CN116768824A

CN116768824A - Imide azole heterocyclic compound and application thereof

Info

Publication number: CN116768824A
Application number: CN202211575763.XA
Authority: CN
Inventors: 汤日元; 黄悦坤; 杨财鑫
Original assignee: South China Agricultural University
Current assignee: South China Agricultural University
Priority date: 2022-12-09
Filing date: 2022-12-09
Publication date: 2023-09-19
Also published as: WO2024119838A1

Abstract

The invention discloses an imide azole heterocyclic compound and application thereof. The imide azole heterocyclic compound shown in the general formula (I) provided by the invention has good biological activity on pests in agriculture and forestry and other fields, can be used as a pesticide, and particularly has good poisoning effect on agricultural pests such as plutella xylostella, spodoptera frugiperda, beet armyworm, prodenia litura and the like.

Description

Imide azole heterocyclic compound and application thereof

Technical Field

The invention belongs to the field of pesticides, and in particular relates to an imidozole heterocyclic compound and application thereof in the field of pesticides

Background

Pesticides are indispensable production data for agricultural production. With the long-term use of the pesticide, the pests can generate different degrees of resistance, so that the pesticide effect of the pesticide is obviously reduced. Development of novel pesticides with different mechanisms of action has been a technical difficulty in creating pesticides. The pesticides developed at present are mainly in an azacyclo structure, for example, recently newly developed pesticides such as cycloxaprid, cyantraniliprole, sulfoxaflor, flupirfenidone, flonicamid, cyflumetofen, spirotetramat, flucyrimin, chlorantraniliprole and the like are all azacyclo derivatives, and are mainly derived from azacyclo such as pyrazole or pyridine. The structure innovation is carried out, and the development of novel pesticides with brand new frameworks has great significance. According to the research progress of the existing pesticide, the inventor creatively develops the imide azole heterocyclic compound with novel framework and excellent insecticidal activity through a large amount of research practices.

Disclosure of Invention

The primary object of the present invention is to provide an imidozole heterocyclic compound which can control various agricultural and forestry pests or other pests in the field.

It is another object of the present invention to provide a route and method for synthesizing the imidozole heterocyclic compounds.

Still another object of the present invention is to provide the use of the imidozole heterocyclic compounds for controlling pests in agricultural or other fields.

The invention aims at realizing the following technical scheme:

an amidazoles compound or agriculturally acceptable salt thereof for controlling agricultural and forestry pests and pests in other fields, which is characterized in that the structure of the amidazoles compound is shown as a general formula (I):

in the general formula (I), R ₁ Selected from substituted or unsubstituted C _6-20 Aryl, substituted or unsubstituted C _2-20 Heteroaryl; wherein the substituted or unsubstituted mesosubstituent is selected from halogen, cyano,Hydroxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C ₁ - ₆ Alkoxy, C _3-6 Cycloalkyl, C _1-6 Alkoxycarbonyl, phenyl, halophenyl, benzyl;

w is selected from O or S;

Y ₁ selected from O, S, se or N;

represents a double bond or a single bond;

R _a ,R _b ,R _c ,R _d independently of each other selected from hydrogen, halogen, hydroxy, cyano, carboxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _3-6 Cycloalkyl, halo C _3-6 Cycloalkyl, substituted or unsubstituted C _6-20 Aryl, substituted or unsubstituted C _2-20 Heteroaryl, C _1-6 An alkoxycarbonyl group; wherein the substituted or unsubstituted mesosubstituent is selected from halogen, cyano, hydroxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _3-6 Cycloalkyl, C _1-6 Alkoxycarbonyl, phenyl, halophenyl, benzyl; alternatively, whenWhen representing a single bond, R _a /R _b And/or R _c /R _d Common constitution = O; when->When representing a double bond, R _a /R _b One is absent and R _c /R _d One is absent;

R ₂ selected from substituted or unsubstituted C _6-20 aryl-C _1-6 Alkyl, substituted or unsubstituted C _6-20 Aryl, substituted or unsubstituted C _2-20 Heteroaryl groupA base; wherein the substituted or unsubstituted mesosubstituent is selected from halogen, cyano, hydroxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _1-6 Alkylthio, halo C _1-6 Alkylthio, C _3-6 Cycloalkyl, C _1-6 Alkoxycarbonyl, phenyl, halophenyl, benzyl,

With the proviso that the compound of formula I is not compound I-15, I-17, I-19, I-20.

Preferably, in formula (I), R ₁ Selected from the group consisting of substituted or unsubstituted phenyl, furyl, thienyl, pyrimidinyl, pyrazinyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, benzofuryl, benzothienyl; wherein the substituted or unsubstituted mid-substituent is selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenyl; phenyl substituted with fluorine, chlorine, bromine and/or iodine; a benzyl group;

W is selected from O;

Y ₁ selected from S, se;

represents a double bond or a single bond;

R _a ,R _b independently of each other selected from hydrogen, methyl, ethyl, n-propylIsopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; a phenyl group;

R _c ,R _d independently of each other, selected from hydrogen, hydroxy, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyrazolyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl; wherein the substituted or unsubstituted mid-substituent is selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenyl; phenyl substituted with fluorine, chlorine, bromine and/or iodine; a benzyl group; alternatively, when When representing a single bond, R _a /R _b And/or R _c /R _d Common constitution = O; when->When representing a double bond, R _a /R _b One is absent and R _c /R _d One is absent;

R ₂ selected from the group consisting of substituted or unsubstituted benzyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyrazolyl, furanyl, thienyl, pyrimidinyl, pyrazinyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, benzofuranyl, benzothienyl; wherein the substituted or unsubstituted middle substituent is selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; methylthio, ethylthio, t-butylthio; methylthio, ethylthio, t-butylthio substituted by fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenyl; phenyl substituted with fluorine, chlorine, bromine and/or iodine; benzyl group,

Further preferably, R ₁ Selected from the group consisting of 2, 6-difluorophenyl, phenyl, 2-chlorophenyl, 4-fluorophenyl, 2-furyl,

w is selected from O;

Y ₁ selected from S, se;

represents a double bond or a single bond;

R _a ,R _b independently of each other selected from hydrogen, methyl, 1-trifluoroethyl, phenyl;

R _c ,R _d independently of one another, from the group consisting of hydrogen, hydroxy, amino, tert-butyl, cyclopropyl, methyl,Trifluoromethyl, 4-chlorophenyl, methoxycarbonyl and ethoxy; alternatively, whenWhen representing a single bond, R _c /R _d Common constitution = O;

when (when)When representing a double bond, R _a /R _b One is absent and R _c /R _d One is absent;

R ₂ selected from 3-fluoro-5-chlorophenyl methyl; substituted or unsubstituted phenyl, wherein the substituents are fluoro, chloro, bromo, trifluoromethyl, trifluoromethoxy, t-butoxycarbonyl, methoxy, nitro, trifluoromethylthio,Substituted or unsubstituted pyrazolyl, wherein the substituents are methyl and/or trifluoromethyl.

The compounds of the general formula (I) according to the invention are exemplified by the specific compounds listed below, but the invention is not limited to these compounds only:

the synthetic routes of the compounds of the general formula (I) of the invention, such as the compounds I-1 to I-64 and I-71 to I-81, are shown in the following formulas:

wherein the substituents R ₁ ，R ₂ ，Y ₁ ，R _a ,R _b ,R _c ,R _d Andsee the foregoing definitions; x is chlorine or bromine.

The alkali is one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine.

The catalyst is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600.

The heating temperature is 40-120 ℃.

The reaction solvent is one or a mixed solvent of more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 4-dioxane, acetone, dichloromethane, ethanol, 1, 2-dichloroethane and 2-butanone.

