Fused ring compounds having sulfur-containing substituents, methods of preparation, insecticidal compositions and uses - Patents.com

Abstract

The present invention belongs to the field of agricultural pesticides, and specifically relates to fused ring compounds containing sulfur substituents, preparation methods, pesticide compositions and uses.Compared with the prior art, the beneficial effect of the present invention is that the fused ring compounds containing sulfur substituents provided by the present invention have good control effects against various pests at relatively low test concentrations, which provides a basis for the research and development of new pesticides. [Formula 1] JPEG2025526392000063.jpg33170

Description

[Technical Field]

[0001] The present invention is in the field of agricultural pesticides, and specifically relates to fused ring compounds containing sulfur substituents, methods of preparation, pesticide compositions and uses. [Background technology]

[0002] Fused bicyclic heterocyclic derivatives having insecticidal properties are described in, for example, WO2014 / 119672A1, WO2015 / 002211A1, WO2017 / 026384A1, WO2018 / 015289A1, and WO2016 / 091731A1. However, the specific active compounds known from the above documents not only have a narrow scope of application, but also lack satisfactory insecticidal or acaricidal activity, which causes drawbacks in use.

[0003] New fused bicyclic heterocyclic derivatives have now been found that have advantages over known compounds, such as better biological or environmental properties, more application methods, better insecticidal or acaricidal activity, and better compatibility with crops and plants. The fused bicyclic heterocyclic derivatives may be used in combination with other agents to improve efficacy, particularly against difficult-to-control insects.

[0004] The present invention provides sulfur-substituted fused heterocyclic compounds, novel structural fused bicyclic heterocyclic derivatives, methods for preparing the same, and intermediates used in the preparation thereof, and further provides their use as acaricides and / or insecticides for controlling animals and pests, particularly arthropods such as insects and arachnids, due to their insecticidal activity. Summary of the Invention

[0005] The technical problem that the present invention aims to solve is as follows: A first object of the present invention is to provide a fused ring compound containing a sulfur substituent represented by general formula (I). [ka] (I) During the ceremony, X is selected from N, NR1, O or S. Y is selected from N or S. wherein when Y is selected from N, X is selected from NR1, O or S. When Y is selected from S, X is selected from N. R1 in the formula is H, C 1~6 Alkyl group, C 1~6 Haloalkyl group, C 3~6 Cycloalkyl groups, C 3~6 halocycloalkyl groups, wherein R is selected from C 1~6 Alkyl group, C 1~6 Substituted alkyl groups, C 3~6 Cycloalkyl groups, C 3~6 Substituted cycloalkyl groups, C 2~6 Epoxy group, C 2~6 Alkenyl group, C 2~6 Alkynyl group, phenyl group, substituted phenyl group, C 5~6 It is selected from heterocycles and substituted heterocycles. The substituents of the substituted alkyl group or substituted cycloalkyl group are halogen, C 1~2 Alkyl group, C 1~2 Alkoxy group, C 1~2 Haloalkoxy group, C 1~2 It is selected from a haloalkyl group, a cyano group, or an ester group. The substituted phenyl group means a phenyl group substituted with 1, 2 or 3 substituents. The substituents include halogen, C 1~2 Alkoxy group, C 1~2 Haloalkoxy group, cyano group, C 1~6 Alkyl group or C 1~6 haloalkyl groups. The heterocycle is selected from five- or six-membered monocyclic rings having at least one non-carbon atom, including aromatic rings and non-aromatic hydrocarbons. The substituted heterocyclic ring means a heterocyclic ring having 1, 2 or 3 substituents. The substituents of the substituted heterocyclic ring are halogen, C 1~6 Alkyl group, C 1~6 Haloalkyl group, C 1~6 Alkoxy group or C1~6 alkylamide groups.

[0006] Preferably, R1 is H, C 1~6 It is selected from an alkyl group, a trifluoromethyl group, or a cyclopropyl group. R is C 1~6 Alkyl group, C 1~6 Haloalkyl group, C 3~6 Cycloalkyl groups, C 2~6 Alkenyl group, C 2~6 Alkynyl group, phenyl group, substituted phenyl group, C 5~6 It is selected from heterocycles and substituted heterocycles. The substituted phenyl group means a phenyl group substituted with 1, 2 or 3 substituents. The substituents include halogen, C 1~2 Alkoxy group, C 1~2 Haloalkoxy group, cyano group, C 1~2 Alkyl group or C 1~2 haloalkyl groups. The heterocycle is selected from a nitrogen-containing 5-membered heterocycle, a sulfur-containing 5-membered heterocycle, an oxygen-containing 5-membered heterocycle, a nitrogen-containing 6-membered heterocycle, a sulfur-containing 6-membered heterocycle, or an oxygen-containing 6-membered heterocycle. The substituents of the substituted heterocycle are halogen, C 1~2 Alkyl group, C 1~2 Haloalkyl group, C 1~2 Alkoxy group or C 1~2 alkylamide groups.

[0007] More preferably, R1 is C 1~4 The alkyl group is selected from the group consisting of:

[0008] R is C 1~6 Alkyl group, C 1~6 Haloalkyl group, C 3~6 Cycloalkyl groups, C 2~6 Alkenyl group, C 2~6 Alkynyl group, phenyl group, substituted phenyl group, C 5~6 It is selected from heterocycles and substituted heterocycles. The substituted phenyl group refers to a phenyl group substituted with one, two or three substituents selected from halogen, methoxy, cyano, ethoxy, methyl, ethyl or trifluoromethyl. The heterocycle is selected from piperazinyl, pyrrolidinyl, dioxanyl, morpholinyl, tetrahydrofuranyl, pyridinyl, furanyl, imidazolyl, pyrimidinyl, oxazolyl, isoxazolyl, tetrazolyl, triazolyl, thiadiazolyl, and thienyl. The substituted heterocycle means a heterocycle having one, two or three substituents selected from halogen, methyl, ethyl, methoxy, trifluoromethyl and difluoromethyl groups.

[0009] More preferably, R1 is selected from methyl groups. R is C 1~6 Alkyl group, C 1~6 Haloalkyl group, C 3~6 Cycloalkyl groups, C 2~6 Alkenyl group, C 2~6 Alkynyl group, phenyl group, substituted phenyl group, C 5~6 It is selected from heterocycles and substituted heterocycles. The substituted phenyl group refers to a phenyl group substituted with one, two or three substituents, the substituents being selected from halogen, methoxy, cyano, methyl or trifluoromethyl. The heterocycle is selected from 2-thienyl, pyridinyl, 2-chloropyridine or 5-bromopyridine. The substituted heterocycle means a heterocycle having 1, 2 or 3 substituents, the substituents of which are selected from halogen, methyl, methoxy and trifluoromethyl groups.

