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WO2024022362A1 - 具有含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途 - Google Patents

具有含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途 Download PDF

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WO2024022362A1
WO2024022362A1 PCT/CN2023/109212 CN2023109212W WO2024022362A1 WO 2024022362 A1 WO2024022362 A1 WO 2024022362A1 CN 2023109212 W CN2023109212 W CN 2023109212W WO 2024022362 A1 WO2024022362 A1 WO 2024022362A1
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formula
compound represented
substituted
compound
substituents
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English (en)
French (fr)
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张璞
赵文
王凤云
姚凯诚
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Jiangsu Flag Chemical Industry Co Ltd
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Jiangsu Flag Chemical Industry Co Ltd
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Priority to EP23845570.3A priority Critical patent/EP4563581A1/en
Priority to AU2023316544A priority patent/AU2023316544A1/en
Priority to US18/996,094 priority patent/US20250361231A1/en
Priority to JP2025504302A priority patent/JP2025526392A/ja
Priority to KR1020257003949A priority patent/KR20250047737A/ko
Publication of WO2024022362A1 publication Critical patent/WO2024022362A1/zh
Priority to ZA2025/00734A priority patent/ZA202500734B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/02—Acaricides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—Ortho-condensed systems

Definitions

  • the invention relates to the field of agricultural pesticides, and specifically relates to a fused ring compound containing a sulfur substituent, a preparation method, a pesticide composition and its use.
  • Fused bicyclic heterocyclic derivatives with insecticidal properties have been described in, for example, WO2014/119672A1, WO2015/002211A1, WO2017/026384A1, WO2018/015289A1, WO2016/091731A1.
  • certain active compounds known from the above-mentioned documents have disadvantages when used, whether they have only a narrow application range or they do not have satisfactory insecticidal or acaricidal activity.
  • New fused bicyclic heterocyclic derivatives have been discovered that have advantages over known compounds, such as better biological or environmental properties, more application methods, better insecticidal or acaricidal effects , as well as good compatibility with crop plants.
  • Fused bicyclic heterocyclic derivatives can be used in combination with other agents for improved efficacy, especially against difficult-to-control insects.
  • the present invention provides a fused heterocyclic compound containing a sulfur substituent, a fused bicyclic heterocyclic derivative involving a new structure, a preparation method thereof and intermediates used for its preparation. and their insecticidal action, their use as acaricides and/or insecticides for the control of animal pests, in particular arthropods and especially insects and arachnids.
  • the technical problem to be solved by the present invention is to provide a fused ring compound containing a sulfur substituent as shown in the general formula (I):
  • X is selected from N, NR 1 , O or S;
  • Y is selected from N or S
  • X is selected from NR 1 , O or S; when Y is selected from S, X is selected from N;
  • R 1 is selected from H, C 1 to 6 alkyl, C 1 to 6 haloalkyl, C 3 to 6 cycloalkyl, C 3 to 6 halocycloalkyl; in the formula, R is selected from C 1 to 6 alkyl group, C 1 to 6 substituted alkyl group, C 3 to 6 cycloalkyl group, C 3 to 6 substituted cycloalkyl group, C 2 to 6 epoxy group, C 2 to 6 alkenyl group, C 2 to 6 alkynyl group, benzene base, substituted phenyl, C 5 ⁇ 6 heterocycle or substituted heterocycle;
  • the substituents of the substituted alkyl or substituted cycloalkyl are selected from halogen, C 1 to 2 alkyl, C 1 to 2 alkoxy, C 1 to 2 haloalkoxy, C 1 to 2 haloalkyl, cyano or ester group;
  • the substituted phenyl group means that the phenyl group is substituted with 1, 2 or 3 substituents, and the substituents are selected from halogen, C 1-2 alkoxy group, C 1-2 haloalkoxy group, cyano group, C 1-6 Alkyl or C 1 ⁇ 6 haloalkyl;
  • the heterocyclic ring is selected from a five-membered or six-membered monocyclic ring with at least one non-carbon ring atom, including aromatic rings and non-aromatic hydrocarbons;
  • the substituted heterocycle refers to a heterocycle with 1, 2 or 3 substituents, and the substituents of the substituted heterocycle are selected from halogen, C 1 to 6 alkyl, C 1 to 6 haloalkyl, C 1 to 6 alkoxy group or C 1 to 6 alkyl amide group.
  • the R 1 is selected from H, C 1 to 6 alkyl, trifluoromethyl or cyclopropyl;
  • R is selected from C 1 to 6 alkyl, C 1 to 6 haloalkyl, C 3 to 6 cycloalkyl, C 2 to 6 alkenyl, C 2 to 6 alkynyl, phenyl, substituted phenyl, C 5 to 6 Heterocycle or substituted heterocycle;
  • the substituted phenyl group means that the phenyl group is substituted with 1, 2 or 3 substituents, and the substituents are selected from halogen, C 1-2 alkoxy group, C 1-2 haloalkoxy group, cyano group, C 1-2 Alkyl or C 1 ⁇ 2 haloalkyl;
  • the heterocycle is selected from a five-membered nitrogen-containing heterocycle, a five-membered sulfur-containing heterocycle, a five-membered oxygen-containing heterocycle, a six-membered nitrogen-containing heterocycle, a six-membered sulfur-containing heterocycle or a six-membered oxygen-containing heterocycle;
  • the substituent of the substituted heterocyclic ring is selected from halogen, C 1-2 alkyl group, C 1-2 haloalkyl group, C 1-2 alkoxy group or C 1-2 alkyl amido group.
  • R 1 is selected from C 1 to 4 alkyl
  • R is selected from C 1 to 6 alkyl, C 1 to 6 haloalkyl, C 3 to 6 cycloalkyl, C 2 to 6 alkenyl, C 2 to 6 alkynyl, phenyl, substituted phenyl, C 5 to 6 Heterocycle or substituted heterocycle;
  • the substituted phenyl group means that the phenyl group is substituted with 1, 2 or 3 substituents, and the substituents are selected from halogen, methoxy, cyano, ethoxy, methyl, ethyl or trifluoromethyl;
  • the heterocyclic ring is selected from piperazinyl, pyrrolidinyl, dioxanyl, morpholinyl, tetrahydrofuranyl, pyridyl, furyl, imidazolyl, pyrimidinyl, oxazolyl, isoxazolyl, tetrazolyl , triazolyl, thiadiazolyl and thienyl;
  • the substituted heterocycle refers to a heterocycle with 1, 2 or 3 substituents, and the substituents of the substituted heterocycle are selected from halogen, methyl, ethyl, methoxy, trifluoromethyl or difluoro methyl.
  • R 1 is selected from methyl
  • R is selected from C 1 to C 6 alkyl, C 1 to C 6 haloalkyl, C 3 to C 6 cycloalkyl, C 2 to C 6 alkenyl, C 2 to C 6 alkynyl, phenyl, substituted phenyl , C 5 ⁇ C 6 heterocycle or substituted heterocycle;
  • the substituted phenyl group means that the phenyl group is substituted with 1, 2 or 3 substituents, and the substituents are selected from halogen, methoxy, cyano, methyl or trifluoromethyl;
  • the heterocyclic ring is selected from 2-thienyl, pyridyl, 2-chloropyridyl or 5-bromopyridyl;
  • the substituted heterocycle means that the heterocycle is substituted with 1, 2 or 3 substituents, and the substituents of the substituted heterocycle are selected from halogen, methyl, methoxy or trifluoromethyl.
  • R is selected from methyl, trifluoromethyl, difluoromethyl, chloromethyl, 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-chloropyridyl or 5-bromopyridyl.
  • R 1 is selected from methyl; R is selected from cyclopropyl or trifluoromethyl.
  • R 1 is selected from methyl; R is selected from methyl, trifluoromethyl, difluoromethyl, cyclopropyl, heptafluoroisopropyl, ethyl, chloromethyl base, 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 base or 5-bromopyridyl.
  • R 1 is selected from methyl; R is selected from cyclopropyl or trifluoromethyl.
  • the 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, it includes the following steps:
  • the organic solvent in step (1) is selected from one or more types of acetic acid, benzene, and toluene, preferably acetic acid; the reaction temperature is 25 to 110°C, preferably 110°C; the organic solvent volume is The molar amount of the compound represented by formula (II) is 0.3 to 9 mL/mmol, preferably 0.4 mL/mmol.
  • the organic solvent used in step (2) is one or more of benzene, toluene, DMF or tetrahydrofuran, preferably tetrahydrofuran;
  • the base is one of sodium hydride, sodium hydroxide and potassium hydroxide.
  • One or more, preferably sodium hydride; the molar ratio of the reaction of the compound represented by formula (IV) with ethyl mercaptan 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 is 0.3 to 9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (IV).
  • the organic solvent used in step (3) is one or more of dichloromethane, dichloroethane, methanol, ethanol, DMF, and tetrahydrofuran, preferably dichloromethane;
  • the oxidizing agent is hydrogen peroxide, methylene chloride, or hydrogen peroxide.
  • chloroperoxybenzoic acid preferably hydrogen peroxide.
  • the reaction temperature is 25-40°C, preferably 25°C; the volume of the organic solvent is 0.3-9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (V).
  • the organic solvent used in step (4) is one or more of benzene, toluene, and 1,4-dioxane, with toluene being preferred.
  • the reaction temperature is 25-150°C, preferably 120°C; the volume of the organic solvent is 0.3-9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (VI).
  • the organic solvent used in step (5) is one or more of dichloromethane, dichloroethane, ethanol, methanol, acetonitrile, and tetrahydrofuran, preferably dichloromethane;
  • the reaction temperature is 25 to 80°C, preferably 25°C;
  • the molar ratio of the compound represented by formula (VII) to trifluoroacetic acid is 1:1 to 10, preferably 1:2;
  • the volumetric amount of the organic solvent is expressed by formula (VII)
  • the molar amount of the compound shown is 3 to 9 mL/mmol, preferably 5 mL/mmol.
  • the organic solvent in step (6) is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, 1,4-dioxane, and acetic acid, preferably acetic acid;
  • the chemical reagent is one or more of bromine and NBS, preferably bromine;
  • the reaction temperature is 25-80°C, preferably 80°C;
  • the volumetric amount of the organic solvent is based on the mole of the compound represented by formula (VIII) The amount is 3 to 9 mL/mmol, preferably 5 mL/mmol.
  • the organic solvent in step (7) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, preferably tetrahydrofuran;
  • the acid binding agent is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, DMAP or sodium hydride, preferably triethylamine;
  • the reaction temperature is 0 to 80 °C, preferably 25°C.
  • the volumetric amount of the organic solvent is 3 to 9 mL/mmol based on the molar amount of the compound represented by formula (IX), preferably 5 mL/mmol.
  • the organic solvent in step (8) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, preferably tetrahydrofuran;
  • the molar ratio of the compound represented by the formula (X) to Lawson's reagent is 1:1 ⁇ 5, preferably 1:1.5; the reaction temperature is 25 ⁇ 80°C, preferably 80°C;
  • the volumetric amount of the organic solvent is as follows:
  • the molar amount of the compound represented by (X) is 3 to 9 mL/mmol, preferably 5 mL/mmol.
  • the organic solvent in step (9) is selected from one of 1,4-dioxane, dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile.
  • the base is one or more of sodium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, preferably cesium carbonate;
  • the reaction temperature is 25-120°C, preferably 80°C; the volume of the organic solvent is 3-9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (XI).
  • the compound represented by formula (X) is stirred under reflux in a solvent in the presence of CuI, a base and a catalyst to prepare a compound represented by formula (Ib).
  • the catalyst in the above steps is 10-phenanthroline;
  • the base is one or more of sodium carbonate, potassium carbonate, and cesium carbonate, preferably cesium carbonate;
  • the solvent is tetrahydrofuran, dichloromethane, dichloromethane, One or more of ethane and ethylene glycol dimethyl ether, preferably ethylene glycol dimethyl ether;
  • the volume of the organic solvent is 3 to 9 mL/mmol based on the molar amount of the compound represented by formula (X), preferably 5mL/mmol.