The synthetic procedure for the specific examples is referred to as follows:

the first step: to a 250ml flask, selenium (thio) potassium cyanate (2 mmol) represented by formula 2 was added, and after the solid was dissolved in a solvent, acid chloride (2 mmol) represented by formula 1 was added during stirring, and the mixture was sealed and stirred at room temperature for 2 hours. After the completion of the reaction, the amine (2 mmol) represented by formula 3 was added and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography, and the solvent was distilled off under reduced pressure to give a product which was an acyl seleno (thio) urea represented by formula 4.

And a second step of: the acyl selenium (sulfur) urea product (0.5 mmol) shown in the formula 4 obtained in the first step is taken in a sealed tube, added with a solvent for dissolution, then added with 0.75mmol of alpha-bromo derivative shown in the formula 5, and the reaction tube is sealed and then placed in an oil bath at 70 ℃ for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and the solvent was distilled off under reduced pressure to give the final product represented by formula 6.

The synthetic routes of the compounds of the general formula (I) of the present invention, such as compounds I-65 to I-67, I-82, are shown in the following formulas:

wherein the substituents R ₁ 2, 6-difluorophenyl; r is R ₂ 3-chloro-4-trifluoromethylphenyl, 3-chloro-4-trifluoromethoxyphenyl, p-chlorophenyl; r is R _a Hydrogen, methyl or 1, 1-trifluoroethyl; r is R _b ,R _c ,R _d Is hydrogen.

The alkali in the first step of reaction is one or more of sodium carbonate, potassium phosphate, cesium carbonate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine.

The heating temperature is 40-120 ℃.

The alkali in the second step of reaction is one or more of sodium carbonate, potassium phosphate, cesium carbonate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine.

The reaction solvent can be one or more than two of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 4-dioxane, acetone, dichloromethane, ethanol, 1, 2-dichloroethane and 2-butanone.

The synthetic procedure for the specific examples is referred to as follows:

the first step: n-cyanamide derivative (1.638 mmol) shown in formula 7, ethylene sulfide derivative (1.646 mmol) shown in formula 8, and base (1.720 mmol) were refluxed in a solvent with heating. After 2 hours, the reaction was cooled, diluted with 100mL of dichloromethane, and washed with water (2X 75 mL) and brine (75 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give an imine compound represented by formula 9.

And a second step of: the imine compound (0.5 mmol) represented by formula 9 obtained above was placed in a sealed tube, a solvent was added, the acid chloride (0.5 mmol) represented by formula 1 was added, the mixture was stirred at room temperature after sealing, the reaction was continued for 1 hour, the solid residue was filtered off after monitoring the reaction by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography and concentrated under reduced pressure to give the objective product represented by formula 10.

The synthetic route of the compound I-68 in the compound of the general formula (I) is shown as follows:

wherein the substituents R ₁ 2, 6-difluorophenyl; r is R ₂ Is phenyl.

The catalyst in the first step is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600.

The catalyst in the second step reaction is one or more of cuprous bromide, cuprous iodide, cuprous chloride, ferric trichloride or cobalt dichloride.

The alkali is one or more of potassium carbonate, sodium hydroxide, sodium carbonate, potassium phosphate, diisopropylethylamine, pyridine, sodium tert-butoxide, potassium tert-butoxide or cesium carbonate.

The heating temperature is 40-120 ℃.

The synthetic procedure for the specific examples is referred to as follows:

the first step: to a 250ml flask, potassium thiocyanate (2 mmol) was added, dissolved in a solvent, and a catalyst was selectively added, and during stirring, acid chloride (2 mmol) was added, and after sealing, the reaction was stirred at room temperature for 2 hours. After the reaction is finished, filtering solid residues, and evaporating the solvent under reduced pressure to obtain the benzoyl isothiocyanate.

And a second step of: the isothiocyanate obtained in the first step was taken out in a reaction tube, allylamine (0.2 mmol) was added under nitrogen protection and stirred for 1 hour, then 1- (trifluoromethyl) -1, 2-phenyliodic-3 (1H) -one (0.3 mmol), catalyst (10 mol%), base (0.5 mmol) and solvent were added, and after sealing, the mixture was placed in an oil bath at 75℃for reaction for 4 hours, after the completion of the reaction was monitored by TLC plate, the solid residue was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) and concentrated under reduced pressure to give the objective product.

The synthetic routes of the compounds I-69 and I-70 of the general formula (I) are shown in the following formula:

wherein the substituents R ₁ 2, 6-difluorophenyl; r is R ₂ Is phenyl; y is Y ₁ Is S, R _a Is hydrogen or phenyl; r is R _b Is hydrogen.

The reaction solvent in the first step may be one of acetonitrile, 1, 4-dioxane, acetone, methylene chloride, ethanol, and 1, 2-dichloroethane.

The reaction solvent in the second step can be more than one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 4-dioxane, acetone, dichloromethane, ethanol and 1, 2-dichloroethane.

The alkali is one or more of sodium carbonate, potassium phosphate, cesium carbonate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine.

The synthetic procedure for the specific examples is referred to as follows:

the first step: selenium (sulfur) potassium cyanate (2 mmol) was added into a 250ml flask, dissolved in a solvent, and optionally a catalyst, and acyl chloride (2 mmol) was added during stirring, and the mixture was sealed and stirred at room temperature for 2 hours. After completion of the reaction, amine (2 mmol) was added and the reaction was continued for 1 hour, and after completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to give the benzoylureas.

The benzoylurea compound (2 mmol) synthesized in the first step was taken and dissolved in a solvent, base (10.50 eq.) and stirred at room temperature (25-30 ℃) for 10 minutes until the solution became pale yellow. To this was added dropwise a bromocyano derivative (2.05 mmol, which was dissolved in a solvent) for 10 minutes, and then a precipitate was obtained after 15 minutes. Concentrating the solvent under reduced pressure to isolate a solid material; filtered or washed with n-hexane to remove excess base. And purifying the obtained crystal compound to obtain a target product.

The compounds of the general formula (I) show a controlling effect on pests in the technical field of agriculture. Thus, another embodiment of the invention relates to the use of a compound of the general formula (I) or a agropharmaceutically acceptable salt thereof as insecticide, i.e. the use of a compound of the general formula (I) or a agropharmaceutically acceptable salt thereof for the preparation of a medicament for controlling pests in agriculture or in other fields.