[0010] More preferably, R is selected from methyl, trifluoromethyl, difluoromethyl, chloromethyl, cyclopropyl, heptafluoroisopropyl, ethyl, isopropyl, n-propyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, ethynyl, propenyl, butenyl, propynyl, butynyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridine, and 5-bromopyridine.

[0011] Even more preferably, R1 is selected from a cyclopropyl group or a trifluoromethyl group.

[0012] In preferred embodiments of the present invention, there are provided compounds of formula (Ia), (Ib), (Ic) and (Id). [ka] (Ia) (Ib) [ka] (Ic) (Id)

[0013] R1 is selected from methyl, trifluoromethyl, difluoromethyl, cyclopropyl, heptafluoroisopropyl, ethyl, chloromethyl, isopropyl, n-propyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, ethynyl, propenyl, butenyl, propynyl, butynyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridine, and 5-bromopyridine.

[0014] Even more preferably, R1 is selected from a methyl group and R is selected from a cyclopropyl group or a trifluoromethyl group.

[0015] As preferred specific compound structures of the present invention, the substituents are as shown in Table 1 (based on general formula (I)).

[0016] [Table 1-a] [Table 1-b] [Table 1-c]

[0017] The substituents are also N-oxides or tautomers of the compounds in Table 1. "Ph" represents a phenyl group, and "Py" represents a pyridyl group.

[0018] A second object of the present invention is to provide a method for preparing fused ring compounds containing sulfur substituents, taking the structure shown in (Ia) as an example, comprising the following steps: [ka] (Ia)

[0019] Step (1): The compound obtained by the reaction of the compound of formula (II) with the compound of formula (III) is stirred and refluxed in acetic acid to obtain the compound of formula (IV). The preparation of the compound of formula (II) is well known, for example, as described in WO 2014 / 119672A and WO2015 / 002211A. The compound of formula (III) can be prepared from commercially available 3-chloro-5-bromopyridine-2-carboxylic acid.

[0020] Step (2): The compound represented by formula (IV) is contacted with ethanethiol under alkaline conditions to obtain a compound represented by formula (V).

[0021] Step (3): The compound represented by formula (V) is reacted with an oxidizing agent to obtain a compound represented by formula (VI).

[0022] Step (4): The compound represented by formula (VI) is subjected to a Buchwald coupling reaction with 2,4-dimethoxybenzylamine to obtain the compound represented by formula (VII).

[0023] Step (5): The compound represented by formula (VII) is reacted with trifluoroacetic acid to obtain the compound represented by formula (VIII).

[0024] Step (6): The compound represented by formula (VIII) is subjected to a catalytic reaction with a brominating reagent to obtain a compound represented by formula (IX).

[0025] Step (7): The compound of formula (IX) is reacted with acyl chloride in the presence of an acid binder to give the compound of formula (X).

[0026] Step (8): The compound represented by formula (X) is reacted with Lawesson's reagent to obtain the compound represented by formula (XI).

[0027] Step (9): The compound of formula (XI) is reacted in the presence of a base to obtain the final target compound of formula (Ia), where R and R1 are as defined above, but are not intended to limit the present invention. [ka]

[0028] Preferably, the organic solvent in step (1) is one or more selected from acetic acid, benzene, and toluene, and is preferably acetic acid. The reaction temperature is 25 to 110° C., and preferably 110° C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 0.4 mL / mmol, calculated based on the molar amount of the compound represented by formula (II).

[0029] Preferably, the organic solvent used in step (2) is one or more of benzene, toluene, N,N-dimethylformamide (DMF), and tetrahydrofuran, preferably tetrahydrofuran. The base is one or more of sodium hydride, sodium hydroxide, and potassium hydroxide, preferably sodium hydride. The reaction molar ratio of the compound represented by formula (IV), ethanethiol, and sodium hydride is 1:1 to 2:1 to 2, preferably 1:1:1.2. The reaction temperature is -10 to 80°C, preferably 0°C. The volume of the organic solvent used is 0.3 to 9 mL / mmol, preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (IV).

[0030] Preferably, the organic solvent used in step (3) is one or more of dichloromethane, dichloroethane, methanol, ethanol, DMF, and tetrahydrofuran, and preferably dichloromethane. The oxidizing agent is one or more of hydrogen peroxide and metachloroperbenzoic acid, and preferably hydrogen peroxide. The reaction temperature is 25 to 40°C, and preferably 25°C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (V).

[0031] Preferably, the organic solvent used in step (4) is one or more of benzene, toluene, and 1,4-dioxane, and preferably toluene. The reaction temperature is 25 to 150° C., and preferably 120° C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (VI).

[0032] Preferably, the organic solvent used in step (5) is one or more of dichloromethane, dichloroethane, ethanol, methanol, acetonitrile, and tetrahydrofuran, and preferably dichloromethane. The reaction temperature is 25 to 80°C, and preferably 25°C. The molar ratio of the compound represented by formula (VII) to trifluoroacetic acid is 1:1 to 10, and preferably 1:2. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (VII).

[0033] Preferably, the organic solvent in step (6) is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, 1,4-dioxane, and acetic acid, and preferably acetic acid. The brominating reagent is one or more of bromine and N-bromosuccinimide (NBS), and preferably bromine. The reaction temperature is 25 to 80°C, and preferably 80°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (VIII).

[0034] Preferably, the organic solvent in step (7) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably tetrahydrofuran. The acid binder is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, 4-dimethylaminopyridine (DMAP), and sodium hydride, and is preferably triethylamine. The reaction temperature is 0 to 80°C, and preferably 25°C. The amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (IX).

[0035] Preferably, the organic solvent in step (8) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably tetrahydrofuran. The molar ratio of the compound represented by formula (X) to Lawesson's reagent is 1:1 to 5, and preferably 1:1.5. The reaction temperature is 25 to 80°C, and preferably 80°C. The volume of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (X).

[0036] Preferably, the organic solvent in step (9) is selected from one or more of 1,4-dioxane, dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably 1,4-dioxane. The base is one or more of sodium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide, and is preferably cesium carbonate. The reaction temperature is 25 to 120°C, and preferably 80°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (XI). [ka] (Ib)

[0037] A similar preparation of the structure shown in (Ib) involves the following steps.

[0038] The compound of formula (X) is refluxed and stirred in a solvent in the presence of copper (I) iodide (CuI), a base and a catalyst to obtain the compound of formula (Ib). [ka]

[0039] Preferably, the catalyst in the above step is 10-phenanthroline. The base is one or more of sodium carbonate, potassium carbonate, and cesium carbonate, preferably cesium carbonate. The solvent is one or more of tetrahydrofuran, dichloromethane, dichloroethane, and ethylene glycol dimethyl ether, preferably ethylene glycol dimethyl ether. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (X). [ka] (I C)

[0040] A similar preparation of the structure shown in formula (Ic) involves the following steps:

[0041] Similar to the method for producing the compound of formula (IV) in formula (Ia), the compound of formula (II) is refluxed and stirred in acetic acid to give the compound of formula (III).

