C6-C 10 Aryl, C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, C3-C6 cycloalkylcarbonyl, C6-C 10 Arylcarbonyl, C1-C3 alkoxycarbonyl, C1-C3 alkyl, C1-C3 alkylsulfoxide, C1-C3 alkylsulfone, C1-C3 alkyloxalyl or C1-C3 alkoxyoxalyl; R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl; A is oxygen or sulfur, and n is 0, 1 or 2.

5. The compound of formula (I) according to claim 4 or its isotope-labeled compound, or its optical isomer, geometric isomer, tautomer or isomer mixture, or acceptable salt, wherein: R1 is selected from methyl, ethyl, n-propyl, isopropyl, CF3, CH3CF2, CF3CH2, CF3CF2, CH3CF2CH2, CH3CF2CF2, CF3CH2CH2, CF3CF2CH2, CF3CF2CF 2、 Cyclopropylmethyl, glycidylmethyl; R2, R3, R4, R5 are independently selected from hydrogen, cyano, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, CF3, CF3CH2, CF3CF2, (CF3)2CF; R6, R7 are independently selected from hydrogen, methyl, ethyl, propyl, cyclopropyl, isopropyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, glycidylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, oxazolyl, thiazolyl, pyranyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, phenyl, indolyl, benzimidazolyl, quinolyl, aryl, methylcarbonyl, ethylcarbonyl, isopropylcarbonyl, isobutylcarbonyl, methoxycarbonyl, ethoxycarbonyl, cyclopropylcarbonyl, cyclobutylcarbonyl, arylcarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, methylsulfoxide, methylsulfone, methyloxalyl, ethyloxalyl, methoxyoxalyl, ethoxyoxalyl; R6 and R7 may be substituted or polysubstituted by one or more identical or different substituents selected from the group consisting of fluorine, chlorine, bromine, cyano, C 1-4 Alkyl, C 1-3 Alkoxy, C 1-3 Halogenated alkyl, C 1-3 Alkoxycarbonyl, C 3-6 Cycloalkyl; A is oxygen or sulfur, and n is 0, 1 or 2.

6. An intermediate compound, which is the intermediate 4 for preparing the derivative according to any one of claims 1 to 5, characterized in that: The structure of the intermediate compound is: Wherein, R1, R2, R3, R4, R5, R6, R7, A, and n are defined as described in claim 1.

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

8. The active composition according to claim 7, wherein the dosage form is selected from the group consisting of powders, baits, granules, liquids, suspensions and sprays, preferably wettable powders, wettable liquids, soluble powders, dispersible liquids, aqueous solutions, microemulsions, emulsifiable concentrates, aqueous 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.

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

10. The use according to claim 9, wherein the pests are selected from the group consisting of pests belonging to the Tetranychidae, Tenebrionidae, Mylidae, Tarsonemidae, Acaridae, and Heteroderae.

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