The compounds of the present invention are useful for controlling and destroying a wide range of agricultural and forestry pests, sanitary pests, and pests that are harmful to animal health. In the present specification, the term "insecticide" is a generic term having a role of controlling all the pests mentioned above. Examples of pests include, but are not limited to: lepidoptera (Lepidoptera) insects: for example, plutella xylostella (Plutella xylostella), spodoptera frugiperda (Spodoptera frugiperda), spodoptera exigua (s. Exigua), spodoptera litura (s. Litura), gypsylla (Lymantria dispar), trichostrongylus, chrysalis (Malacoscma neustria testacea), cotton bollworm (Diaphania perspectalis), armyworm (Clania variegata), yellow thorn (Cnidocampa flauescens), pine moth (Dendrolimus punctatus), archaea (Orgyia antipquata), white poplar diatom moth (Paranthrene tabaniformis), chilo suppressalis (Chilo suppressalis), corn borer (Ostrinia nubilalis), pink bollworm (Ephestia cautella), cotton bollworm (adophis orana), chestnut plutella (laspyresia splendana), tiger (Agrotis fucosa), large wax moth (Galleria mellonella), citrus moth (Phyllocnistis citrella), oriental myxoma (Mythimna separata), and the like; coleopteran (Coleoptera) insects: for example, corn weevil (Sitophilus zeamais), red larch (Tribolium castaneum), potato ladybug (Henosepilachna vigintioctcmaculata), eicosmosla (h.sparsa), fine chest click beetle (Agriotes fusciollis), red foot mossback (anchala cuprapes), red foot mossback (Popillia quadriguttata), potato leaf beetle (Monolepta hieroglyphica), monochamus alternatus (Monochamus alternatus), rice root weevil (Echinocnemus squameus), paulownia leaf beetle (Basiprionota bisignata), star beetle (Anoplophora chinensis), mulberry beetle (Apripona germari), umbilical bark beetle (socytus scheve), or fine chest flammule (Agriotes fuscicollis), etc.; hemiptera (Hemiptera) insects: for example, lygus lucorum (Stephanitis nashi), lygus lucorum (Nezara viridula), theragra chalcogramma (Poecilocoris latus), theragra chalcogramma (Cletus pubtiger), lygus sorghum halepense (Dimorphopterus japonicus), lygus lucorum (Dysdercus cingulatus), etc.; homoptera (Hcmoptera) insects: for example, leafhoppers (Nephotettix cincticeps), cerclage (Unaspis yanonensis), myzus persicae (Myzus persicae), cotton aphid (Aphis gossypdii), bemisia tabaci (Bemisia tabaci), brown planthopper (Laodelphax striatellus), brown planthopper (Nilaparvata lugens), white-back planthopper (Sogatella furcifera), and the like; orthoptera (Orthoptera) insects: for example, mole cricket africa (Gryllotalpa africana), locusta migratoria (locusta migratoria), etc.; hymenoptera (Hymenoptera) insects: for example, solenopsis invicta (Solenopsis invicta), apis cerana (Tremex fuscicornis), etc.; insects of the order blattaria: for example, german cockroaches (Blattella germanica), american cockroaches (Periplaneta american), coptotermes (Copotermes formosamus), and the like; diptera (Diptera) insects: for example, house flies (Musca dcmestica), aedes aegypti (Aedes aegypti), seed flies (Delia platura), culex (Culex fatigans), anopheles sinensis (Anopheles sinensis), and the like; plant parasitic nematodes: such as root-knot nematodes, root-rot nematodes, aphelenchus xylophilus, pine nematodes, etc. Pests that are harmful to animal health include tick (Boophilus microplus) of nigella minutissima, tick (Haemaphysalis longicornis) of rhizus, tick (Hyalcmma anatolicum) of rhizus, cow fly (Hypoderma bovis), fasciola hepatica (Fasciola hepatica), taenia bellifer (Moniezia blanchard), protozoa (Trypanoscma enansi), barbus Bei Sichong (Babesia bigemina), and the like.

The invention also provides an insecticidal composition which contains an active component (a compound shown as a general formula (I)) and an agriculturally acceptable carrier, wherein the weight percentage of the active component in the composition is 0.01-99.99%.

A process for the preparation of a composition as defined above: the compound of formula (I) is admixed with a carrier. The active ingredient in such a composition may comprise a single compound of the invention or a mixture of several compounds.

The above composition may be applied in the form of a formulation. The compounds of formula (I) are dissolved or dispersed as active ingredients in a carrier or formulated into a formulation for easier dispersion when used as pesticides; for example: the chemical preparation can be prepared into powder, wettable powder, emulsifiable concentrate, concentrated emulsion and microemulsion, suspension emulsion, granule, oil agent, ultra-low volume spray, smoke type, slow release agent and other pesticide formulations. In these compositions, at least one liquid or solid carrier is added, and a suitable surfactant may be added as needed.

The carrier in the composition of the invention is a substance that satisfies the following conditions: the compound can be conveniently applied to the sites to be treated after being prepared with active ingredients, and can be plants, seeds or soil; or to facilitate storage, transport or handling. The carrier may be a solid or a liquid, including substances that are normally gaseous but which have been compressed into a liquid, and commonly used in formulating insecticidal compositions.

The agricultural composition can be used for killing or preventing agricultural and forestry pests, sanitary pests or pest pesticides which harm animal health, killing or preventing plant pathogenic bacteria and killing or preventing agricultural weeds.

The specific method for the application comprises the following steps: the pesticide is applied to the pest or to the medium on which the pest is growing.

For certain applications, for example, agriculture, one or more other types of insecticides, nematicides, acaricides, plant growth regulators or fertilizers, etc. may be added to the insecticide compositions of the present invention, thereby producing additional advantages and effects.

It should be understood that various changes and modifications can be made within the scope of the invention as defined in the appended claims.

In addition, the invention also provides application of the imide oxazole heterocyclic compound shown in the general formula (I) or the agropharmaceutically acceptable salt thereof in preparing pesticides, wherein the pesticides are used for killing pests, and the pests are plutella xylostella, spodoptera frugiperda, asparagus caterpillar, prodenia litura, aedes aegypti, solenopsis invicta and meloidogyne incognita.

Compared with the prior art, the invention has the following advantages:

the general formula (I) shows good biological activity to pests in agriculture, forestry and other fields; the compound of the general formula (I) can be used as an insecticide, and particularly has better poisoning effect on agricultural pests such as plutella xylostella, spodoptera frugiperda, asparagus caterpillar, prodenia litura and the like.

Detailed Description

The present invention will be described in further detail with reference to examples, but embodiments of the present invention are not limited thereto. The raw materials related to the invention can be directly purchased from the market. For process parameters not specifically noted, reference may be made to conventional techniques.

Synthesis example 1: preparation of Compound I-3

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Acetone (Acetone), and 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the mixture was sealed and stirred at room temperature for 2 hours. After the completion of the reaction, t-butyl 4-aminobenzoate (2 mmol) was added and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, 4ml of DCM was added for dissolution, then 1-bromo-3, 3-dimethyl-2-butanone (0.75 mmol) was added, and the reaction tube was sealed and placed in an oil bath at 70 ℃ for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a white solid.

By adopting the same steps, the compounds I-1 to I-2, I-4 and I-81 can be synthesized by changing the corresponding raw materials.

Compound I-1: pale yellow solid: ¹ H NMR(500MHz,CDCl ₃ )：δ7.84(d,J＝8.4Hz,1H),7.54(s,1H),7.39(d,J＝8.3Hz,1H),7.30-7.21(m,1H),7.05(s,1H),6.84(t,J＝8.3Hz,2H),1.21(s,9H)。

compound I-2: white solid: ¹ H NMR(500MHz,CDCl ₃ )：δ7.84(d,J＝8.4Hz,1H),7.73(s,1H),7.44(dd,J＝7.4,1.6Hz,1H),7.29-7.23(m,1H),7.05(s,1H),6.84(t,J＝8.1Hz,2H),1.21(s,9H)。

compound I-3: white solid: ¹ H NMR(500MHz,CDCl ₃ )：δ8.11(d,J＝8.1Hz,2H),7.39(d,J＝8.1Hz,2H),7.25–7.15(m,1H),7.04(s,1H),6.80(t,J＝8.0Hz,2H),1.63(s,9H),1.17(s,9H)。

compound I-4: pale yellow solid: ¹ H NMR(500MHz,CDCl ₃ )：δ7.69(d,J＝8.1Hz,1H),7.24(tt,J＝8.4,6.1Hz,1H),7.05(s,1H),7.04-6.98(m,2H),6.82(t,J＝8.1Hz,2H),3.92(s,3H),1.22(s,9H)。

compound I-81: white solid: delta 7.49 (d, j=2.6 hz, 1H), 7.46 (dd, j=8.8, 1.5hz, 1H), 7.30 (dd, j=8.8, 2.6hz, 1H), 7.28-7.20 (m, 1H), 7.03 (s, 1H), 6.83 (t, j=8.1 hz, 2H), 1.22 (s, 9H).