[0042] The compound of formula (III) is reacted with ethanethiol in the presence of a base to give the compound of formula (IV).

[0043] The compound of formula (IV) is oxidized to give the compound of formula (V).

[0044] The compound of formula (V) is contacted with a substituted amine in a solvent to provide a compound of formula (VI).

[0045] The compound of formula (VI) is dissolved in concentrated sulfuric acid, and then diluted nitric acid is added dropwise at low temperature to obtain the compound of formula (VII).

[0046] The compound of formula (VII) is reduced to give the compound of formula (VIII).

[0047] The method for preparing the compound of formula (IX) is the same as the method for preparing the compound of formula (X) in formula (Ia).

[0048] The compound of formula (IX) is refluxed and stirred in acetic acid to finally give the compound of formula (Ic). [ka]

[0049] Preferably, the organic solvent in step (1) is one or more selected from acetic acid, benzene, and toluene, and is preferably acetic acid. The reaction temperature is 25 to 110° C., and preferably 110° C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 0.4 mL / mmol, calculated based on the molar amount of the compound represented by formula (II).

[0050] Preferably, the organic solvent used in step (2) is one or more of benzene, toluene, DMF, and tetrahydrofuran, and preferably tetrahydrofuran. The base is one or more of sodium hydride, sodium hydroxide, and potassium hydroxide, and preferably sodium hydride. The reaction molar ratio of the compound represented by formula (IV) to ethanethiol and sodium hydride is 1:1 to 2:1 to 2, and preferably 1:2:2. The reaction temperature is -10 to 80°C, and preferably 0°C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (IV).

[0051] Preferably, the organic solvent used in step (3) is one or more of dichloromethane, dichloroethane, methanol, ethanol, DMF, and tetrahydrofuran, and preferably dichloromethane. The oxidizing agent is one or more of hydrogen peroxide and metachloroperbenzoic acid, and preferably hydrogen peroxide. The reaction temperature is 25 to 40°C, and preferably 25°C. The volumetric amount of the organic solvent used is 0.3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (V).

[0052] Preferably, the solvent used in step (4) is one or more of methanol, ethanol, DMF, and tetrahydrofuran, and preferably tetrahydrofuran. The reaction temperature is 25 to 120°C, and preferably 100°C.

[0053] Preferably, the reaction temperature in step (5) is -10 to 25°C, and more preferably 0°C.

[0054] Preferably, the reducing agent in step (6) is iron powder or palladium on carbon, preferably palladium on carbon.

[0055] Preferably, the organic solvent in step (7) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably tetrahydrofuran. The acid binder is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, DMAP, and sodium hydride, and is preferably triethylamine. The reaction temperature is 0 to 80°C, and preferably 25°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (VIII).

[0056] Preferably, the reaction temperature in step (8) is 90 to 150°C, and more preferably 110°C. [ka] (Id)

[0057] A similar preparation of the structure shown in formula (Id) involves the following steps:

[0058] The compound of formula (V) obtained by formula (Ic) is contacted with aqueous ammonia in a solvent to obtain a compound of formula (X).

[0059] The compound represented by formula (X) is subjected to a bromination reaction in a solvent in the presence of a base to obtain a compound represented by formula (XI).

[0060] The preparation method of formula (XII) is the same as the preparation method of formula (IX) in (Ic).

[0061] The preparation method of formula (XIII) is the same as the preparation method of formula (XI) in (Ia).

[0062] The preparation method of formula (Id) is the same as the preparation method of formula (Ia). [ka]

[0063] Preferably, the solvent used in step (1) is one or more of methanol, ethanol, DMF, and tetrahydrofuran, and preferably tetrahydrofuran. The reaction temperature is 25 to 120°C, and preferably 100°C.

[0064] Preferably, the organic solvent in step (2) is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, 1,4-dioxane, and acetic acid, and preferably acetic acid. The brominating reagent is one or more of bromine and NBS, and preferably bromine. The base is sodium acetate or potassium acetate, and preferably potassium acetate. The reaction temperature is 25 to 80°C, and preferably 80°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (VIII).

[0065] Preferably, the organic solvent in step (3) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably tetrahydrofuran. The acid binder is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, DMAP, and sodium hydride, and is preferably triethylamine. The reaction temperature is 0 to 80°C, and preferably 25°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (XI).

[0066] Preferably, the organic solvent in step (4) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably tetrahydrofuran. The molar ratio of the compound represented by formula (XII) to Lawesson's reagent is 1:1 to 5, and preferably 1:1.5. The reaction temperature is 25 to 80°C, and preferably 80°C. The volume of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated based on the molar amount of the compound represented by formula (XII).

[0067] Preferably, the organic solvent in step (5) is selected from one or more of 1,4-dioxane, dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide, and acetonitrile, and is preferably 1,4-dioxane. The base is one or more of sodium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, and potassium hydroxide, and is preferably cesium carbonate. The reaction temperature is 25 to 120°C, and preferably 80°C. The volumetric amount of the organic solvent used is 3 to 9 mL / mmol, and preferably 5 mL / mmol, calculated in terms of the molar amount of the compound represented by formula (XIII).

[0068] A third aspect of the present invention provides the use of a fused ring compound containing a sulfur substituent as shown in formula (I) in the manufacture of a pesticide.

[0069] Preferably, the insecticide is an insecticide that controls insects of the order Lepidoptera and / or Coleoptera. Furthermore, the pest may be one or more of the brown planthopper, the striate brown planthopper, the sweet potato whitefly, the diamondback moth, the armyworm, the green peach aphid, and the false spider mite.

[0070] A fourth aspect of the present invention provides an insecticide comprising a fused ring compound containing a sulfur substituent and an adjuvant, wherein the concentration of the fused ring compound containing a sulfur substituent in the insecticide is 1 to 600 ppm. Furthermore, the concentration of the fused ring compound containing a sulfur substituent in the insecticide is 4 to 100 ppm.

[0071] In the event that the Chinese name of a compound in the present invention contradicts its structural formula, the structural formula shall prevail.

[0072] Compared with the prior art, the beneficial effects of the present invention are as follows: The fused ring compounds containing sulfur substituents provided by the present invention have good control effects against various pests at relatively low test concentrations, which provides a basis for the research and development of new pesticides. DETAILED DESCRIPTION OF THE INVENTION

[0073] The present invention will be described in detail below with reference to the following examples, but the present invention is not limited thereto. Any simple substitutions or improvements made by those skilled in the art to the present invention are included in the technical solutions protected by the present invention.