  • the organic solvent in step (1) is selected from one or more types of acetic acid, benzene, and toluene, preferably acetic acid; the reaction temperature is 25 to 110°C, preferably 110°C; the organic solvent volume is The molar amount of the compound represented by formula (II) is 0.3 to 9 mL/mmol, preferably 0.4 mL/mmol.
  • the organic solvent used in step (2) is one or more of benzene, toluene, DMF or tetrahydrofuran, preferably tetrahydrofuran;
  • the base is one of sodium hydride, sodium hydroxide and potassium hydroxide.
  • the reaction temperature is -10 to 80°C, preferably 0°C;
  • the volume of the organic solvent is 0.3 to 9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (IV).
  • the organic solvent used in step (3) is one or more of dichloromethane, dichloroethane, methanol, ethanol, DMF, and tetrahydrofuran, preferably dichloromethane;
  • the oxidizing agent is hydrogen peroxide, methylene chloride, or hydrogen peroxide.
  • chloroperoxybenzoic acid preferably hydrogen peroxide.
  • the reaction temperature is 25-40°C, preferably 25°C; the volume of the organic solvent is 0.3-9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (V).
  • the solvent used in step (4) is one or more of methanol, ethanol, DMF or tetrahydrofuran, preferably tetrahydrofuran; the reaction temperature is 25-120°C, preferably 100°C.
  • the reaction temperature in step (5) is -10 to 25°C, preferably 0°C.
  • the reducing agent in step (6) is iron powder or palladium carbon, preferably palladium carbon.
  • the organic solvent in step (7) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, preferably tetrahydrofuran; as shown
  • the acid agent is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, DMAP or sodium hydride, preferably triethylamine; the reaction temperature is 0 to 80°C. 25°C is preferred.
  • the volumetric amount of the organic solvent is 3 to 9 mL/mmol based on the molar amount of the compound represented by formula (VIII), preferably 5 mL/mmol;
  • the reaction temperature in step (8) is 90-150°C, preferably 110°C.
  • the solvent used in step (1) is one or more of methanol, ethanol, DMF or tetrahydrofuran, preferably tetrahydrofuran; the reaction temperature is 25-120°C, preferably 100°C.
  • the organic solvent in step (2) is one or more of dichloromethane, dichloroethane, tetrahydrofuran, toluene, 1,4-dioxane, and acetic acid, preferably acetic acid;
  • the chemical reagent is one or more of bromine and NBS, preferably bromine;
  • the base is sodium acetate or potassium acetate, preferably potassium acetate;
  • the reaction temperature is 25 to 80°C, preferably 80°C;
  • the organic The volume of the solvent is 3 to 9 mL/mmol based on the molar amount of the compound represented by formula (VIII), preferably 5 mL/mmol.
  • the organic solvent in step (3) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, preferably tetrahydrofuran; as shown
  • the acid agent is one or more of triethylamine, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, pyridine, DMAP or sodium hydride, preferably triethylamine; the reaction temperature is 0 to 80°C. 25°C is preferred.
  • the volumetric amount of the organic solvent is 3 to 9 mL/mmol based on the molar amount of the compound represented by formula (XI), preferably 5 mL/mmol.
  • the organic solvent in step (4) is selected from one or more of dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, preferably tetrahydrofuran; the formula
  • the molar ratio of the compound shown in (XII) to Lawson's reagent is 1:1 to 5, preferably 1:1.5; the reaction temperature is 25 to 80°C, preferably 80°C; the volumetric amount of the organic solvent is calculated by the formula (XII
  • the molar amount of the compound represented by ) is 3 to 9 mL/mmol, preferably 5 mL/mmol.
  • the organic solvent in step (5) is selected from one of 1,4-dioxane, dichloromethane, dichloroethane, tetrahydrofuran, N,N-dimethylformamide or acetonitrile, or A variety of, preferably 1,4-dioxane;
  • the base is one or more of sodium hydride, sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, preferably cesium carbonate;
  • the reaction temperature is 25-120°C, preferably 80°C;
  • the volume of the organic solvent is 3-9 mL/mmol, preferably 5 mL/mmol based on the molar amount of the compound represented by formula (XIII).
  • the third aspect of the present invention provides the use of a fused ring compound containing a sulfur substituent represented by formula (I) in the preparation of pesticides.
  • the insecticide is an insecticide for controlling Lepidoptera and/or Coleoptera; further, the insect pests can be brown planthopper, Bose planthopper, Bemisia tabaci, diamondback moth, armyworm, green peach aphid, cinnabar One or more species of spider mites.
  • the fourth aspect of the present invention provides a pesticide.
  • the pesticide includes a fused ring compound containing a sulfur substituent and an auxiliary agent.
  • the concentration of the fused ring compound containing a sulfur substituent in the pesticide is is 1 to 600 ppm; further, the concentration of the fused ring compound containing sulfur substituents in the pesticide is 4 to 100 ppm.
  • the beneficial effect of the present invention is that the fused ring compound containing sulfur substituents provided by the present invention has good control effects on a variety of pests at lower test concentrations, and provides information for the research and development of new pesticides. foundation.
  • Step E Synthesis of 3,6-dichloro-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)pyridinamide
  • the reaction mixture was then diluted with saturated NH 4 Cl, the organic phase was separated, and the aqueous phase was back-extracted with dichloromethane.
  • the combined organic phases were washed with water, brine, dried over Na2SO4 , filtered and concentrated in vacuo to give crude product.
  • the crude product was purified by column chromatography.
  • Step F Synthesis of 2-(3,6-dichloropyridin-2-yl)-3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridine
  • the product obtained in the previous step (8.556g, 23mmol) was added with formic acid (5.29g, 115mmol) and hydrogen peroxide at room temperature. (3.0 g, 161 mmol) and the mixture was stirred at room temperature for 5 hours. After the reaction is completed, dilute with water, add sodium bisulfite solution and stir for one hour, then add saturated sodium bicarbonate solution. 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 obtain 6.6 g of white solid, with a yield of 74.5%.
  • Step I 5-(ethylsulfonyl)-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyridin-2-amine
  • Step J 5-(ethylsulfonyl)-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyridine-2-methyl amine
  • step H Dissolve the compound obtained in step H in methanol, then add 3 times the methylamine alcohol solution, put it in a pressure-resistant bottle, and react overnight at 120 degrees. After the reaction was monitored by LC-MS, the reaction solution was cooled to room temperature. At this time, solids precipitate, filter out the solids, and dry to obtain the product.
  • Step K 5-(ethylsulfonyl)-N-methyl-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl) -Synthesis of 3nitro-2-amine
  • step J Dissolve the compound obtained in step J in concentrated sulfuric acid, and then add an equal amount of nitric acid dropwise in an ice bath. After the addition is completed, stir at room temperature for several hours. After the reaction was monitored by LC-MS, the reaction solution was poured into ice water and a yellow solid precipitated. The solid was filtered out, dried, and used directly in the next reaction without purification.
  • Step L 5-(ethylsulfonyl)-N-methyl-6-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl) Synthesis of pyridine-2,3-diamine
  • step K Dissolve the crude product obtained in step K in THF, then add 5% palladium carbon catalyst by raw material mass thereto, replace the air in the bottle with hydrogen three times, and then stir the reaction at 30 degrees overnight. After LC-MS monitoring shows that the reaction is completed, the reaction solution is filtered, the filtrate is spun dry, and the crude product obtained can be purified by column chromatography.
  • step L The compound obtained in step L (1 mmol) was dissolved in THF, then cyclopropanecarboxylic acid chloride (1 mmol) was added thereto, and then triethylamine (1.5 mmol) was added. Stir at room temperature. After the reaction is completed, the reaction solution is directly spun to dryness, then dissolved in acetic acid, and refluxed at 120°C for several hours. After the reaction was detected by LC-MS, water was added to the reaction solution, extracted with ethyl acetate, and the organic phase was dried and purified by column chromatography to obtain 109 mg of the title compound. The two-step yield was 20%, m.p. 201-204°C.
  • step M in Preparation Example 1 compound I-2 of the present invention represented by the following formula was prepared by replacing cyclopropanecarbonyl chloride with acetyl chloride.
  • intermediate compound 1 represented by the following formula can be obtained by replacing 3,6-dichloropyridine-2-carboxyl chloride with 3-chloro-5-bromopyridine-2-carboxylic acid chloride. .
  • Intermediate compound 5 (3.31 mmol) was dissolved in dichloromethane (20 mL) at ambient temperature and trifluoroacetic acid (3.31 mmol) was added. The orange-red solution was stirred at ambient temperature for 5 h. Volatiles were removed under reduced pressure. The residue was basified with saturated NaHCO solution and extracted with ethyl acetate. The organic phase is separated, dried and concentrated. The residue was purified on 40 g of silica gel with ethyl acetate as eluent to give intermediate compound 6 represented by the following formula.
  • Intermediate compound 6 (1 mmol) was dissolved in 10 mL acetic acid, then sodium acetate (1 mmol) was added, and a 5 mL acetic acid solution of bromine (1.2 mmol) was added dropwise at room temperature. Then place the reaction solution at the current temperature and continue stirring. After the reaction is completed, the reaction solution is quenched with an 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 represented by the following formula.
  • This test example is used to illustrate the insecticidal activity inhibition (%) of the compound with the structure represented by formula (I) (dose is 100 ppm).
  • Test Example 1 Activity against peach aphid (green peach aphid):
  • the roots of pea seedlings infested with a mixed-age aphid colony were placed directly into an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. The samples were evaluated for mortality after placing the seedlings in the test solution for 6 days.
  • Test Example 2 Activity against Diamondback Moth (Plutella xylostella):
  • 24-well microtiter plates with artificial feed were treated by pipetting with aqueous test solutions prepared from 10’000 ppm DMSO stock solution. After drying, each plate was infested with L2 stage larvae (10 to 15/well). After 5 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
  • Test Example 3 Activity against Armyworm:
  • the agar layer in a 24-well microtiter plate was treated by spraying with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, each plate was infested with L2 stage larvae (6 to 10/well). Four days after infection, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
  • Test Example 4 Activity against brown planthopper:
  • Cotton leaf disks were placed on agar in a 24-well microtiter plate and sprayed with an aqueous test solution prepared from a 10,000 ppm DMSO stock solution. After drying, the leaf disks were infested with adult brown planthoppers. After 6 days of incubation, the samples were evaluated for mortality.
  • Test Example 5 Activity against Spodoptera exigua:
  • 24-well microtiter plates with artificial feed were treated by pipetting with aqueous test solutions prepared from 10’000 ppm DMSO stock solution. After drying, each plate was infested with L2 stage larvae (10 to 15/well). After 5 days of infestation, these samples were evaluated for mortality and growth inhibition compared to untreated samples.
  • Test Example 6 Activity against alfalfa sprouts:
  • the roots of pea seedlings infested with a mixed-age aphid colony were placed directly into an aqueous test solution prepared from a 10'000 ppm DMSO stock solution. The samples were evaluated for mortality after placing the seedlings in the test solution for 6 days.