Synthesis example 2: preparation of Compound I-5

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Acetone (Acetone), and 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the mixture was sealed and stirred at room temperature for 2 hours. After the reaction was completed, 4-chloro-3- ((3-chloro-5- (trifluoromethyl) pyridin-2-yl) oxy) aniline (2 mmol) was added and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by monitoring the TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by adding 1-cyclopropyl-2-bromoethanone (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-5: pale yellow solid: MS (ESI) M/z (M+H) ⁺ ：633.96.EA:C,47.44；H,2.25；N,6.66.

Synthesis example 3: preparation of Compound I-10

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature for 2h after sealing. After the reaction was completed, 2-methyl-5-trifluoromethyl-2H-pyrazol-3-amine (2 mmol) was added to continue the reaction for 1 hour, and after the completion of the reaction was monitored by TLC plate, the solid residue was filtered off, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by adding 1-cyclopropyl-2-bromoethanone (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

By adopting the same experimental steps, the compounds I-6 to I-9 and I-21 can be synthesized by changing the corresponding reaction raw materials.

Compound I-6: pale yellow solid: ¹ H NMR(500MHz,CDCl ₃ ):δ7.87(d,J＝8.4Hz,1H),7.54(d,J＝2.0Hz,1H),7.38(d,J＝8.4Hz,1H),7.28(t,J＝8.4Hz,1H),6.93(s,1H),6.86(t,J＝8.1Hz,2H),2.09(s,3H)。

compound I-7, pale yellow solid: MS (ESI) M/z (M+H) ⁺ ：463.03,EA:C,46.88；H,2.41；N,6.09。

Compound I-8, pale yellow solid: MS (ESI) M/z (M+H) ⁺ ：496.99,EA:C,43.60；H,2.04；N,5.63。

Compound I-9: pale yellow solid: ¹ H NMR(500MHz,CDCl ₃ ):δ8.15(d,J＝8.5Hz,2H),7.37(d,J＝8.5Hz,2H),7.24(t,J＝8.4,Hz,1H),6.92(s,1H),6.83(t,J＝8.0Hz,2H),2.05(s,3H),1.63(s,9H)。

compound I-10: pale yellow solid: ¹ H NMR(500MHz,CDCl ₃ ):δ7.33(t,J＝8.4Hz,1H),6.93–6.87(m,3H),6.59(s,1H),3.77(s,3H),2.10(m,3H)。

compound I-21: white solid: delta 8.07 (d, j=7.4 hz, 1H), 7.65-7.54 (m, 3H), 7.45-7.40 (m, 1H), 7.37-7.31 (m, 4H), 6.84 (s, 1H), 2.07 (s, 3H).

Synthesis example 4: preparation of Compound I-11

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (1.5 mmol) was added during stirring, and after sealing, the reaction was stirred at room temperature for 2h. After the completion of the reaction, 3-chloro-4-trifluoromethylaniline (2 mmol) was added thereto for further reaction for 1 hour, and after the completion of the reaction was monitored by TLC plate, the solid residue was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, then 1-bromo-3, 3-trifluoroacetone (0.75 mmol) and triethylamine (0.5 mmol) were added, and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

And a third step of: the second step (0.2 mmol) was taken in a 100ml flask, 6ml Dichloromethane (DCM) was added, triethylamine (0.4 mmol) was added, after cooling to 0deg.C, trifluoroacetic anhydride (0.3 mmol) was added, then the reaction was carried out at room temperature for 12h, after the reaction was completed, 6ml water was poured, extracted with DCM, the organic layer was separated, washed with brine, dried over anhydrous sodium sulfate, and the residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the desired product.

Compound I-11: pale yellow solid: MS (ESI) M/z (M+H) ⁺ ：534.97.EA:C,40.50；H,1.34；N,5.27

Synthesis example 5: preparation of Compound I-13

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature for 2h after sealing. After the completion of the reaction, 3, 5-dichloroaniline (2 mmol) was added thereto for further 1 hour, and after the completion of the reaction, the solid residue was filtered off by monitoring the reaction by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by alpha-bromo-4-chloroacetophenone (0.75 mmol) and triethylamine (0.5 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

By adopting the same experimental steps, the compounds I-12, I-15-I-20 and I-80 can be synthesized by changing corresponding reaction raw materials.

Compound I-12: white solid, MS (ESI): m/z (M+H) ⁺ ：576.98.EA:C,47.97；H,1.93；N,4.88.。

Compound I-13: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ7.35–7.28(m,4H),7.23(s,1H),7.17(d,J＝1.8Hz,1H),7.09(d,J＝8.5Hz,2H),6.91(t,J＝8.2Hz,2H).。

compound I-15 is a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ ):δ8.14(dd,J＝8.4,1.4Hz,2H),7.47–7.43(m,1H),7.37(t,J＝7.2Hz,2H),7.21(d,J＝8.5Hz,2H),7.15(d,J＝9.0Hz,2H),7.13(s,1H),7.08(d,J＝8.5Hz,2H),6.91(d,J＝9.0Hz,2H),3.85(s,3H)。

compound I-16: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ ):δ8.13(d,J＝7.4Hz,1H),7.49–7.35(m,6H),7.30–7.24(m,2H),7.23–7.18(m,3H),7.09(d,J＝4.8Hz,2H).。

compound I-17: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ ):δ8.13(dd,J＝7.8,1.7Hz,2H),7.45(t,J＝7.2Hz,1H),7.35(t,J＝7.5Hz,2H),7.22–7.15(m,4H),7.15(s,1H),7.14–7.05(m,4H,),2.41(s,3H).。

compound I-18: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ ):δ7.90(dd,J＝7.8,1.7Hz,1H),7.41(dd,J＝8.1,1.3Hz,1H),7.33(td,J＝7.6,1.8Hz,1H),7.31–7.22(m,8H),7.07(d,J＝8.5Hz,2H).。

compound I-19: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ ):δ8.17–8.11(m,2H),7.21(d,J＝8.5Hz,2H),7.16–7.11(m,3H),7.11–7.01(m,4H),6.90(d,J＝8.6Hz,2H),3.85(s,3H).。

compound I-20: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ ):δ8.30(d,J＝8.7Hz,2H),8.09(dd,J＝8.5,1.6Hz,2H),7.45–7.51(m,3H),7.40(t,J＝7.6Hz,2H),7.24(d,J＝8.5Hz,2H),7.22(s,1H),7.06(d,J＝8.5Hz,2H).。

compound I-80: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ ):δ7.66(d,J＝8.5Hz,1H),7.56(s,1H),7.38–7.31(m,1H),7.29(d,J＝8.5Hz,2H),7.26(s,1H),7.18(d,J＝8.4,1H),7.08(d,J＝6.6Hz,2H),6.92(t,J＝8.2Hz,2H).。

synthesis example 6: preparation of Compound I-22

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature for 2h after sealing. After the completion of the reaction, 3-chloro-4-trifluoromethylaniline (2 mmol) was added thereto for further reaction for 1 hour, and the solid residue was filtered off after the completion of the reaction by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, then 1-bromo-3, 3-trifluoroacetone (0.75 mmol) and triethylamine (0.5 mmol) were added, and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a white solid.