[0074] <Production Example 1> Synthesis of target compound I-1 [ka]

[0075] Step A: Synthesis of 2-methylamino-5-trifluoromethylpyridine [ka]

[0076] 2-Chloro-5-trifluoromethylpyridine (90.5 g, 0.5 mol) was dissolved in acetonitrile (50 mL) and methylamine alcohol solution (46.5 g, 1.5 mol) was added. The mixture was placed in a 350 mL pressure bottle and stirred overnight at 100°C. The reaction endpoint was monitored by TLC and LC-MS. The reaction mixture was then concentrated in vacuo to give white crystals of 2-methylamino-5-trifluoromethylpyridine in 95% yield.

[0077] Step B: Synthesis of 2-methylamino-3-nitro-5-trifluoromethylpyridine [ka]

[0078] 2-Methylamino-3-nitro-5-trifluoromethylpyridine (52.8 g, 0.3 mol) was dissolved in concentrated sulfuric acid (100 mL) and nitric acid (18.9 g, 0.3 mol) was added dropwise in an ice bath. After the addition was completed within 30 minutes, the ice bath was removed, and the reaction mixture was heated to 80 °C and reacted for 3 hours. The end point of the reaction was monitored by LC and GC-MS. The reaction mixture was then slowly poured into ice water to precipitate a solid, which was then filtered and washed with water. The filter cake was dried to give the title compound (47.7 g, 72% yield) as a yellow solid.

[0079] Step C: Synthesis of 2-methylamino-3-amino-3-trifluoromethylpyridine [ka]

[0080] 2-Methylamino-3-nitro-5-trifluoromethylpyridine (11.05 g, 50 mmol) was dissolved in tetrahydrofuran (100 mL), 5% palladium on carbon (Pd / C) was added, and the mixture was stirred under a stream of hydrogen gas at room temperature for 24 hours. The end point of the reaction was monitored by TLC and GC-MS. The reaction mixture was then filtered to remove the palladium on carbon, and the filtrate was concentrated in vacuo to give the title compound (10.9 g, 99% yield) as reddish-brown crystals.

[0081] Step D: Synthesis of 3,6-dichloropyridine-2-carbonyl chloride [ka]

[0082] A sample of 3,6-dichloropyridine-2-carboxylic acid (5.00 g, 24.7 mmol) was diluted with dichloromethane (200 mL) and dimethylformamide (0.124 mL, 1.6 mmol) was added. To this solution, oxalyl chloride (3.15 mL, 34.6 mmol) was added dropwise at room temperature within 10 minutes (gas evolution). The reaction mixture was stirred at room temperature, and after 2.5 hours, an additional 1 mL of oxalyl chloride was added and stirring was continued for 1 hour. After this time, the reaction mixture was concentrated in vacuo and used in the next step without further purification.

[0083] Step E: Synthesis of 3,6-dichloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)picolinamide [ka]

[0084] To a solution of 2-methylamino-3-amino-3-trifluoromethylpyridine (16.70 g, 87.37 mmol) in tetrahydrofuran (THF) (167.0 mL) was added triethylamine EtN (22.32 g, 218.4 mmol). The reaction mixture was cooled to 0 °C, and 3,6-dichloropyridine-2-carbonyl chloride (18.37 g, 87.37 mmol) dissolved in dichloromethane (170 mL) was added dropwise over 1 h at 0–10 °C. After 1.5 h, the desired product was detected by LC-MS. The ice bath was removed, and the reaction mixture was allowed to warm to ambient temperature and stirred for 12 h. The reaction mixture was then diluted with saturated ammonium chloride (NHCl), the organic phase was separated, and the aqueous phase was back-extracted with dichloromethane. The combined organic phase was washed with water, brine, and sodium sulfate (NaSO). 4) The mixture was dried at 4°C, filtered and concentrated in vacuo to give the crude product, which was purified by column chromatography.

[0085] Step F: Synthesis of 2-(3,6-dichloropyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine [ka]

[0086] A yellow solution of 3,6-dichloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)picolinamide (15.6 g, 42.75 mmol) in acetic acid (50 mL) was stirred overnight at a bath temperature of 110 °C. After that, LC-MS analysis showed that the reaction was complete. The reaction mixture was then poured into ice water and extracted with ethyl acetate (EA) (20 mL × 3). The organic phases were combined and washed with saturated sodium bicarbonate solution (20 mL × 3), dried over Na2SO4, and purified by column chromatography to give a white solid (8 g, crude yield 54%).

[0087] Step G: Synthesis of 2-(6-chloro-3-(ethylthio)pyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine [ka]

[0088] 2-(3,6-Dichloropyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (1.14 g, 3.28 mmol) was dissolved in tetrahydrofuran. Sodium hydride (NaH) (3.28 mmol) was added portionwise at room temperature and stirred for 30 minutes. After that, ethanethiol (0.2 g, 3.28 mmol) was added dropwise and stirred at room temperature until the reaction was complete. The reaction mixture was treated with NH4Cl and then extracted with ethyl acetate. The organic layer was separated, washed with water and brine, dried over Na2SO4, and the crude product was purified by silica gel flash chromatography to give the title compound as a beige solid in 80% yield.

[0089] Step H: Synthesis of 2-(6-chloro-3-(ethylsulfonyl)pyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine [ka]

[0090] To the product obtained in the previous step (8.556 g, 23 mmol), formic acid (5.29 g, 115 mmol) and aqueous hydrogen peroxide (3.0 g, 161 mmol) were added at room temperature, and the mixture was stirred at room temperature for 5 hours. After the reaction was complete, the mixture was diluted with water, sodium bisulfite solution was added, and the mixture was stirred for 1 hour. After that, saturated sodium bicarbonate solution was added. The organic phase was separated, and the aqueous phase was extracted twice with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and purified by column chromatography to give a white solid (6.6 g, 74% yield).

[0091] Step I: 5-(ethylsulfonyl)-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyridin-2-amine [ka]

[0092] 2-(6-chloro-3-(ethylsulfonyl)pyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.4 g, 1 mmol) was dissolved in ethanol. The solution was placed in a pressure bottle, 3 equivalents of aqueous ammonia was added, and the mixture was allowed to react at 120°C overnight. LC-MS showed the reaction was complete. The solution was cooled to room temperature, and the precipitated solid was filtered and washed with a small amount of methanol. After drying, a yellow solid was obtained in 90% yield.

[0093] Step J: 5-(ethylsulfonyl)-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyridine-2-methylamine [ka]

[0094] The compound obtained in step H was dissolved in methanol, followed by the addition of a three-fold methylamine alcohol solution. The mixture was placed in a pressure-resistant bottle and reacted overnight at 120°C. After monitoring the completion of the reaction by LC-MS, the reaction mixture was cooled to room temperature. At this time, a solid precipitated, which was filtered and dried to obtain the product.