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Abstract

本发明属于农用杀虫剂领域，具体涉及一种含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途。与现有技术相比，本发明的有益效果在于：本发明提供的含硫取代基的稠环化合物在较低的测试浓度下对多种害虫均有良好的防治效果，为新农药的研发提供了基础。

Description

具有含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途 技术领域
本发明涉及属于农用杀虫剂领域，具体涉及一种含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途。
背景技术
具有杀虫特性的稠合双环杂环衍生物已记载于以下文献中：例如，WO2014/119672A1、WO2015/002211A1、WO2017/026384A1、WO2018/015289A1、WO2016/091731A1。然而，由上述文献已知的某些活性化合物在使用时具有缺点，不论是它们仅具有窄的施用范围，还是它们不具有令人满意的杀虫活性或杀螨活性。
现已发现新的稠合双环杂环衍生物，它们具有优于已知化合物的优点，例如更好的生物学特性或环境特性、更多的施用方法、更好的杀虫作用或杀螨作用，以及与作物植物良好的相容性。稠合双环杂环衍生物可以与用于改进功效的其他试剂结合使用，特别是对抗难以防治的昆虫。
本发明则提供了一种含硫取代基的稠杂环化合物、涉及新结构的稠合双环杂环衍生物；以及其制备方法和用于其制备的中间体。及其在杀虫方面的作用，其作为杀螨剂和/或杀虫剂用于防治动物害虫、特别是节肢动物且尤其是昆虫和蛛形纲动物的用途。
发明内容
本发明要解决的技术问题是：提供一种本发明的第一目的在于提供一类如通式(Ⅰ)所示的含硫取代基的稠环类化合物：
式中
X选自N、NR1、O或S；
Y选自N或S；
其中当Y选自N时，X选自NR1、O或S；当Y选自S时，X选自N；
式中R1选自H、C1～6烷基、C1～6卤代烷基、C3～6环烷基、C3～6卤代环烷基；式中R选自C1～6烷基、C1～6取代烷基、C3～6环烷基、C3～6取代环烷基、C2～6环氧基、C2～6烯基、C2～6炔基、苯基、取代苯基、C5～6杂环或取代杂环；
所述取代烷基或取代环烷基的取代基选自卤素、C1～2烷基、C1～2烷氧基、C1～2卤代烷氧基、C1～2卤代烷基、氰基或酯基；
所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、C1～2烷氧基、C1～2卤代烷氧基、氰基、C1～6烷基或C1～6卤代烷基；
所述杂环选自至少一个非碳环原子的五元或六元单环，包括芳香环和非芳烃；
所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、C1～6烷基、C1～6卤代烷基、C1～6烷氧基或C1～6烷基酰胺基。
优选的，所述R1选自H、C1～6烷基、三氟甲基或环丙基；
R选自C1～6烷基、C1～6卤代烷基、C3～6环烷基、C2～6烯基、C2～6炔基、苯基、取代苯基、C5～6杂环或取代杂环；
所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、C1～2烷氧基、C1～2卤代烷氧基、氰基、C1～2烷基或C1～2卤代烷基；
所述杂环选自五元含氮杂环、五元含硫杂环、五元含氧杂环，六元含氮杂环、六元含硫杂环或六元含氧杂环；
所述取代杂环的取代基选自卤素、C1～2烷基、C1～2卤代烷基、C1～2烷氧基或C1～2烷基酰胺基。
更加优选的，R1选自C1～4烷基；
R选自C1～6烷基、C1～6卤代烷基、C3～6环烷基、C2～6烯基、C2～6炔基、苯基、取代苯基、C5～6杂环或取代杂环；
所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、甲氧基、氰基、乙氧基、甲基、乙基或三氟甲基；
所述杂环选自哌嗪基、吡咯烷基、二噁烷基、吗啉基、四氢呋喃基、吡啶基、呋喃基、咪唑基、嘧啶基、恶唑基、异恶唑基、四唑基、三唑基、噻二唑基和噻吩基；
所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、甲基、乙基、甲氧基、三氟甲基或二氟甲基。
进一步优选的，R1选自甲基；
R选自C1～C6烷基、C1～C6卤代烷基、C3～C6环烷基、C2～C6烯基、C2～C6炔基、苯基、取代苯基、C5～C6杂环或取代杂环；
所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、甲氧基、氰基、甲基或三氟甲基；
所述杂环选自2-噻吩基、吡啶基、2-氯吡啶基或5-溴吡啶基；
所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、甲基、甲氧基或三氟甲基。
更进一步优选的，R选自甲基、三氟甲基、二氟甲基、氯甲基、环丙基、七氟异丙基、乙基、氯甲基、异丙基、正丙基、异丁基、叔丁基、环丁基、环戊基、环己基、乙烯基、乙炔基、丙烯基、丁烯基、丙炔基、丁炔基、苯基、氰基环丙基、4-氟苯基、2-氟苯基、3-氟苯基、2,4-二氟苯基、2-噻吩基、2-吡啶基、2-氯吡啶基或5-溴吡啶基。
更进一步优选的，R1选自甲基；R选自环丙基或三氟甲基。
在本发明的优选实施方式中，提供了具有化学式(I-a)、(I-b)、(I-c)和(I-d)的化合物：
R1选自甲基；R选自甲基、三氟甲基、二氟甲基、环丙基、七氟异丙基、乙基、氯甲 基、异丙基、正丙基、异丁基、叔丁基、环丁基、环戊基、环己基、乙烯基、乙炔基、丙烯基、丁烯基、丙炔基、丁炔基、苯基、氰基环丙基、4-氟苯基、2-氟苯基、3-氟苯基、2,4-二氟苯基、2-噻吩基、2-吡啶基、2-氯吡啶基或5-溴吡啶基。
更进一步优选的，R1选自甲基；R选自环丙基或三氟甲基。
作为本发明优选的具体化合物结构，其取代基如表1所示(基于通式Ⅰ)：
表1