Compounds I-26 to I-31, I-78 can all be synthesized by this procedure

Compound I-22: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ ):δ7.38(d,J＝6.7Hz,2H),7.35–7.29(m,1H),7.28(d,J＝8.5Hz,2H),6.86(t,J＝8.3Hz,2H),5.40(m,1H),3.77(d,J＝12.5Hz,1H),3.36(d,J＝12.1Hz,1H).。

compound I-26: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ7.76(d,J＝3.8Hz,1H),7.74(s,1H),7.46(d,J＝8.4,2.0Hz,1H),7.36(t,J＝8.4Hz,1H),6.90(t,J＝8.3Hz,1H),6.13(s,1H),3.80(d,J＝12.6Hz,1H),3.43(d,J＝12.6Hz,1H).。

compound I-27: white solid, MS (ESI): m/z (M+H) ⁺ ：518.96,EA:C,39.43；H,1.72；N,5.41.。

Compound I-28: a white solid was used as a solid, ¹ H NMR(500MHz,DMSO-d ₆ )δ8.88(s,1H),7.65–7.60(m,2H),7.42(dd,J＝8.8,2.4Hz,1H),7.41–7.34(m,1H),7.00(t,J＝8.2Hz,2H),3.83(d,J＝12.7Hz,1H),3.56(d,J＝12.7Hz,1H).。

compound I-29: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ7.63(d,J＝8.2Hz,1H),7.37–7.30(m,1H),7.06–6.99(m,2H),6.86(t,J＝8.3Hz,2H),5.24–4.76(s,1H),3.91(s,3H),3.78(d,J＝12.5Hz1H),3.39(d,J＝12.5Hz,1H).。

compound I-30: a white solid was used as a solid, ¹ H NMR(500MHz,CDCl ₃ )：δ8.06(d,J＝8.3Hz,2H),7.39(d,J＝8.2Hz,2H),7.33–7.26(m,1H),6.84(t,J＝8.2Hz,2H),4.82(s,1H),3.77(d,J＝12.4Hz,1H),3.37(d,J＝12.4Hz,1H),1.61(s,9H).。

compound I-31: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ7.76(d,J＝8.4Hz,1H),7.57(s,1H),7.41(d,J＝8.4Hz,1H),7.35(t,J＝8.4Hz,1H),6.89(t,J＝8.3Hz,2H),5.86(s,1H),3.80(d,J＝12.5Hz,1H),3.41(d,J＝12.5Hz,1H).。

compound I-78: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ8.12(s,1H),8.03(s,1H),7.55(d,J＝8.5Hz,1H),7.37–7.22(m,3H),6.83(t,J＝8.2Hz,2H),5.54(s,1H),3.74(d,J＝12.4Hz,1H),3.37(d,J＝12.6Hz,1H).。

synthesis example 7: preparation of Compound I-23

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Acetone (Acetone), and 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the mixture was sealed and stirred at room temperature for 2 hours. After the reaction was completed, 4-chloro-3- ((3-chloro-5- (trifluoromethyl) pyridin-2-yl) oxy) aniline (2 mmol) was added and the reaction was continued for 1 hour, after which the solid residue was filtered off after the completion of the reaction by TLC plate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by methyl bromopyruvate (0.75 mmol), and the reaction tube was sealed and placed in a 50℃oil bath with stirring for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compounds I-24 to I-25 can be synthesized by this procedure

Compound I-23: a pale yellow solid, which is a mixture of a light yellow solid, ¹ H NMR(500MHz,CDCl ₃ )：δ8.12(s,1H),8.02(s,1H),7.49(d,J＝8.5Hz,1H),7.35–7.24(m,3H),6.79(t,J＝8.1Hz,2H),5.18(s,1H),3.79(d,J＝11.4Hz,1H),3.76(s,3H),3.33(d,J＝11.4Hz,1H)。

compound I-24: pale yellow solid, MS (ESI): m/z (M+H) ⁺ ：540.99.EA:C,42.33；H,2.44；N,5.20；S,5.95。

Compound I-25: pale yellow solid, MS (ESI): m/z (M+H) ⁺ ：558.97.EA:C,40.94；H,2.18；N,5.04。

Synthesis example 8: preparation of Compound I-35

The first step: to a 250mL flask, potassium thiocyanate (2 mmol) was added, and dissolved in 8mL of Acetone (Acetone), while stirring, 2, 6-difluorobenzoyl chloride (2 mmol) was added, and after sealing, the reaction was stirred at room temperature for 2 hours. After the completion of the reaction, t-butyl 4-aminobenzoate (2 mmol) was added and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml DCM, followed by adding 1-bromo-3, 3-dimethyl-2-butanone (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a white solid.

Compounds I-33, I-34, I-36 can all be synthesized by this procedure

Compound I-33: white solid, MS (ESI) M/z (M+H) ⁺ ：491.07.EA:C,51.40；H,3.30；N,5.73；S,6.53。

Compound I-34: white solid, MS (ESI) M/z (M+H) ⁺ ：519.06.EA:C,48.58；H,3.13；N,5.40；S,6.19。

Compound I-35: white solid, MS (ESI) M/z (M+H) ⁺ ：473.18.EA:C,63.54；H,5.55；N,5.93；S,6.78。

Compound I-36: white solid, MS (ESI) M/z (M+H) ⁺ ：471.14.EA:C,56.19；H,4.09；N,5.96；S,6.83。

Synthesis example 9: preparation of Compound I-37

The first step: to a 250mL flask, potassium thiocyanate (2 mmol) was added, and dissolved in 8mL of Acetone (Acetone), while stirring, 2, 6-difluorobenzoyl chloride (2 mmol) was added, and after sealing, the reaction was stirred at room temperature for 2 hours. After the reaction was completed, 4-chloro-3- ((3-chloro-5- (trifluoromethyl) pyridin-2-yl) oxy) aniline (2 mmol) was added and the reaction was continued for 1 hour, after which the solid residue was filtered off after the completion of the reaction by TLC plate, and then the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by adding 1-cyclopropyl-2-bromoethanone (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for stirring reaction for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-37: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：586.03.EA:C,51.22；H,2.42；N,7.19S,5.49。

Synthesis example 10: preparation of Compound I-43

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (1.5 mmol) was added during stirring, and after sealing, the reaction was stirred at room temperature for 2h. After the completion of the reaction, 3-chloro-4-trifluoromethylaniline (2 mmol) was added thereto for further reaction for 1 hour, and after the completion of the reaction was monitored by TLC plate, the solid residue was filtered off, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by 1-bromo-3, 3-trifluoroacetone (0.75 mmol) and triethylamine (0.5 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for reaction with stirring for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a white solid.

Compound I-43: white solid: MS (ESI) M/z (M+H) ⁺ ：487.03,EA:C,44.44；H,1.43；N,5.77；S,6.60。

Synthesis example 11: preparation of Compound I-45

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (1.5 mmol) was added during stirring, and after sealing, the reaction was stirred at room temperature for 2h. After the completion of the reaction, 3, 5-dichloroaniline (1.5 mmol) was added thereto and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by monitoring the TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a pale yellow solid product, which was the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by alpha-bromo-4-chloroacetophenone (0.75 mmol) and triethylamine (0.5 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for 5h with stirring. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compounds I-44, I-47 to I-52 can all be synthesized by this procedure

Compound I-44: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：529.01.EA:C,52.20；H,2.11；N,5.27；S,6.04。

Compound I-45: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：494.98.EA:C,53.31；H,2.24；N,5.67；S,6.49。

Compound I-47: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：421.11.EA:C,65.65；H,4.10；N,6.66；S,7.60。

Compound I-48: white solid, MS (ESI) M/z (M+H) ⁺ ：391.09.EA:C,67.59；H,3.89；N,7.18；S,8.22。

Compound I-49: white solid, MS (ESI) M/z (M+H) ⁺ ：405.05.EA:C,68.25；H,4.24；N,6.90；S,7.90。

Compound I-50: white solid, MS (ESI) M/z (M+H) ⁺ ：509.01.EA:C,54.26；H,2.59；N,5.52；S,6.30。

Compound I-51: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：439.02.EA:C,62.96；H,3.69；N,6.40；S,7.32。

Compound I-52: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：436.09.EA:C,60.65；H,3.26；N,9.61；S,7.38。

Synthesis example 12: preparation of Compound I-54

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (1.5 mmol) was added during stirring, and after sealing, the reaction was stirred at room temperature for 2h. After the completion of the reaction, p-trifluoromethoxyaniline (2 mmol) was added thereto for further 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the objective benzoylthiourea.