[0095] 1 H NMR (400 MHz,Chloroform-d) δ 8.73 (d,J = 1.9 Hz,1H), 8.28 (d,J = 2.0 Hz,1H), 8.10 (d,J = 9.0 Hz,1H), 6.60 (d,J = 8.9 Hz,1H), 5.30 (s,1H), 3.86 (s,3H), 3.60 (q,J = 7.4 Hz,2H), 3.03 (d,J = 5.1 Hz,3H), 1.31 (t,J = 7.4 Hz,3H). Step K: Synthesis of 5-(ethylsulfonyl)-N-methyl-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)-3nitro-2-amine [ka]

[0096] The compound obtained in Step J was dissolved in concentrated sulfuric acid, and then an equal volume of nitric acid was added dropwise in an ice bath. After the addition was complete, the mixture was stirred at room temperature for several hours. After confirming the completion of the reaction by LC-MS, the reaction mixture was poured into ice water, and a yellow solid precipitated. The solid was filtered, dried, and used directly in the next reaction without further purification.

[0097] Step L: Synthesis of 5-(ethylsulfonyl)-N-methyl-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyridine-2,3-diamine [ka]

[0098] The crude product obtained in Step K was dissolved in THF, and then palladium-carbon catalyst (5% of the raw material mass) was added thereto. The air in the bottle was replaced with hydrogen gas three times, and the reaction was allowed to proceed overnight with stirring at 30°C. After LC-MS monitoring showed the reaction was complete, the reaction solution was filtered, the filtrate was spin-dried, and the crude product obtained could be purified by column chromatography.

[0099] Step M: Synthesis of target compound I-1 [ka]

[0100] The compound obtained in Step L (1 mmol) was dissolved in THF, followed by the addition of cyclopropanecarbonyl chloride (1 mmol), followed by triethylamine (1.5 mmol). The mixture was stirred at room temperature. After the reaction was completed, the reaction mixture was directly spun dry, dissolved in acetic acid, and refluxed at 120°C for several hours. After the completion of the reaction was confirmed by LC-MS, water was added to the reaction mixture, extracted with ethyl acetate, and the organic phase was dried and purified by column chromatography to give 109 mg of the title compound in a two-step yield of 20%, with a melting point (mp) of 201-204°C. 1 H NMR (400 MHz,CDCl3) δ 8.79 - 8.74 (m,1H), 8.65 (s,1H), 8.31 (d,J = 2.0 Hz,1H), 3.99 (s,3H), 3.83 (s,3H), 3.68 (q,J = 7.4 Hz,2H), 2.14 (tt,J = 8.1, 4.8 Hz, 1H), 1.42 (dt,J = 4.8, 3.2 Hz,2H), 1.35 - 1.28 (m,5H).EI-MS: 465[M+H]+

[0101] <Production Example 2> Compound I-2 of the present invention represented by the following formula was obtained according to the method described in Step M of Preparation 1, except that cyclopropanecarbonyl chloride was replaced with acetyl chloride. [ka] Compound I-2 of the present invention 1 H NMR (400 MHz,CDCl3) δ 8.79 - 8.73 (m,2H), 8.33 (d,J = 2.0 Hz,1H), 3.89 (s,3H), 3.82 (s,3H), 3.68 (q, J = 7.5 Hz,2H), 2.79 (s,3H), 1.33 (t,J = 7.4 Hz,3H).

[0102] <Production Example 3> Synthesis of target compound I-73 [ka]

[0103] Step A: Synthesis of intermediate compound 1. Following the method described in Step E of Preparation 1, but substituting 3-chloro-5-bromopyridine-2-carbonyl chloride for 3,6-dichloropyridine-2-carbonyl chloride, intermediate compound 1 represented by the following formula could be obtained. [ka] Intermediate compound 1 1 H NMR (400 MHz,CDCl3) δ 9.33 (s,1H), 8.60 (d,J = 1.9 Hz,1H), 8.36 (dd,J = 2.2, 1.1 Hz,1H), 8.10 (d,J = 1.9 Hz,1H), 7.86 (d,J = 2.1 Hz,1H), 5.03 (d,J = 5.9 Hz,1H), 3.08 (d,J = 4.8 Hz,3H).

[0104] Step B: Synthesis of intermediate compound 2 According to the method described in Step F of Preparation Example 1, intermediate compound 2 represented by the following formula could be obtained. [ka] Intermediate compound 2 1 H NMR (400 MHz,CDCl3) δ 8.77 (d,J = 1.9 Hz,2H), 8.40 (d,J = 2.0 Hz,1H), 8.16 (d,J = 1.9 Hz,1H), 3.98 (d,J = 1.2 Hz,3H).

[0105] Step C: Synthesis of intermediate compound 3 According to the method described in Step G of Preparation 1, intermediate compound 3 represented by the following formula could be obtained. [ka] Intermediate compound 3

[0106] Step D: Synthesis of intermediate compound 4 According to the method described in Step H of Preparation 1, intermediate compound 4 represented by the following formula could be obtained. [ka] Intermediate compound 4

[0107] Step E: Synthesis of Intermediate Compound 5 Intermediate compound 4 (5 mmol) was dissolved in dry toluene (35 mL) and then cesium carbonate (7.5 mmol) was added. The mixture was degassed with argon, and then tris(dibenzylideneacetone)dipalladium(0) (0.11 mmol), 2,2'-bis(diphenylphosphino)-1,1'-dihydronaphthalene (0.2 mmol), and 2,4-dimethoxybenzylamine (5 mmol) were added. The mixture was stirred at 105 °C (bath) under argon. The dark purple color of the mixture turned to pale yellow within 15 minutes. After 20 hours, the reaction was cooled and the solvent was removed under reduced pressure. The residue was purified on 50 g of silica gel using 50% ethyl acetate in hexane as the eluent. Intermediate compound 5, represented by the following formula, was obtained. [ka] Intermediate compound 5

[0108] Step F: Synthesis of intermediate compound 6 Intermediate compound 5 (3.31 mmol) was dissolved in dichloromethane (20 mL) at ambient temperature, followed by the addition of trifluoroacetic acid (3.31 mmol). The orange-red solution was stirred at ambient temperature for 5 hours. The volatiles were removed under reduced pressure. The residue was basified with saturated sodium bicarbonate (NaHCO3) solution and extracted with ethyl acetate. The organic phase was separated, dried, and concentrated. The residue was purified on 40 g of silica gel using ethyl acetate as the eluent to give intermediate compound 6, which is represented by the following formula: [ka] intermediate compound 6