以及表1的化合物的N-氧化物或互变异构体。“Ph”表示苯基基团，“Py”表示吡啶基团。
本发明的第二目的在于提供一种含硫取代基的稠环类化合物的制备方法，以(I-a)所示结构为例，包括如下步骤：
(1)将式(II)与式(III)反应所得到的化合物在醋酸中搅拌回流得到式(IV)化合物；式(II)化合物的制备是熟知的并且已经描述于例如WO 2014/119672A和WO2015/002211A中；式(III)化合物可通过商购的3-氯-5-溴吡啶-2-甲酸来制备；
(2)将式(IV)所示化合物与乙硫醇在碱性条件下接触制得式(V)所示化合物；
(3)将式(V)所示化合物与氧化剂反应制得式(VI)所示化合物；
(4)将式(VI)所示化合物与2,4-二甲氧基苄胺通过Buchwald偶联反应制得式(VII)所示化合物；
(5)将式(VII)所示化合物与三氟乙酸反应制得式(VIII)所示化合物；
(6)将式(VIII)所示化合物与溴化试剂接触反应制得式(IX)所示化合物；
(7)将式(IX)所示化合物与酰氯在缚酸剂存在下反应制得式(X)所示的化合物；
(8)将(X)所示化合物与劳森试剂反应制得式(XI)所示化合物；
(9)将式(XI)所示化合物在碱存在下反应制得式(I-a)所示的最终目标化合物；其中R和R1如前文所描述的，但不限制本发明；
优选的，所述步骤(1)中有机溶剂选自醋酸、苯、甲苯中的一种或种，优选醋酸；所述反应温度为25～110℃，优选110℃；所述有机溶剂体积用量以式(II)所示化合物的摩尔量计为0.3～9mL/mmol，优选0.4mL/mmol。
优选的，所述步骤(2)中所用的有机溶剂为苯、甲苯、DMF或四氢呋喃中的一种或多种，优选四氢呋喃；所述碱为氢化钠、氢氧化钠、氢氧化钾中的一种或多种，优选氢化钠；所述式(IV)所示化合物与乙硫醇、氢化钠反应的摩尔量之比为1：1～2:1～2，优选1:1：1.2；所述反应温度为-10～80℃，优选0℃；所述有机溶剂体积用量以式(IV)所示化合物的摩尔量计为0.3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(3)中所用有机溶剂为二氯甲烷、二氯乙烷、甲醇、乙醇、DMF、四氢呋喃中的一种或多种，优选二氯甲烷；所述氧化剂为双氧水、间氯过氧苯甲酸中的一种或多种，优选双氧水。所述反应温度为25～40℃，优选25℃；所述有机溶剂体积用量以式(V)所示化合物的摩尔量计为0.3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(4)中所用有机溶剂为苯、甲苯、1,4二氧六环中的一种或多种，优选甲苯。所述反应温度为25～150℃，优选120℃；所述有机溶剂体积用量以式(VI)所示化合物的摩尔量计为0.3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(5)中所用有机溶剂为二氯甲烷、二氯乙烷、乙醇、甲醇、乙腈、四氢呋喃中的一种或多种，优选二氯甲烷；所述反应温度为25～80℃，优选25℃；所述式(VII)所示化合物与三氟乙酸的摩尔量之比为1:1～10，优选1:2；所述有机溶剂的体积用量以式(VII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(6)中有机溶剂为二氯甲烷、二氯乙烷、四氢呋喃、甲苯、1,4-二氧六环、醋酸中的一种或多种，优选醋酸；所述溴化试剂为溴素、NBS中的一种或多种，优选溴素；所述反应温度为25～80℃，优选80℃；所述有机溶剂的体积用量以式(VIII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(7)中所述有机溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选四氢呋喃；所示缚酸剂为三乙胺、碳酸钾、碳酸钠、氢氧化钾、氢氧化钠、吡啶、DMAP或氢化钠中的一种或多种，优选三乙胺；所述反应温度为0～80℃，优选25℃。所述有机溶剂的体积用量以式(IX)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(8)中所述有机溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选四氢呋喃；所述式(X)所示化合物与劳森试剂的摩尔量之比为1:1～5，优选1:1.5；所述反应温度为25～80℃，优选80℃；有机溶剂的体积用量以式(X)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(9)中所述有机溶剂选自1,4-二氧六环、二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选1,4-二氧六环；所述碱为氢化钠、碳酸钠、碳酸钾、碳酸铯、氢氧化钠、氢氧化钾中的一种或多种，优选碳酸铯；所述反应温度为25～120℃，优选80℃；所述有机溶剂的体积用量以式(XI)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
类似的制备(I-b)所示结构包括如下步骤：
将式(X)所示化合物在CuI、碱和催化剂存在下于溶剂中回流搅拌制得式(I-b)所示化合物。
优选的，上述步骤中所述催化剂为10-phenanthroline；所述碱为碳酸钠、碳酸钾、碳酸铯中的一种或多种，优选碳酸铯；所述溶剂为四氢呋喃、二氯甲烷、二氯乙烷、乙二醇二甲醚中的一种或多种，优选乙二醇二甲醚；有机溶剂的体积用量以式(X)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
类似的制备(I-c)所示结构包括如下步骤：
(1)同制备(I-a)中式(IV)方法相同，将式(II)所示化合物在醋酸中回流搅拌得到式(III)所示化合物；
(2)将式(III)所示化合物在碱存在下与乙硫醇反应制得式(IV)所示化合物；
(3)式(IV)所示化合物通过氧化制得式(V)所示化合物；
(4)将式(V)所示化合物在溶剂中与取代胺接触制得式(VI)所示化合物；
(5)将式(VI)所示化合物溶于浓硫酸中，然后在低温下滴加稀硝酸制得式(VII)所示化合物；
(6)式(VII)所示化合物通过还原制得式(VIII)所示化合物；
(7)式(IX)的制备同(I-a)中式(X)的制备方法相同；
(8)将式(IX)所示化合物在醋酸中回流搅拌最终制得式(I-c)所示化合物。
优选的，所述步骤(1)中有机溶剂选自醋酸、苯、甲苯中的一种或种，优选醋酸；所述反应温度为25～110℃，优选110℃；所述有机溶剂体积用量以式(II)所示化合物的摩尔量计为0.3～9mL/mmol，优选0.4mL/mmol。
优选的，所述步骤(2)中所用的有机溶剂为苯、甲苯、DMF或四氢呋喃中的一种或多种，优选四氢呋喃；所述碱为氢化钠、氢氧化钠、氢氧化钾中的一种或多种，优选氢化钠；所述式(IV)所示化合物与乙硫醇、氢化钠反应的摩尔量之比为1：1～2:1～2，优选1:2:2；所述反应温度为-10～80℃，优选0℃；所述有机溶剂体积用量以式(IV)所示化合物的摩尔量计为0.3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(3)中所用有机溶剂为二氯甲烷、二氯乙烷、甲醇、乙醇、DMF、四氢呋喃中的一种或多种，优选二氯甲烷；所述氧化剂为双氧水、间氯过氧苯甲酸中的一种或多种，优选双氧水。所述反应温度为25～40℃，优选25℃；所述有机溶剂体积用量以式(V)所示化合物的摩尔量计为0.3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(4)中所用溶剂为甲醇、乙醇、DMF或四氢呋喃中的一种或多种，优选四氢呋喃；反应温度为25～120℃，优选100℃。
优选的，所述步骤(5)中反应温度为-10～25℃，优选0℃。
优选的，所述步骤(6)中还原剂为铁粉或钯碳，优选钯碳。
优选的，所述步骤(7)中有机溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选四氢呋喃；所示缚酸剂为三乙胺、碳酸钾、碳酸钠、氢氧化钾、氢氧化钠、吡啶、DMAP或氢化钠中的一种或多种，优选三乙胺；所述反应温度为0～80℃，优选25℃。所述有机溶剂的体积用量以式(VIII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol；
优选的，所述步骤(8)中反应温度为90～150℃，优选110℃。
类似的制备(I-d)所示结构包括如下步骤：
(1)将(I-c)中所制得的式(V)化合物在溶剂中与氨水接触制得式(X)所示化合物；
(2)将式(X)所示化合物在溶剂中在碱存在下溴化反应制得式(XI)所示化合物；
(3)式(XII)的制备与(I-c)中式(IX)的制备方法相同；
(4)式(XIII)的制备与(I-a)中式(XI)的制备方法相同；