Compounds I-58 to I-64 can all be synthesized by this procedure

Compound I-54: white solid, MS (ESI) M/z (M+H) ⁺ ：487.06.EA:C,44.43；H,2.09；N,5.78；S,6.61。

Compound I-58: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：548.99.EA:C,39.34；H,1.63；N,5.11；S,5.85。

Compound I-59: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：480.00.EA:C,43.35；H,1.95；N,5.96；S,6.81。

Compound I-60: white solid, MS (ESI) M/z (M+H) ⁺ ：521.01.EA:C,41.53；H,1.75；N,5.40；S,6.17。

Compound I-61: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：501.08.EA:C,45.63；H,2.40；N,5.61；S,6.40。

Compound I-62: white solid, MS (ESI) M/z (M+H) ⁺ ：503.09.EA:C,52.58；H,3.79；N,5.56；S,6.36。

Compound I-63: white solid, MS (ESI) M/z (M+H) ⁺ ：505.01.EA:C,42.85；H,1.82；N,5.53；S,6.37。

Compound I-64: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：475.02.EA:C,40.50；H,1.93；N,5.91；S,6.77。

Synthesis example 13: preparation of Compound I-55

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by methyl bromopyruvate (0.75 mmol), and the reaction tube was sealed and placed in a 50℃oil bath with stirring for 5h. After the completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a yellow solid.

Compounds I-56 to I-57, I-79 can be synthesized by this procedure

Compound I-55: yellow solid, MS (ESI) M/z (M+H) ⁺ ：622.00,EA:C,46.34；H,2.30；N,6.78；S,5.17。

Compound I-56: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：493.03,EA:C,46.36；H,2.67；N,5.69；S,13.04。

Compound I-57: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：511.03,EA:C,44.70；H,2.39；N,5.49；S,6.30。

Compound I-79 as a pale yellow solid, ¹ H NMR(500MHz,CDCl ₃ ):δ7.37(d,J＝7.6Hz,2H),7.30–7.20(m,3H),6.82(t,J＝8.2Hz,2H),4.77(s,1H),3.90(d,J＝12.3Hz,1H),3.78(s,3H),3.49(d,J＝12.3Hz,1H)。

synthesis example 14: preparation of Compound I-73

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), furoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature after sealing for 2h. After the completion of the reaction, 3-chloro-4-trifluoromethoxy aniline (2 mmol) was added thereto for further reaction for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product, which was the target furan acyl selenourea.

And a second step of: the furoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by adding methyl bromopyruvate (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 80℃for stirring reaction for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-14 can be synthesized by this procedure

Compound I-14: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：524.98,EA:C,43.59；H,1.95；N,5.33。

Compound I-73: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：478.94EA:C,42.75；H,2.10；N,5.87。

Synthesis example 15: preparation of Compound I-74

The first step: to a 250mL flask was added potassium selenocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature for 2h after sealing. After the completion of the reaction, 2-chloro-4-trifluoromethylaniline (2 mmol) was added thereto for further reaction for 1 hour, and the solid residue was filtered off after the completion of the reaction by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a yellow solid product as the target benzoyl selenourea.

And a second step of: the benzoyl selenourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by ethyl bromoacetate (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃for 5h with stirring. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-32 can be synthesized by this procedure

Compound I-32: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：509.02.EA:C,45.00；H,2.57；N,5.53；S,6.34。

Compound I-74: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：510.97.EA:C,44.75；H,2.39；N,5.51。

Synthesis example 16: preparation of Compound I-75

The first step: to a 250mL flask, potassium thiocyanate (2 mmol) was added, and dissolved in 8mL of Acetone (Acetone), o-chlorobenzoyl chloride (1.5 mmol) was added during stirring, and the mixture was sealed and then stirred at room temperature for 2 hours. After the completion of the reaction, 3-chloro-5-fluorobenzylamine (1.5 mmol) was added thereto and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a pale yellow solid product, which was the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by bromoacetone (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃with stirring for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compounds I-38 to I-42, I-53 can all be synthesized by this procedure

Compound I-38: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：433.02.EA:C,49.97；H,2.31；N,6.49；S,7.43。

Compound I-39: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：415.09.EA:C,52.20；H,2.69；N,6.78；S,7.74。

Compound I-40: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：449.05.EA:C,48.19；H,2.27；N,6.25；S,7.11。

Compound I-41: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：431.14.EA:C,61.39；H,4.65；N,6.53；S,7.42。

Compound I-42: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：403.10.EA:C,47.73；H,2.78；N,13.95；S,7.97。

Compound I-53: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：295.11.EA:C,69.38；H,4.80；N,9.52；S,10.91。

Compound I-75: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：395.03.EA:C,54.73；H,3.31；N,7.11；S,8.08。

Synthesis example 17: preparation of Compound I-76

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop) and furoyl chloride (1.5 mmol) with stirring, and the reaction was stirred at room temperature for 2h after sealing. After the completion of the reaction, 3-chloro-4-trifluoromethoxy-aniline (1.5 mmol) was added and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a white solid product, which was the target furan acyl thiourea.

And a second step of: the furoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by methyl bromopyruvate (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 80℃for reaction with stirring for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-46 can be synthesized by this procedure

Compound I-46, yellow solid, MS (ESI) M/z (M+H) ⁺ ：477.03.EA:C,47.88；H,2.13；N,5.89；S,6.74。

Compound I-76: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：431.02.EA:C,47.40；H,2.34；N,6.50；S,7.44。

Synthesis example 18: preparation of Compound I-77

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 8mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (1.5 mmol) was added during stirring, and after sealing, the reaction was stirred at room temperature for 2h. After the completion of the reaction, 2-chloro-4-trifluoromethylaniline (1.5 mmol) was added thereto for further reaction for 1 hour, and the solid residue was filtered off after the completion of the reaction by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give a pale yellow solid product, which was the objective benzoylthiourea.

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, dissolved by adding 4ml of DCM, followed by ethyl bromoacetate (0.75 mmol), and the reaction tube was sealed and placed in an oil bath at 70℃with stirring for 5h. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product as a pale yellow solid.

Compound I-72 can be synthesized by this procedure

Compound I-72: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：460.03.EA:C,49.58；H,2.87；N,6.04；S,13.92。

Compound I-77: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：463.00.EA:C,49.32；H,2.61；N,6.03；S,6.95。

Synthesis example 19 preparation of Compound I-82

The first step: n- (4-chlorophenyl) cyanamide (1.638 mmol), ethylene oxide (1.646 mmol) and potassium carbonate (1.720 mmol) were heated under reflux in 2-butanone. After 2 hours, the reaction was cooled, diluted with 100mL of dichloromethane, and washed with water (2X 75 mL) and brine (75 mL). The organic phase was dried over magnesium sulfate, filtered, and concentrated under reduced pressure to give an imine compound.

And a second step of: the imine compound (0.5 mmol) obtained above was put in a sealed tube, 4mL of Dichloromethane (DCM) was added, 2, 6-difluorobenzoyl chloride (0.5 mmol) was added thereto, the reaction was stirred at room temperature after sealing for 1 hour, the solid residue was filtered off after the completion of the reaction by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) and concentrated under reduced pressure to give the objective product.

Compounds I-65 to I-67 can be synthesized by reference to this step

Compound I-65: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：432.99,EA:C,49.91；H,2.30；N,6.48；S,7.39。

Compound I-66: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：449.05,EA:C,48.19；H,2.22；N,6.25；S,7.12。

Compound I-67: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：349.01,EA:C,58.60；H,3.19；N,8.02；S,9.21。

Compound I-82: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：350.99,EA:C,54.81；H,2.58；N,7.97；S,9.16。

Synthesis example 20 preparation of Compound I-68

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 2mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), benzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature after sealing for 2h. After the reaction is finished, filtering solid residues, and removing the solvent by reduced pressure distillation to obtain the benzoyl isothiocyanate.