[0109] Step G: Synthesis of intermediate compound 7 Intermediate compound 6 (1 mmol) was dissolved in 10 mL of acetic acid, followed by the addition of sodium acetate (1 mmol) and the dropwise addition of bromine (1.2 mmol) in 5 mL of acetic acid at room temperature. The reaction mixture was then stirred at its current temperature. After completion of the reaction, the mixture was quenched with aqueous sodium thiosulfate solution, extracted with ethyl acetate, and dried over anhydrous sodium sulfate. The residue was purified by column chromatography to obtain intermediate compound 7, which is represented by the following formula: [ka] Intermediate compound 7

[0110] Step H: Synthesis of intermediate compound 8 Intermediate compound 7 (1 mmol) was dissolved in THF, and cyclopropanecarbonyl chloride (1 mmol) was added, followed by triethylamine (1.5 mmol), and the mixture was stirred at room temperature. After the reaction was completed, the mixture was purified by column chromatography to obtain intermediate compound 8 represented by the following formula as a white solid. [ka] Intermediate compound 8 1 H NMR (400 MHz,Chloroform-d) δ 9.44 (d,J = 1.6 Hz,1H), 8.75 (d,J = 2.0 Hz,1H), 8.30 (d,J = 2.0 Hz,1H), 8.12 (s,1H), 3.91 (d,J = 1.6 Hz,3H), 3.81 (q,J = 7.5 Hz,2H), 1.74 - 1.68 (m,1H), 1.39 (t,J = 7.5 Hz,3H), 1.26 - 1.22 (m,3H), 1.06 (dt,J = 7.5, 3.5 Hz,2H).

[0111] Step I: Synthesis of intermediate compound 9 Intermediate compound 8 (1 mmol) was dissolved in THF (15 mL), and Lawesson's reagent (1.5 mmol) was added and stirred under reflux. After the reaction was completed, the solvent was distilled off and the residue was purified by column chromatography to obtain intermediate compound 9 (represented by the following formula) as a pale yellow solid in a yield of 40%. [ka]

[0112] Step J: Synthesis of target compound I-73 Intermediate compound 9 (1 mmol) was dissolved in 1,4-dioxane (15 mL), and then cesium carbonate (1.5 mmol) was added and stirred in an oil bath at 80°C. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate. Finally, the mixture was purified by column chromatography to obtain compound I-73 of the present invention, represented by the following formula, as a white solid with a yield of 80% and an mp of 216-219°C. [ka] Compound I-73 of the present invention 1 H NMR (400 MHz,CDCl3) δ 8.84 (s,1H), 8.77 (d,J = 1.9 Hz,1H), 8.34 (d,J = 2.1 Hz,1H), 3.86 (s,3H), 3.75 (q, J = 7.4 Hz,2H), 2.51 (tt,J = 8.1, 5.3 Hz,1H), 1.46 - 1.41 (m,4H), 1.35 (t,J = 7.4 Hz,3H).EI-MS: 468[M+H]+.

[0113] <Production Example 4> Synthesis of target compound I-37 Intermediate compound 8 (1 mmol) was dissolved in 1,4-dioxane (15 mL), and then CuI (1.5 mmol) was added and stirred under reflux under a nitrogen atmosphere. After completion of the reaction, the solvent was distilled off, and the residue was purified by column chromatography to obtain compound I-37 (represented by the following formula) as a white solid in a 40% yield with an mp of 224-227°C. [ka] Compound I-37 of the present invention 1 H NMR (400 MHz,CDCl3) δ 8.77 (dd,J = 2.0, 0.8 Hz,1H), 8.69 (s,1H), 8.31 (d,J = 2.0 Hz,1H), 3.87 (s,3H), 3.83 (q, J = 7.4 Hz,2H), 2.35 (tt,J = 8.2, 4.9 Hz,1H), 1.50 - 1.45 (m,2H), 1.42 - 1.39 (m,2H), 1.36 (d,J = 7.5 Hz,3H).EI-MS: 452[M+H]+

[0114] <Production Example 5> Synthesis of target compound I-109 Step A: Synthesis of intermediate compound 10 Following the procedure described in Step I of Preparation Example 3, the substrate (1 mmol) was dissolved in THF (15 mL), followed by the addition of Lawesson's reagent (1.5 mmol) and stirring under reflux. After completion of the reaction, the solvent was distilled off, and the residue was purified by column chromatography to obtain intermediate compound 10 represented by the following formula in a 70% yield. [ka] Intermediate compound 10

[0115] Step B: Synthesis of target compound I-109 Intermediate compound 10 (1 mmol) was dissolved in 1,4-dioxane (15 mL), cesium carbonate (1.5 mmol) was added, and the mixture was stirred in an oil bath at 80 °C. After the reaction was completed, water was added and the mixture was extracted with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate. Finally, the mixture was purified by column chromatography to obtain compound I-109 of the present invention, represented by the following formula, in 85% yield with an mp of 207-210 °C. [ka] Compound I-109 of the present invention 1 H NMR (400 MHz,CDCl3) δ 8.99 (s,1H), 8.79-8.73 (m,2H), 8.30 (dd,J = 8.8, 1.9 Hz,2H), 3.94 (s,3H), 3.93-3.88 (m,2H), 2.52 (tt,J = 8.0, 4.7 Hz,1H), 1.59-1.54 (m,2H), 1.47 (dt,J = 8.1, 3.4 Hz,2H), 1.41-1.37 (m,3H).EI-MS: 468[M+H]+.

[0116] Similarly to the examples, the following compounds of formula (I) were synthesized according to the above preparation methods. [ka] (I)

[0117] [Table 2-1] [Table 2-2] [Table 2-3] [Table 2-4]

[0118] Nuclear magnetic resonance (NMR) data for the above preferred compounds are shown in Table 3. [Table 3-1] [Table 3-2]

[0119] Biological Testing This test example is used to illustrate the inhibition (%) of the insecticidal activity of compounds having the structure of formula (I) (at a dose of 100 ppm).

[0120] Test Example 1: Activity against green peach aphid (green peach aphid) Roots of pea seedlings infested with mixed-age aphid populations were placed directly into aqueous test solutions prepared from a 10,000 ppm dimethyl sulfoxide (DMSO) stock solution. The seedlings were left in the test solutions for 6 days, after which the samples were evaluated for mortality.

[0121] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73, and I-109 showed at least 90% mortality at an application rate of 100 ppm.

[0122] Test Example 2: Activity against diamondback moth (Plutella xylostella) Twenty-four-well microtiter plates containing artificial diet were treated by pipetting with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, each plate was infected with L2 stage larvae (10–15 larvae per well). Five days after infection, these samples were assessed for mortality and growth inhibition compared with untreated samples.

[0123] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73 and I-109 showed at least 90% efficacy in at least one of two categories (mortality or growth inhibition) at an application rate of 100 ppm.

[0124] Furthermore, the compounds I-73 and I-109 gave 100% mortality at an application rate of 4 ppm.