(5)式(I-d)的制备与式(I-a)的制备方法相同。
优选的，所述步骤(1)中所用溶剂为甲醇、乙醇、DMF或四氢呋喃中的一种或多种，优选四氢呋喃；反应温度为25～120℃，优选100℃。
优选的，所述步骤(2)中有机溶剂为二氯甲烷、二氯乙烷、四氢呋喃、甲苯、1,4-二氧六环、醋酸中的一种或多种，优选醋酸；所述溴化试剂为溴素、NBS中的一种或多种，优选溴素；所述碱为醋酸钠或醋酸钾，优选醋酸钾；所述反应温度为25～80℃，优选80℃；所述有机溶剂的体积用量以式(VIII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(3)中有机溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选四氢呋喃；所示缚酸剂为三乙胺、碳酸钾、碳酸钠、氢氧化钾、氢氧化钠、吡啶、DMAP或氢化钠中的一种或多种，优选三乙胺；所述反应温度为0～80℃，优选25℃。所述有机溶剂的体积用量以式(XI)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(4)中有机溶剂选自二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选四氢呋喃；所述式(XII)所示化合物与劳森试剂的摩尔量之比为1:1～5，优选1:1.5；所述反应温度为25～80℃，优选80℃；有机溶剂的体积用量以式(XII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
优选的，所述步骤(5)中有机溶剂选自1,4-二氧六环、二氯甲烷、二氯乙烷、四氢呋喃、N,N-二甲基甲酰胺或乙腈中的一种或多种，优选1,4-二氧六环；所述碱为氢化钠、碳酸钠、碳酸钾、碳酸铯、氢氧化钠、氢氧化钾中的一种或多种，优选碳酸铯；所述反应温度为25～120℃，优选80℃；所述有机溶剂的体积用量以式(XIII)所示化合物的摩尔量计为3～9mL/mmol，优选5mL/mmol。
本发明的第三方面提供了一种如式(Ⅰ)所示的含硫取代基的稠环类化合物在制备杀虫剂中的应用。
优选的，所述杀虫剂为防治鳞翅目和/或鞘翅目的杀虫剂；进一步的，所述害虫可以为褐飞虱、灰飞虱、烟粉虱、小菜蛾、粘虫、桃蚜、朱砂叶螨中的一种或多种。
本发明的第四方面提供了一种杀虫剂，所述杀虫剂包括含硫取代基的稠环类化合物和助剂，所述含硫取代基的稠环化合物在杀虫剂中的浓度为1～600ppm；进一步的，所述含硫取代基的稠环化合物在杀虫剂中的浓度为4～100ppm。
本发明中化合物的中文命名与结构式有冲突的，以结构式为准。
与现有技术相比，本发明的有益效果在于：本发明提供的含硫取代基的稠环化合物在较低的测试浓度下对多种害虫均有良好的防治效果，为新农药的研发提供了基础。
具体实施方式
以下结合实例说明本发明，但不限制本发明。在本领域内，技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案内。
制备例1：
目标化合物I-1的合成
步骤A：2-甲氨基-5-三氟甲基吡啶的合成
将2-氯-5-三氟甲基吡啶(90.5g，0.5mol)溶于乙腈(50mL)，向其中添加甲胺醇溶液(46.5g，1.5mol)。将上述混合溶液于350mL耐压瓶中在100度条件下搅拌过夜。用TLC和LC-MS监测其反应终点。然后将反应混合物在真空中浓缩，以给出白色晶体，即为2-甲氨基-5-三氟甲基吡啶，收率95％。
步骤B：2-甲氨基-3-硝基-5-三氟甲基吡啶的合成
将2-甲氨基-3-硝基-5-三氟甲基吡啶(52.8g，0.3mol)溶于浓硫酸(100mL)，在冰浴条件下向其中滴加硝酸(18.9g，0.3mol)。30分钟内滴加完毕后撤去冰浴，将反应液加热到80度反应3小时。用LC和GC-MS监测其反应终点。然后将反应液缓慢地倒入冰水中以析出固体，过滤水洗，烘干滤饼以给出黄色固体的标题化合物47.7g，收率72％。
步骤C：2-甲氨基-3-氨基-3-三氟甲基吡啶的合成
将2-甲氨基-3-硝基-5-三氟甲基吡啶(11.05g，50mmol)溶于四氢呋喃(100mL)，向其中加入5％的Pd/C，再向其中通入氢气，室温下搅拌24小时。TLC和GC-MS监测反应终点。然后将反应液过滤除去钯碳，滤液在真空中浓缩，以给出红棕色晶体的标题化合物，10.9g，收率99％。
步骤D：3,6-二氯吡啶-2-甲酰氯的合成
将3,6-二氯吡啶-2-甲酸(5.00g，24.7mmol)的样品在二氯甲烷(200mL)中稀释，并添加二甲基甲酰胺(0.124mL，1.6mmol)。在室温下，在10分钟内(气体逸出)向该溶液中滴加草酰氯 (3.15mL，34.6mmol)。将该反应混合物在室温下搅拌，并且2.5小时后添加另外的1mL草酰氯并继续搅拌1小时。在这时之后，将反应混合物在真空中浓缩并不经进一步纯化而用于下一步骤。
步骤E：3,6-二氯-N-(2-(甲氨基)-5-(三氟甲基)吡啶-3-基)吡啶酰胺的合成
向2-甲氨基-3-氨基-3-三氟甲基吡啶(16.70g，87.37mmol)在THF(167.0mL)中的溶液中添加Et 3N(22.32g，218.4mmol)。将反应混合物冷却至0℃，并且在0-10℃下，经1小时将溶解于二氯甲烷(170mL)中的3,6-二氯吡啶-2-甲酰氯(18.37g，87.37mmol)滴加到混合物中。1.5小时后，LC-MS检测到所希望的产物。去除冰浴，并且允许将反应混合物加温至环境温度并搅拌12小时。然后将反应混合物用饱和NH4Cl稀释,将有机相分离，并且将水相用二氯甲烷反萃取。将合并的有机相用水、盐水洗涤,经Na2SO4干燥，过滤并在真空中浓缩，以给出粗产物。将粗产物进行柱层析纯化。
步骤F：2-(3,6-二氯吡啶-2-基)-3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶的合成
将3,6-二氯-N-(2-(甲氨基)-5-(三氟甲基)吡啶-3-基)吡啶酰胺(15.6g，42.75mmol)在乙酸(50mL)中的黄色溶液在110℃浴温下搅拌过夜。之后LC-MS分析显示反应完毕。然后将反应液倒入冰水中，EA萃取(20mL*3),合并有机相，有机相再用饱和碳酸氢钠溶液洗(20mL*3)，经Na2SO4干燥,柱层析纯化得白色固体8g。粗收率54％。
步骤G：2-(6-氯-3-(乙硫基)吡啶-2-基)-3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶的合成
将2-(3,6-二氯吡啶-2-基)-3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶(1.14g，3.28mmol)溶解于四氢呋喃中。在室温下分批添加入NaH(3.28mmol)，搅拌30分钟后滴加乙硫醇(0.2g,3.28mmol),室温搅拌，直至反应完毕。将反应混合物用NH4Cl处理，然后用乙酸乙酯萃取。将有机层分离，用水和盐水洗涤，经Na2SO4干燥，将粗品通过硅胶快速色谱法进行纯化，以得到呈米黄色固体的标题化合物。收率80％。
步骤H：2-(6-氯-3-(乙磺酰基)吡啶-2-基)-3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶的合成
将上步所得产物(8.556g,23mmol)，在室温下加入甲酸(5.29g，115mmol)和双氧水 (3.0g，161mmol)，然后混合物在室温下搅拌5小时。反应完毕后用水稀释，加入亚硫酸氢钠溶液搅拌一小时，再加入饱和碳酸氢钠溶液。分离出有机相，水相用二氯甲烷萃取两次，合并有机相，无水硫酸钠干燥，经柱层析纯化得到白色固体6.6g，收率74.5％。
步骤I：5-(乙磺酰基)-6-(3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶-2-基)吡啶-2-胺
将2-(6-氯-3-(乙磺酰基)吡啶-2-基)-3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶(0.4g，1mmol)，溶于乙醇。将上述溶液加入到耐压瓶中，在加入3当量的氨水，于120度反应过夜。LC-MS显示反应完全。将溶液冷却至室温，有固体析出，过滤用少量甲醇洗涤。烘干得黄色固体。收率90％。
步骤J：5-(乙磺酰基)-6-(3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶-2-基)吡啶-2-甲胺
将步骤H中所得化合物溶于甲醇，再加入3倍的甲胺醇溶液，于耐压瓶中，在120度下反应过夜。LC-MS监测反应完毕后将反应液冷却到室温。此时析出固体，过滤出固体，烘干即得产品。
1H NMR(400MHz,Chloroform-d)δ8.73(d,J＝1.9Hz,1H),8.28(d,J＝2.0Hz,1H),8.10(d,J＝9.0Hz,1H),6.60(d,J＝8.9Hz,1H),5.30(s,1H),3.86(s,3H),3.60(q,J＝7.4Hz,2H),3.03(d,J＝5.1Hz,3H),1.31(t,J＝7.4Hz,3H).