And a second step of: the isothiocyanate obtained in the first step was taken out in a reaction tube and allylaniline (0.2 mmol) was added under nitrogen protection for reaction for 1 hour, then 1- (trifluoromethyl) -1, 2-phenyliodiyl-3 (1H) -one (0.3 mmol), cuprous chloride (10 mol%), cesium carbonate (0.5 mmol) and 8ml of 1, 2-Dichloroethane (DCE) were added, the mixture was sealed and placed in an oil bath at 75℃for reaction for 4 hours, the solid residue was filtered off after the completion of the reaction by TLC plate monitoring, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) and concentrated under reduced pressure to give the objective product.

Compound I-68: light yellow solid, MS (ESI) M/z (M+H) ⁺ ：401.10.EA:C,54.01；H,3.25；N,6.99；S,8.02。

Synthesis example 21 preparation of Compound I-70

The first step: to a 250mL flask was added potassium thiocyanate (2 mmol), dissolved in 2mL Dichloromethane (DCM), followed by polyethylene glycol-400 (PEG-400,6-7 drop), 2, 6-difluorobenzoyl chloride (2 mmol) was added during stirring, and the reaction was stirred at room temperature after sealing for 2h. After the reaction was completed, aniline (2 mmol) was added thereto and the reaction was continued for 1 hour, and after the completion of the reaction, the solid residue was filtered off by monitoring the TLC plate, and the solvent was distilled off under reduced pressure. Purifying the residue by column chromatography (eluting with mixed solvent of petroleum ether and ethyl acetate) to obtain white solid product which is benzoylthiourea

And a second step of: the thiourea derivative (2 mmol) synthesized in the first step was taken and dissolved in an acetone solution, and triethylamine (10.50 equivalents) was added and stirred at room temperature (25-30 ℃) for 10 minutes until the solution became pale yellow. To this was added dropwise bromobenzyl cyanide (2.05 mmol, which was dissolved in 1mL of acetonitrile) for 10 minutes, followed by obtaining a yellow precipitate after 15 minutes. Concentrating the solvent under reduced pressure to isolate a solid material; filtered and washed with n-hexane to remove excess triethylamine. And purifying the obtained yellow crystal compound to obtain a target product.

Compound I-69 can be synthesized by reference to this step

Compound I-69: yellow solid, MS (ESI) M/z (M+H) ⁺ ：332.11.EA:C,57.99；H,3.36；N,12.69；S,9.70。

Compound I-70: yellow solid, MS (ESI) M/z (M+H) ⁺ ：408.11.EA:C,64.82；H,3.68；N,10.29；S,7.84。

Synthesis example 22 preparation of Compound I-71

And a second step of: the benzoylthiourea product (0.5 mmol) obtained in the first step was taken in a sealed tube, then sodium acetate (1.0 mmol), acetone (4 mL) and then ethyl bromoacetate (0.75 mmol) were added in sequence, and the reaction tube was sealed and placed in an oil bath at 60℃for stirring reaction for 4 hours. After completion of the reaction, the solid residue was filtered off by TLC plate, and the solvent was removed by distillation under the reduced pressure. The residue was purified by column chromatography (eluting with a mixed solvent of petroleum ether and ethyl acetate) to give the product I-71 as a white solid.

Compound I-71: white solid, MS (ESI) M/z (M+H) ⁺ ：333.01.EA:C,57.80；H,3.01；N,8.45；S,9.65。

Examples of biological Activity assays

The compound of the present invention shows excellent activity against various pests in the agricultural field. The results of the insecticidal activity measurement are shown in the following examples.

Example 1: evaluation of insecticidal Activity of partial Compounds on Plutella xylostella

The tested insects are lepidoptera plutella xylostella, and sensitive strains are fed indoors. The method takes the larvae of plutella xylostella 3 years as test objects, and the test method is a leaf dipping method.

The operation process comprises the following steps: each sample was accurately weighed, and 10g/L of mother liquor was prepared by adding DMSO, and diluted with an aqueous solution containing 0.5% tween-80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating 3-instar larvae of plutella xylostella with consistent growth into the vessel, inoculating 10 heads of test insects in each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution containing an equivalent amount of 0.5% Tween-80-DMSO, with 3 replicates. After 96 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%.

The synthesized compound (I) was tested according to the above experimental procedure.

When the compound concentration is 50mg/L, the compounds with the plutella xylostella mortality rate of more than 50 percent are as follows: i-6 to I-11, I-14, I-22 to I-32, I-38 to I-43, I-46, I-54 to I-68, I-72 to I-79.

When the compound concentration is 10mg/L, the compounds with the plutella xylostella mortality rate of more than 80 percent are as follows:

I-14、I-22～I-31、I-43、I-46、I-55～I-63、I-73、I-76、I-78。

example 2: evaluation of insecticidal Activity of some Compounds against Spodoptera frugiperda

The test insects were spodoptera littoralis and sensitive lines were raised indoors. The test method is a leaf dipping method by taking spodoptera frugiperda 2-year-old terminal larvae as test objects.

The operation process comprises the following steps: each sample was accurately weighed, and 10g/L of mother liquor was prepared by adding DMSO, and diluted to 50ppm with an aqueous solution containing 0.5% Tween-80. The clean corn She Zhi is formed into leaf discs by a puncher with the diameter of 1.0cm and immersed in the liquid medicine, taken out after 10 seconds, naturally dried and moved into a clean vessel. And (3) inoculating spodoptera frugiperda 2-year-end larvae with consistent growth into the vessel, inoculating 10 heads of test insects for each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution containing an equivalent amount of 0.5% Tween-80-DMSO, with 3 replicates. After 96 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.

At a compound concentration of 50mg/L, compounds with a spodoptera frugiperda mortality of greater than 50% have:

I-6～I-11、I-14、I-22～I-32、I-38～I-43、I-46、I-54～I-68、I-72～I-79。

example 3: evaluation of insecticidal Activity of partial Compounds on Spodoptera exigua

The tested insects are lepidoptera asparagus caterpillar, and sensitive strains are fed indoors. The method takes beet armyworm 1-year middle-period larvae as test objects, and the test method is a leaf dipping method.

The operation process comprises the following steps: each sample was accurately weighed, and 10g/L of mother liquor was prepared by adding DMSO, and diluted to 50ppm with an aqueous solution containing 0.5% Tween-80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating 1-year middle-period larvae of asparagus caterpillar with consistent growth into the vessel, inoculating 10 heads of test insects after each treatment, and feeding in a constant-temperature incubator at 28 ℃. The control group was treated with an aqueous solution containing an equivalent amount of 0.5% Tween-80-DMSO, with 3 replicates. After 96 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.

When the compound concentration is 50mg/L, the compounds with the spodoptera exigua mortality rate of more than 50 percent are as follows: i-6 to I-11, I-14, I-22 to I-32, I-38 to I-43, I-46, I-54 to I-68, I-72 to I-79.

Example 4: evaluation of insecticidal Activity of partial Compounds on Spodoptera litura

The tested insects are lepidoptera prodenia litura and are raised into sensitive strains indoors. The test method is a leaf dipping method by taking the larva of prodenia litura at the end stage of 1 age as a test object.