[0125] Test Example 3: Activity against armyworm Agar layers in 24-well microtiter plates were spray-treated with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the plates were infested with L2 stage larvae (6–10 per well). Four days after infection, these samples were assessed for mortality and growth inhibition compared with untreated samples.

[0126] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73 and I-109 showed at least 90% efficacy in at least one of two categories (mortality or growth inhibition) at an application rate of 100 ppm.

[0127] Test Example 4: Activity against brown planthoppers Cotton leaf discs were placed on agar in 24-well microtiter plates and sprayed with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, the discs were infested with adult brown planthoppers. After 6 days of incubation, the samples were assessed for mortality.

[0128] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73, I-100 and I-109 showed at least 90% mortality at an application rate of 100 ppm.

[0129] Furthermore, the compounds I-73, I-100 and I-109 provided at least 95% mortality at an application rate of 45 ppm.

[0130] Test Example 5: Activity against beet armyworm Twenty-four-well microtiter plates containing artificial diet were treated by pipetting with test solutions prepared from a 10,000 ppm DMSO stock solution. After drying, each plate was infected with L2 stage larvae (10–15 larvae / well). Five days after infection, these samples were assessed for mortality and growth inhibition compared with untreated samples.

[0131] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73, I-74, I-86 and I-109 showed at least 90% efficacy in at least one of two categories (mortality or growth inhibition) at an application rate of 100 ppm.

[0132] Furthermore, the compounds I-73 and I-109 gave 100% mortality at an application rate of 4 ppm.

[0133] Test Example 6: Activity against bean aphids Roots of pea seedlings infested with mixed-age aphid populations were placed directly into aqueous test solutions prepared from a 10,000 ppm DMSO stock solution. The seedlings were left in the test solutions for 6 days, after which the samples were assessed for mortality.

[0134] Compounds I-1, I-2, I-3, I-5, I-7, I-8, I-9, I-10, I-14, I-16, I-17, I-29, I-37, I-73, I-74, I-86, I-88 and I-109 showed at least 90% mortality at an application rate of 100 ppm.

[0135] Furthermore, compounds I-1, I-37, I-73, I-100 and I-109 gave 100% mortality at an application rate of 4 ppm.

[0136] Test Example 7: Activity against rice stem borer Five or six rice seedlings, 3-4 cm in diameter, were thoroughly immersed in the compounded solution, allowed to dry naturally in the shade, and then placed in test tubes. Ten second-instar larvae of the rice stem borer were inoculated into each tube, and the tubes were then placed in an observation chamber for rearing and observation. 0.1% Tween water (polysorbate 80) was used as a blank control. The samples were then placed in an observation chamber at 25-27°C, and the results were examined after 96 hours, and the mortality rate was assessed.

[0137] The compounds I-73 and I-109 gave 100% mortality at an application rate of 5 ppm.

[0138] It should be noted that the above-described embodiments are merely preferred embodiments of the present invention, and those skilled in the art can make multiple modifications and improvements without departing from the creative concept of the present invention, all of which fall within the scope of protection of the present invention.

Claims

1. A fused ring compound containing a sulfur substituent represented by general formula (I): 【Chemical 1】 (I) During the ceremony, X is N, NR 1 , O or S; Y is selected from N or S; If Y is selected from N, then X is NR 1 , O or S, and when Y is selected from S, X is selected from N; R in the formula 1 is H, C 1～6 Alkyl group, C 1～6 Haloalkyl group, C 3～6 Cycloalkyl groups, C 3～6 halocycloalkyl groups, R in the formula is H, C 1～6 Alkyl group, C 1～6 Substituted alkyl groups, C 3～6 Cycloalkyl groups, C 3～6 Substituted cycloalkyl groups, C 2～6 Epoxy group, C 2～6 Alkenyl group, C 2～6 Alkynyl group, phenyl group, substituted phenyl group, C 5～6 selected from heterocycles or substituted heterocycles; The substituents of the substituted alkyl group or substituted cycloalkyl group are halogen, C 1～2 Alkyl group, C 1～2 Alkoxy group, C 1～2 Haloalkoxy group, C 1～2 selected from a haloalkyl group, a cyano group, or an ester group; The substituted phenyl group is a phenyl group substituted with one, two or three substituents, the substituents being halogen, C 1～2 Alkoxy group, C 1～2 Haloalkoxy group, cyano group, C 1～6 Alkyl group or C 1～6 haloalkyl groups, the heterocycle is selected from 5- or 6-membered monocyclic rings having at least one non-carbon atom, including aromatic rings and non-aromatic hydrocarbons; The substituted heterocycle is a heterocycle having one, two or three substituents, and the substituents of the substituted heterocycle are halogen, C 1～6 Alkyl group, C 1～6 Haloalkyl group, C 1～6 Alkoxy group or C 1～6 A fused ring compound selected from alkylamide groups.

2. The X is N, NR 1 , O or S; wherein Y is selected from N or S, and when Y is selected from N, X is NR 1 , O or S, and when Y is selected from S, X is selected from N; R 1 is H, C 1～6 selected from an alkyl group, a trifluoromethyl group, or a cyclopropyl group; The R is C 1～6 Alkyl group, C 1～6 Haloalkyl group, C 3～6 Cycloalkyl groups, C 2～6 Alkenyl group, C 2～6 Alkynyl group, phenyl group, substituted phenyl group, C 5～6 selected from heterocycles or substituted heterocycles; the substituted phenyl group is a phenyl group substituted with one, two or three substituents, the substituents being selected from halogen, methoxy, cyano, ethoxy, methyl, ethyl or trifluoromethyl; said heterocycle is selected from piperazinyl, pyrrolidinyl, dioxanyl, morpholinyl, tetrahydrofuranyl, pyridinyl, furanyl, imidazolyl, pyrimidinyl, oxazolyl, isoxazolyl, tetrazolyl, triazolyl, thiadiazolyl, and thienyl; 2. The fused ring compound containing a sulfur substituent according to claim 1, wherein the substituted heterocycle is substituted with a heterocycle having one, two, or three substituents, and the substituents of the substituted heterocycle are selected from halogen, a methyl group, an ethyl group, a methoxy group, a trifluoromethyl group, and a difluoromethyl group.

3. R is C 1～6 Alkyl group, C 1～6 Haloalkyl group, C 3～6 Cycloalkyl groups, C 2～6 Alkenyl group, C 2～6 Alkynyl group, phenyl group, substituted phenyl group, C 5～6 selected from heterocycles or substituted heterocycles; the substituted phenyl group is a phenyl group substituted with one, two or three substituents, the substituents of the substituted phenyl group being selected from halogen, methoxy, cyano, methyl or trifluoromethyl; the heterocycle is selected from 2-thienyl, pyridinyl, 2-chloropyridine or 5-bromopyridine; 2. The fused ring compound containing a sulfur substituent according to claim 1, wherein the substituted heterocycle is substituted with a heterocycle having one, two, or three substituents, and the substituents of the substituted heterocycle are selected from halogen, methyl, methoxy, and trifluoromethyl groups.