步骤K：5-(乙磺酰基)-N-甲基-6-(3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶-2-基)-3硝基-2-胺的合成
将步骤J所得化合物溶于浓硫酸，然后冰浴下滴加等当量的硝酸。滴加完毕后在室温下搅拌数小时。LC-MS监测反应完毕后，将反应液倒入冰水中，析出黄色固体，将固体滤出，烘干，不经纯化直接用于下一步反应。
步骤L：5-(乙磺酰基)-N-甲基-6-(3-甲基-6-(三氟甲基)-3H-咪唑并[4,5-b]吡啶-2-基)吡啶-2,3-二胺的合成
将步骤K所得到的粗产品溶于THF，然后向其中加入原料质量5％的钯碳催化剂，再用氢气置换瓶内空气3次，然后再30度下搅拌反应过夜。LC-MS监测显示反应完毕后，过滤反应液，滤液旋干，所得粗产品可经柱层析纯化。
步骤M：目标化合物I-1的合成
将步骤L所得化合物(1mmol)溶于THF中，然后向其中加入环丙甲酰氯(1mmol)，再加入三乙胺(1.5mmol)。于室温搅拌。反应完毕后将反应液直接旋干然后溶于醋酸，于120℃回流反应数小时。LC-MS检测反应完毕后，向反应液中加入水，用乙酸乙酯萃取，然后有机相干燥后经柱层析纯化得标题化合物109mg，两步收率20％，m.p.201-204℃。
1H NMR(400MHz,CDCl3)δ8.79–8.74(m,1H),8.65(s,1H),8.31(d,J＝2.0Hz,1H),3.99(s,3H),3.83(s,3H),3.68(q,J＝7.4Hz,2H),2.14(tt,J＝8.1,4.8Hz,1H),1.42(dt,J＝4.8,3.2Hz,2H),1.35–1.28(m,5H).EI-MS:465[M+H]+
制备例2：
根据制备例1中步骤M所描述的方法，替换环丙甲酰氯为乙酰氯制得由下式表示的本发明化合物I-2。
本发明化合物I-2
1H NMR(400MHz,CDCl3)δ8.79–8.73(m,2H),8.33(d,J＝2.0Hz,1H),3.89(s,3H),3.82(s,3H),3.68(q,J＝7.5Hz,2H),2.79(s,3H),1.33(t,J＝7.4Hz,3H).
制备例3：
目标化合物I-73的合成
步骤A：中间体化合物1的合成
根据制备例1步骤E中描述的方法，将3,6-二氯吡啶-2-甲酰氯替换为3-氯-5-溴吡啶-2-甲酰氯可得由下式表示的中间体化合物1。
中间体化合物1
1H NMR(400MHz,CDCl3)δ9.33(s,1H),8.60(d,J＝1.9Hz,1H),8.36(dd,J＝2.2,1.1Hz,1H),8.10(d,J＝1.9Hz,1H),7.86(d,J＝2.1Hz,1H),5.03(d,J＝5.9Hz,1H),3.08(d,J＝4.8Hz,3H).
步骤B：中间体化合物2的合成
根据制备例1中步骤F中描述的方法可得由下式表示的中间体化合物2。
中间体化合物2
1H NMR(400MHz,CDCl3)δ8.77(d,J＝1.9Hz,2H),8.40(d,J＝2.0Hz,1H),8.16(d,J＝1.9Hz,1H),3.98(d,J＝1.2Hz,3H).
步骤C:中间体化合物3的合成
根据制备例1中步骤G的描述方法可得由下式表示的中间体化合物3。
步骤D：中间体化合物4的合成
根据制备例1中步骤H描述的方法可得由下式表示的中间体化合物4。
步骤E：中间体化合物5的合成
将中间体化合物4(5mmol)溶解于干燥的甲苯(35mL)中，并且然后添加碳酸铯(7.5mmol)。将混合物用氩气脱气，并且然后添加三(二亚苄基丙酮)二钯(0)(0.11mmol)、2,2’-双(二苯基膦基)-1,1’-二氢萘(0.2mmol)和2,4-二甲氧基苄胺(5mmol)。将混合物在氩气下在105℃(浴)下搅拌。混合物的深紫色在15min内变成淡黄色。20h之后，将反应冷却，并且在减压下除去溶剂。将残余物在50g的硅胶上纯化，洗脱剂为己烷中的50％乙酸乙酯。可得由下式表示的中间体化合物5。
步骤F：中间体化合物6的合成
在环境温度下，将中间体化合物5(3.31mmol)溶解于二氯甲烷(20mL)中，然后添加三氟乙酸(3.31mmol)。将橙红色溶液在环境温度下搅拌5h。在减压下除去挥发物。将残余物用饱和NaHCO3溶液碱化，并且用乙酸乙酯萃取。分离有机相，干燥并浓缩。将残余物在40g的硅胶上纯化，洗脱剂为乙酸乙酯，以给出由下式表示的中间体化合物6。
步骤G：中间体化合物7的合成
将中间体化合物6(1mmol)溶于10mL醋酸中，然后添加醋酸钠(1mmol),在室温下滴加溴(1.2mmol)的5mL醋酸溶液。然后将反应液置于当前温度下继续搅拌。反应完毕后用硫代硫酸钠水溶液淬灭反应液，然后用乙酸乙酯萃取并用无水硫酸钠干燥。将残余物经过柱层析纯化得到由下式表示的中间体化合物7。
步骤H：中间体化合物8的合成
将中间体化合物7(1mmol)溶于THF中，然后向其中加入环丙甲酰氯(1mmol)，再加入三乙胺(1.5mmol)，于室温搅拌。反应完毕后经柱层析纯化得到由下式表示的呈白色固体的中间体化合物8。
中间体化合物8
1H NMR(400MHz,Chloroform-d)δ9.44(d,J＝1.6Hz,1H),8.75(d,J＝2.0Hz,1H),8.30(d,J＝2.0Hz,1H),8.12(s,1H),3.91(d,J＝1.6Hz,3H),3.81(q,J＝7.5Hz,2H),1.74–1.68(m,1H),1.39(t,J＝7.5Hz,3H),1.26–1.22(m,3H),1.06(dt,J＝7.5,3.5Hz,2H).
步骤I:中间体化合物9的合成
将中间体化合物8(1mmol)溶于THF(15mL)，然后添加劳森试剂(1.5mmol),于回流下搅拌。反应完毕后蒸除溶剂，剩余物经柱层析纯化以给出由下式表示的呈淡黄色固体的中间体化合物9，收率40％。
步骤J：目标化合物I-73的合成
将中间体化合物9(1mmol)溶于1,4-二氧六环(15mL)中，然后加入碳酸铯(1.5mmol)，于80℃油浴中搅拌。反应完毕后向其中加入水，然后用乙酸乙酯萃取。有机相用无水硫酸钠干燥。最后经柱层析纯化以给出由下式表示的呈白色固体的本发明化合物I-73,收率80％，m.p.216-219℃。
本发明化合物I-73
1H NMR(400MHz,CDCl3)δ8.84(s,1H),8.77(d,J＝1.9Hz,1H),8.34(d,J＝2.1Hz,1H),3.86(s,3H),3.75(q,J＝7.4Hz,2H),2.51(tt,J＝8.1,5.3Hz,1H),1.46–1.41(m,4H),1.35(t,J＝7.4Hz,3H).EI-MS:468[M+H]+。
制备例4：
目标化合物I-37的合成
将中间体化合物8(1mmol)溶于1,4-二氧六环(15mL)，然后添加CuI(1.5mmol),在氮气气氛下，于回流下搅拌。反应完毕后蒸除溶剂，剩余物经柱层析纯化以给出由下式表示的呈白色固体的本发明化合物I-37，收率40％。m.p.224-227℃.
本发明化合物I-37
1H NMR(400MHz,CDCl3)δ8.77(dd,J＝2.0,0.8Hz,1H),8.69(s,1H),8.31(d,J＝2.0Hz,1H),3.87(s,3H),3.83(q,J＝7.4Hz,2H),2.35(tt,J＝8.2,4.9Hz,1H),1.50–1.45(m,2H),1.42–1.39(m,2H),1.36(d,J＝7.5Hz,3H).EI-MS:452[M+H]+
制备例5：
目标化合物I-109的合成
步骤A：中间体化合物10的合成
根据制备例3中步骤I描述的方法，将底物(1mmol)溶于THF(15mL)，然后添加劳森试剂(1.5mmol),于回流下搅拌。反应完毕后蒸除溶剂，剩余物经柱层析纯化以给出由下式表示的中间体化合物10，收率70％。
步骤B：目标化合物I-109的合成
将中间体化合物10(1mmol)溶于1,4-二氧六环(15mL)中，然后加入碳酸铯(1.5mmol)，于80℃油浴中搅拌。反应完毕后向其中加入水，然后用乙酸乙酯萃取。有机相用无水硫酸钠干燥。最后经柱层析纯化以给出由下式表示的本发明化合物I-109，收率85％。m.p.207-210℃.
本发明化合物I-109
1H NMR(400MHz,CDCl3)δ8.99(s,1H),8.79-8.73(m,2H),8.30(dd,J＝8.8,1.9Hz,2H),3.94(s,3H),3.93-3.88(m,2H),2.52(tt,J＝8.0,4.7Hz,1H),1.59-1.54(m,2H),1.47(dt,J＝8.1,3.4Hz,2H),1.41-1.37(m,3H).EI-MS:468[M+H]+。
类似于实施例并根据上述制备方法，合成了以下式(I)的化合物：
表2