The operation process comprises the following steps: each sample was accurately weighed, and 10g/L of mother liquor was prepared by adding DMSO, and diluted to 50ppm with an aqueous solution containing 0.5% Tween-80. Preparing the clean cabbage leaves into leaf discs by using a puncher with the diameter of 1.0cm, immersing the leaf discs in the liquid medicine, taking out the leaf discs after 10 seconds, naturally airing the leaf discs, and transferring the leaf discs into a clean vessel. And (3) inoculating the prodenia litura end-stage larvae with consistent growth into a vessel, inoculating 10 heads of test insects in each treatment, and raising at a constant temperature of 28 ℃. The control group was treated with an aqueous solution containing an equivalent amount of 0.5% Tween-80-DMSO, with 3 replicates. After 96 hours the test results were observed and mortality (%) was calculated according to the formula. Mortality (%) =number of dead insects/number of test insects×100%. The test results are shown in Table 1.

When the concentration of the compound is 50mg/L, the compounds with the prodenia litura mortality rate of more than 50 percent are as follows:

the above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims

1. An amidazoles compound or agriculturally acceptable salt thereof for controlling agricultural and forestry pests and pests in other fields, which is characterized in that the structure of the amidazoles compound is shown as a general formula (I):

in the general formula (I), R ₁ Selected from substituted or unsubstituted C _6-20 Aryl, substituted or unsubstituted C _2-20 Heteroaryl; wherein the substituted or unsubstituted mesosubstituent is selected from halogen, cyano, hydroxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C ₁ - ₆ Alkoxy, C _3-6 Cycloalkyl, C _1-6 Alkoxycarbonyl, phenyl, halophenyl, benzyl;

w is selected from O or S;

Y ₁ selected from O, S, se or N;

represents a double bond or a single bond;

R ₂ selected from substituted or unsubstituted C _6-20 aryl-C _1-6 Alkyl, substituted or unsubstituted C _6-20 Aryl, substituted or unsubstituted C _2-20 Heteroaryl; wherein the substituted or unsubstituted mesosubstituent is selected from halogen, cyano, hydroxy, amino, nitro, C _1-6 Alkyl, halogenated C _1-6 Alkyl, C _1-6 Alkoxy, halo C _1-6 Alkoxy, C _1-6 Alkylthio, halo C _1-6 Alkylthio, C _3-6 Cycloalkyl, C _1-6 Alkoxycarbonyl, phenyl, halophenyl, benzyl,

Provided that the compound of formula I is not:

2. the amidazoles according to claim 1 or agriculturally acceptable salts thereof, wherein in the general formula (I), R ₁ Selected from the group consisting of substituted or unsubstituted phenyl, furyl, thienyl, pyrimidinyl, pyrazinyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, benzofuryl, benzothienyl; wherein the substituted or unsubstituted mid-substituent is selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenyl; phenyl substituted with fluorine, chlorine, bromine and/or iodine; a benzyl group;

w is selected from O;

Y ₁ selected from S, se;

represents a double bond or a single bond;

R _a ,R _b independently of each other selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; methyl, ethyl, substituted by fluorine, chlorine, bromine and/or iodine, N-propyl, isopropyl, n-butyl, isobutyl, tert-butyl; a phenyl group;

R ₂ selected from substituted or unsubstitutedSubstituted or unsubstituted benzyl, substituted or unsubstituted phenyl, furyl, thienyl, pyrimidinyl, pyrazinyl, pyrazolyl, thiazolyl, oxazolyl, imidazolyl, triazolyl, indolyl, benzimidazolyl, benzothiazolyl, benzoxazolyl, benzofuryl, benzothienyl; wherein the substituted or unsubstituted middle substituent is selected from fluorine, chlorine, bromine, iodine, cyano, hydroxyl, amino, nitro, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl; methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl substituted by fluorine, chlorine, bromine and/or iodine; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy substituted with fluorine, chlorine, bromine and/or iodine; methylthio, ethylthio, t-butylthio; methylthio, ethylthio, t-butylthio substituted by fluorine, chlorine, bromine and/or iodine; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, phenyl; phenyl substituted with fluorine, chlorine, bromine and/or iodine; benzyl group,

3. The amidazoles according to claim 1 or agriculturally acceptable salts thereof, wherein in the general formula (I), R ₁ Selected from 2, 6-difluorophenyl, phenyl, 2-chlorophenyl, 4-fluorophenyl, 2-furyl;

w is selected from O;

Y ₁ selected from S, se;

represents a double bond or a single bond;

R _c ,R _d independently of one another, from the group consisting of hydrogen, hydroxy, amino, tert-butyl, cyclopropyl, methyl, trifluoromethyl, 4-chlorophenyl, methoxycarbonyl, ethoxy; alternatively, whenWhen representing a single bond, R _c /R _d Common constitution = O;

4. The amidazoles according to claim 1 or an agriculturally acceptable salt thereof, wherein the compound of general formula (I) is selected from the following compounds:

5. the method for preparing the amidazoles compound according to claim 1, wherein the synthetic route of the method is as follows:

Substituent R in the reaction ₁ ，R ₂ ，Y ₁ ，R _a ,R _b ,R _c ,R _d Andis as defined in claim 1; x is chlorine or bromine;

the catalyst is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600;

the alkali is one or more of sodium carbonate, potassium carbonate, cesium carbonate, potassium phosphate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine;

the heating temperature is 40-120 ℃.

6. The method for preparing the amidazoles compound according to claim 1, wherein the synthetic route of the method is as follows:

substituent R in the reaction ₁ 2, 6-difluorophenyl; r is R ₂ 3-chloro-4-trifluoromethylphenyl, 3-chloro-4-trifluoromethoxyphenyl, p-chlorophenyl; r is R _a Hydrogen, methyl or 1, 1-trifluoroethyl; r is R _b ,R _c ,R _d Is hydrogen;

the alkali in the first reaction step is any one or more of sodium carbonate, potassium phosphate, cesium carbonate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine;

the heating temperature is 40-120 ℃;

the alkali in the second step of reaction refers to any one or more of sodium carbonate, potassium phosphate, cesium carbonate, sodium acetate, potassium acetate, triethylamine, diisopropylethylamine and pyridine.

7. According toThe method for preparing the amidazoles compound of claim 1, wherein the synthetic route of the method is as follows:

substituent R in the reaction ₁ 2, 6-difluorophenyl; r is R ₂ Is phenyl;

the catalyst in the first step is one or more of polyethylene glycol-200, polyethylene glycol-400 and polyethylene glycol-600;

the catalyst in the second step is one or more of cuprous bromide, cuprous iodide, cuprous chloride, ferric trichloride or cobalt dichloride;

the alkali is one or more of potassium carbonate, sodium hydroxide, sodium carbonate, potassium phosphate, diisopropylethylamine, pyridine, sodium tert-butoxide, potassium tert-butoxide or cesium carbonate;

the heating temperature is 40-120 ℃.

8. The method for preparing the amidazoles compound according to claim 1, wherein the synthetic route of the method is as follows:

substituent R in the reaction ₁ 2, 6-difluorophenyl; r is R ₂ Is phenyl; y is Y ₁ Is S, R _a Is hydrogen or phenyl; r is R _b Is hydrogen;

the reaction solvent in the first step is one or more of acetonitrile, 1, 4-dioxane, acetone, methylene dichloride, ethanol and 1, 2-dichloroethane;

The reaction solvent in the second step is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, 1, 4-dioxane, acetone, dichloromethane, ethanol and 1, 2-dichloroethane;

9. Use of an amidazoles compound of general formula (I) according to claim 1 or an agriculturally acceptable salt thereof for controlling and combating agroforestry pests, hygiene pests and pests which are harmful to animal health.

10. An insecticidal composition comprising an active ingredient and an agriculturally acceptable carrier, characterized in that said active ingredient comprises one or more amidazoles according to general formula (I) of claim 1 or an agriculturally acceptable salt thereof; preferably, the weight percentage of active components in the composition is 0.01-99.99%.