4. R 1 is selected from a methyl group or an ethyl group, The R is C 1～6 Alkyl group, C 1～3 Haloalkyl group, C 3～6 Cycloalkyl groups, C 2～6 Alkenyl group, C 2～6 Alkynyl group, phenyl group, substituted phenyl group, C 5～6 selected from heterocycles or substituted heterocycles; the substituted phenyl group is a phenyl group substituted with one, two or three substituents, the substituents being selected from halogen, methoxy, cyano, methyl or trifluoromethyl; the heterocycle is selected from 2-thienyl, pyridinyl, 2-chloropyridine or 5-bromopyridine; 2. The fused ring compound containing a sulfur substituent according to claim 1, wherein the substituted heterocycle is substituted with a heterocycle having one, two, or three substituents, and the substituents of the substituted heterocycle are selected from halogen, methyl, methoxy, and trifluoromethyl groups.

5. 2. The fused ring compound containing a sulfur substituent according to claim 1, wherein R is selected from the group consisting of methyl, ethyl, trifluoromethyl, difluoromethyl, chloromethyl, cyclopropyl, heptafluoroisopropyl, isopropyl, n-propyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, ethynyl, propenyl, butenyl, propynyl, butynyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridine, and 5-bromopyridine.

6. Compounds having formula (Ia), (Ib), (Ic) and (Id): 【Chemistry 2】 (Ia) (Ib) 【Chemistry 3】 (Ic) (Id) R 1 is selected from a methyl group or an ethyl group, 2. The fused ring compound containing a sulfur substituent according to claim 1, wherein R is selected from the group consisting of methyl, trifluoromethyl, difluoromethyl, chloromethyl, cyclopropyl, heptafluoroisopropyl, ethyl, isopropyl, n-propyl, isobutyl, tert-butyl, cyclobutyl, cyclopentyl, cyclohexyl, vinyl, ethynyl, propenyl, butenyl, propynyl, butynyl, phenyl, cyanocyclopropyl, 4-fluorophenyl, 2-fluorophenyl, 3-fluorophenyl, 2,4-difluorophenyl, 2-thienyl, 2-pyridyl, 2-chloropyridine, and 5-bromopyridine.

7. R 1 7. The fused ring compound containing a sulfur substituent according to claim 6, wherein R is selected from a methyl group and R is selected from a cyclopropyl group or a trifluoromethyl group.

8. A process for preparing the fused ring compound (Ia) containing a sulfur substituent according to claim 6, comprising the steps of: 【Chemistry 4】 (Ia) Step (1) of stirring and refluxing the compound obtained by the reaction of the compound of formula (II) with the compound of formula (III) in acetic acid to obtain a compound of formula (IV); Step (2) of contacting a compound represented by formula (IV) with ethanethiol under alkaline conditions to obtain a compound represented by formula (V); Step (3) of reacting the compound of formula (V) with an oxidizing agent to obtain a compound of formula (VI); Step (4) of obtaining a compound represented by formula (VII) by Buchwald coupling reaction of the compound represented by formula (VI) with 2,4-dimethoxybenzylamine; Step (5) of reacting the compound of formula (VII) with trifluoroacetic acid to obtain a compound of formula (VIII); Step (6) of catalytically reacting the compound represented by formula (VIII) with a brominating reagent to obtain a compound represented by formula (IX); Step (7) of reacting the compound of formula (IX) with acyl chloride in the presence of an acid binder to obtain a compound of formula (X); Step (8) of reacting the compound of formula (X) with Lawesson's reagent to obtain a compound of formula (XI); and (9) reacting a compound of formula (XI) in the presence of a base to obtain the final target compound of formula (Ia). 【Chemistry 5】

9. A process for preparing the fused ring compound (Ib) containing a sulfur substituent according to claim 6, comprising the steps of: 【Chemistry 6】 (Ib) A method for preparing a compound of formula (X), comprising refluxing and stirring the compound of formula (X) in a solvent in the presence of CuI, a base and a catalyst to obtain a compound of formula (Ib). 【Chemistry 7】

10. A process for preparing the fused ring compound (Ic) containing a sulfur substituent according to claim 6, comprising the steps of: 【Chemistry 8】 (I C) Step (1) of refluxing and stirring a compound represented by formula (II) in acetic acid to obtain a compound represented by formula (III); Step (2) of reacting the compound of formula (III) with ethanethiol in the presence of a base to obtain a compound of formula (IV); Step (3) of oxidizing the compound of formula (IV) to obtain a compound of formula (V); Step (4) of contacting the compound of formula (V) with a substituted amine in a solvent to obtain a compound of formula (VI); Step (5) of dissolving the compound represented by formula (VI) in concentrated sulfuric acid, and then adding dilute nitric acid dropwise at low temperature to obtain the compound represented by formula (VII); Step (6) of reducing the compound of formula (VII) to obtain a compound of formula (VIII); Step (7) of reacting the compound of formula (VIII) with a substituted acid chloride to obtain a compound of formula (IX); and (8) refluxing and stirring the compound of formula (IX) in acetic acid to finally obtain the compound of formula (Ic). 【Chemistry 9】

11. A process for preparing a fused ring compound (Id) containing a sulfur substituent according to claim 6, comprising the steps of: 【Chemistry 10】 (Id) Step (1) of contacting the compound of formula (V) obtained in (Ic) with aqueous ammonia in a solvent to obtain a compound of formula (X); Step (2) of brominating the compound represented by formula (X) in a solvent in the presence of a base to obtain a compound represented by formula (XI); Step (3) of reacting a compound of formula (XI) with a substituted acid chloride to obtain a compound of formula (XII); Step (4) of reacting the compound of formula (XII) with Lawesson's reagent to obtain a compound of formula (XIII); and (5) a step of cyclizing the compound represented by formula (XIII) in the presence of a base to obtain compound (Id). 【Chemistry 11】

12. 1. Use of a fused ring compound containing a sulfur substituent of formula (I) in the manufacture of an insecticide.

13. 12. Use according to claim 11, characterized in that the insecticide is an insecticide for controlling lepidopteran and / or coleopteran insects.

14. 12. The use according to claim 11, wherein the pests targeted by the insecticide are one or more of the brown planthopper, the striate brown planthopper, the tobacco whitefly, the diamondback moth, the armyworm, the green peach aphid, and the false spider mite.

15. 7. An insecticide comprising the fused ring compound having a sulfur substituent according to claim 1 and an auxiliary agent, wherein the concentration of the fused ring compound having a sulfur substituent in the insecticide is 1 to 600 ppm.

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