上述优选化合物的核磁数据如表3所示：
表3

生物学测试：
本测试例用于说明式(I)所示结构的化合物的杀虫活性抑制(％)(剂量为100ppm)。
测试例1：对抗桃蚜(绿色桃蚜虫)的活性：
将受到混合年龄的蚜虫群体侵染的豌豆幼苗的根部直接放在从10'000ppm DMSO储备溶液中制备的水性测试溶液中。将幼苗放置在测试溶液中6天之后，针对死亡率对这些样品进行评估。
以下化合物在100ppm施用率下得到至少90％的死亡率：
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、和I-109。
测试例2：对抗小菜蛾(Plutella xylostella)的活性：
将具有人工饲料的24孔微量滴定板用从10’000ppm DMSO储备溶液中制备的水性测试溶液通过移液进行处理。在干燥之后，用L2期幼虫对各板进行侵染(10至15只/孔)。侵染5天之后，相比于未处理样品，针对死亡率和生长抑制对这些样品进行评估。
以下化合物在100ppm施用率下给出了两个类别(死亡率或生长抑制)中至少一个的至少90％的效果：
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和I-109。
进一步以下化合物在4ppm施用率下得到100％的死亡率：
I-73和I-109。
测试例3：对抗粘虫的活性：
将24孔微量滴定板中的置于琼脂层通过喷雾用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行处理。在干燥之后，用L2期幼虫对各板进行侵染(6至10只/孔)。侵染4天之后，相比于未处理样品，针对死亡率和生长抑制对这些样品进行评估。
以下化合物在100ppm施用率下给出了两个类别(死亡率或生长抑制)中至少一个的至少90％的效果：
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和I-109。
测试例4：对抗褐飞虱的活性：
将棉花叶圆片置于24孔微量滴定板中的琼脂上并且用从10’000ppm DMSO储备溶液中制备的水性测试溶液进行喷雾。在干燥之后，将叶圆片用成年褐飞虱进行侵染。孵育6天之后，针对死亡率对这些样品进行评估。
以下化合物在100ppm施用率下得到至少90％的死亡率：
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和I-109。
进一步以下化合物在45ppm施用率下得到至少95％的死亡率：
I-73、I-100和I-109。
测试例5：对抗甜菜夜蛾的活性：
将具有人工饲料的24孔微量滴定板用从10’000ppm DMSO储备溶液中制备的水性测试溶液通过移液进行处理。在干燥之后，用L2期幼虫对各板进行侵染(10至15只/孔)。侵染5天之后，相比于未处理样品，针对死亡率和生长抑制对这些样品进行评估。
以下化合物在100ppm施用率下给出了两个类别(死亡率或生长抑制)中至少一个的至少90％的效果：
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和I-109。
进一步以下化合物在4ppm施用率下得到100％的死亡率：
I-73和I-109。
测试例6：对抗苜蓿芽的活性：
将受到混合年龄的蚜虫群体侵染的豌豆幼苗的根部直接放在从10'000ppm DMSO储备溶液中制备的水性测试溶液中。将幼苗放置在测试溶液中6天之后，针对死亡率对这些样品进行评估。
以下化合物在100ppm施用率下得到至少90％的死亡率：
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和I-109。
进一步以下化合物在4ppm施用率下得到100％的死亡率：
I-1、I-37、I-73、I-100和I-109。
测试例7：对抗二化螟的活性：
取5～6株3～4cm水稻苗，于配好的药液中充分浸润后自然阴干，放入试管中，接二化螟2龄幼虫10头/管，置于观察室内饲养和观察。以0.1％吐温水为空白对照。置于25～27℃的观察室内培养，96h后调查结果，针对死亡率对这些样品进行评估。
以下化合物在5ppm施用率下得到100％的死亡率：
I-73和I-109。
以上所述的仅是本发明的优选实施方式，应当指出，对于本领域的普通技术人员来说，在不脱离本发明创造构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。

Claims (15)

  1. 一种如通式(Ⅰ)所示的含硫取代基的稠环类化合物：
    式中
    X选自N、NR1、O或S；
    Y选自N或S；
    其中当Y选自N时，X选自NR1、O或S；当Y选自S时，X选自N；
    式中R1选自H、C1～6烷基、C1～6卤代烷基、C3～6环烷基、C3～6卤代环烷基；
    式中R选自H、C1～6烷基、C1～6取代烷基、C3～6环烷基、C3～6取代环烷基、C2～6环氧基、C2～6烯基、C2～6炔基、苯基、取代苯基、C5～6杂环或取代杂环；
    所述取代烷基或取代环烷基的取代基选自卤素、C1～2烷基、C1～2烷氧基、C1～2卤代烷氧基、C1～2卤代烷基、氰基或酯基；
    所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、C1～2烷氧基、C1～2卤代烷氧基、氰基、C1～6烷基或C1～6卤代烷基；
    所述杂环选自至少一个非碳环原子的五元或六元单环，包括芳香环和非芳烃；
    所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、C1～6烷基、C1～6卤代烷基、C1～6烷氧基或C1～6烷基酰胺基。
  2. 如权利要求1所述的含硫取代基的稠环类化合物，其特征在于：
    所述X选自N、NR1、O或S；
    所述Y选自N或S；其中当Y选自N时，X选自NR1、O或S；当Y选自S时，X选自N；
    所述R1选自H、C1～6烷基、三氟甲基或环丙基；
    所述R选自C1～6烷基、C1～6卤代烷基、C3～6环烷基、C2～6烯基、C2～6炔基、苯基、取代苯基、C5～6杂环或取代杂环；
    所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、甲氧基、氰基、乙氧基、甲基、乙基或三氟甲基；
    所述杂环选自哌嗪基、吡咯烷基、二噁烷基、吗啉基、四氢呋喃基、吡啶基、呋喃基、咪唑基、嘧啶基、恶唑基、异恶唑基、四唑基、三唑基、噻二唑基或噻吩基；
    所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、甲基、乙基、甲氧基、三氟甲基或二氟甲基。
  3. 如权利要求1所述的含硫取代基的稠环类化合物，其特征在于：
    R选自C1～C6烷基、C1～C6卤代烷基、C3～C6环烷基、C2～C6烯基、C2～C6炔基、苯基、取代苯基、C5～C6杂环或取代杂环；
    所述取代苯基是指苯基上具有1、2或3个取代基取代，所述取代苯基的取代基选自卤素、甲氧基、氰基、甲基或三氟甲基；
    所述杂环选自2-噻吩基、吡啶基、2-氯吡啶基或5-溴吡啶基；
    所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、甲基、甲氧基或三氟甲基。
  4. 如权利要求1所述的含硫取代基的稠环类化合物，其特征在于：
    所述R1选自甲基或乙基；
    所述R选自C1～C6烷基、C1～C3卤代烷基、C3～C6环烷基、C2～C6烯基、C2～C6炔基、苯基、取代苯基、C5～C6杂环或取代杂环；
    所述取代苯基是指苯基上具有1、2或3个取代基取代，取代基选自卤素、甲氧基、氰基、甲基或三氟甲基；
    所述杂环选自2-噻吩基、吡啶基、2-氯吡啶基或5-溴吡啶基；
    所述取代杂环是指杂环上具有1、2或3个取代基取代，所述取代杂环的取代基选自卤素、甲基、甲氧基或三氟甲基。
  5. 如权利要求1所述的含硫取代基的稠环类化合物，其特征在于：
    所述R选自甲基、乙基、三氟甲基、二氟甲基、氯甲基、环丙基、七氟异丙基、乙基、氯甲基、异丙基、正丙基、异丁基、叔丁基、环丁基、环戊基、环己基、乙烯基、乙炔基、丙烯基、丁烯基、丙炔基、丁炔基、苯基、氰基环丙基、4-氟苯基、2-氟苯基、3-氟苯基、2,4-二氟苯基、2-噻吩基、2-吡啶基、2-氯吡啶基或5-溴吡啶基。
  6. 如权利要求1所述的含硫取代基的稠环类化合物，其特征在于：
    具有化学式(I-a)、(I-b)、(I-c)和(I-d)的化合物：
    所述R1选自甲基或乙基；
    所述R选自甲基、三氟甲基、二氟甲基、氯甲基、环丙基、七氟异丙基、乙基、氯甲基、异丙基、正丙基、异丁基、叔丁基、环丁基、环戊基、环己基、乙烯基、乙炔基、丙烯基、丁烯基、丙炔基、丁炔基、苯基、氰基环丙基、4-氟苯基、2-氟苯基、3-氟苯基、2,4-二氟苯基、2-噻吩基、2-吡啶基、2-氯吡啶基或5-溴吡啶基。
  7. 如权利要求6所述的含硫取代基的稠环类化合物，其特征在于：
    所述R1选自甲基；R选自环丙基或三氟甲基。
  8. 一种制备权利要求6所述的含硫取代基的稠环类化合物(I-a)的制备方法，其特征在于包括如下步骤：
    (1)将式(II)与式(III)反应所得到的化合物在醋酸中搅拌回流得到式(IV)化合 物；
    (2)将式(IV)所示化合物与乙硫醇在碱性条件下接触制得式(V)所示化合物；
    (3)将式(V)所示化合物与氧化剂反应制得式(VI)所示化合物；
    (4)将式(VI)所示化合物与2,4-二甲氧基苄胺通过Buchwald偶联反应制得式(VII)所示化合物；
    (5)将式(VII)所示化合物与三氟乙酸反应制得式(VIII)所示化合物；
    (6)将式(VIII)所示化合物与溴化试剂接触反应制得式(IX)所示化合物；
    (7)将式(IX)所示化合物与酰氯在缚酸剂存在下反应制得式(X)所示的化合物；
    (8)将(X)所示化合物与劳森试剂反应制得式(XI)所示化合物；
    (9)将式(XI)所示化合物在碱存在下反应制得式(I-a)所示的最终目标化合物；
  9. 一种制备权利要求6所述的含硫取代基的稠环类化合物(I-b)的制备方法，其特征在于包括如下步骤：

    将式(X)所示化合物在CuI、碱和催化剂存在下于溶剂中回流搅拌制得式(I-b)所示化合物；
  10. 一种制备权利要求6所述的含硫取代基的稠环类化合物(I-c)的制备方法，其特征在于包括如下步骤：
    (1)将式(II)所示化合物在醋酸中回流搅拌得到式(III)所示化合物；
    (2)将式(III)所示化合物在碱存在下与乙硫醇反应制得式(IV)所示化合物；
    (3)式(IV)所示化合物通过氧化制得式(V)所示化合物；
    (4)将式(V)所示化合物在溶剂中与取代胺接触制得式(VI)所示化合物；
    (5)将式(VI)所示化合物溶于浓硫酸中，然后在低温下滴加稀硝酸制得式(VII)所示化合物；
    (6)式(VII)所示化合物通过还原制得式(VIII)所示化合物；
    (7)将(VIII)所示化合物与取代酰氯反应得到式(IX)化合物；
    (8)将式(IX)所示化合物在醋酸中回流搅拌最终制得式(I-c)所示化合物；
  11. 一种制备权利要求6所述的含硫取代基的稠环类化合物(I-d)的制备方法，其特征在于包括如下步骤：
    (1)将(I-c)中所制得的式(V)化合物在溶剂中与氨水接触制得式(X)所示化合物；
    (2)将式(X)所示化合物在溶剂中在碱存在下溴化反应制得式(XI)所示化合物；
    (3)式(XI)所示化合物与取代酰氯反应制得式(XII)所示化合物；
    (4)式(XII)所示化合物与劳森试剂反应制得(XⅢ)所示化合物；
    (5)式(XⅢ)所示化合物在碱存在下发生环合反应制得(I-d)化合物；
  12. 一种如式(Ⅰ)所示的含硫取代基的稠环类化合物在制备杀虫剂中的应用。
  13. 如权利要求11所述的所述的应用，其特征在于所述杀虫剂为防治鳞翅目和/或鞘翅目的杀虫剂。
  14. 如权利要求11所述的应用，其特征在于所述杀虫剂针对的害虫为褐飞虱、灰飞虱、烟粉虱、小菜蛾、粘虫、桃蚜、朱砂叶螨中的一种或多种。
  15. 一种杀虫剂，其特征在于所述杀虫剂包括如权利要求1～6任一项所述的含硫取代基的稠环类化合物和助剂，所述含硫取代基的稠环化合物在杀虫剂中的浓度为1～600ppm。
PCT/CN2023/109212 2022-07-29 2023-07-26 具有含硫取代基的稠环化合物、制备方法、杀虫剂组合物及用途 Ceased WO2024022362A1 (zh)

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