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WO2022166837A1 - 芳基硫化物及其制备方法和应用 - Google Patents

芳基硫化物及其制备方法和应用 Download PDF

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Publication number
WO2022166837A1
WO2022166837A1 PCT/CN2022/074734 CN2022074734W WO2022166837A1 WO 2022166837 A1 WO2022166837 A1 WO 2022166837A1 CN 2022074734 W CN2022074734 W CN 2022074734W WO 2022166837 A1 WO2022166837 A1 WO 2022166837A1
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WO
WIPO (PCT)
Prior art keywords
methyl
aryl sulfide
formula
haloalkyl
alkyl
Prior art date
Application number
PCT/CN2022/074734
Other languages
English (en)
French (fr)
Inventor
柳英帅
李宁
刘祥伟
李先江
刘瑞宾
刘保红
盛国柱
项效忠
陈瑜
冯睿杰
崔迎蕊
韩勤安
王杰
王世玲
Original Assignee
山东康乔生物科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 山东康乔生物科技有限公司 filed Critical 山东康乔生物科技有限公司
Priority to CN202280010782.XA priority Critical patent/CN117062800A/zh
Publication of WO2022166837A1 publication Critical patent/WO2022166837A1/zh

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Classifications

    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom not containing sulfur-to-oxygen bonds, e.g. polysulfides
    • 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
    • A01P5/00—Nematocides
    • 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
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
    • C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/31—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/33—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring
    • C07C323/35—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group
    • C07C323/36—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton having at least one of the nitrogen atoms bound to a carbon atom of the same non-condensed six-membered aromatic ring the thio group being a sulfide group the sulfur atom of the sulfide group being further bound to an acyclic carbon atom

Definitions

  • the invention relates to the technical field of pesticides, in particular to an aryl sulfide and a preparation method and application thereof, an agricultural composition and a method for preventing and controlling invertebrate pests.
  • JP201142611A discloses that the compound of the following general formula has acaricidal activity:
  • A is oxygen or sulfur
  • R 5 is substituted or unsubstituted C 1-20 alkyl, substituted or unsubstituted amino, nitrogen-containing heterocycle, and the like.
  • WO2018015852 (CN109803956A) discloses a compound with the following general formula, which has acaricidal activity
  • R 4 represents hydrogen, formyl, C 1-6 alkyl, etc.
  • R 5 , R 6 are the same or different and each represents hydrogen, halogen or C 1-6 alkyl, etc.
  • R 7 , R 8 , R 9 , R 10 and R 11 are the same or different and each represents hydrogen, halogen, etc.
  • X represents oxygen or sulfur.
  • CN111825585A discloses a compound of the following general formula, which has acaricidal activity
  • the above compounds still have relatively low killing activity in the control of harmful substances, especially mites, and their acaricidal activity is often unsatisfactory especially at low usage rates, and has a control effect on the spider mites that have acquired drug resistance. Therefore, there is still an urgent need for new drugs with high efficiency, low toxicity and excellent killing effect against mites in agricultural production.
  • the object of the present invention is to provide a kind of aryl sulfide and preparation method thereof in order to overcome the technical problem that the existing compounds in the prior art have lower killing activity in the control of invertebrate pests (especially mites). and uses, agricultural compositions and methods of controlling invertebrate pests.
  • the inventors of the present invention have unexpectedly found that after replacing the hydrogen on the nitrogen of the compound (aryl sulfide disclosed by CN111825585A) with a substituted acyl group, an alkyl group, a sulfonyl group, etc., the compound previously disclosed by the inventor of the present invention can be effective against invertebrate pests. (especially mites) showed more efficient killing activity.
  • a first aspect of the present invention provides an aryl sulfide, the aryl sulfide is a compound whose structure is shown in formula I or an agriculturally acceptable salt thereof,
  • n 0 or 1
  • X and Y are each independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;
  • R 1 is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyloxy, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 2 -C 10 alkenyloxycarbonyl, C 2 -C 10 alkynyloxy Carbonyl, C 1 -C 10 alkylcarbonyl, aminocarbonyl, C 2 -C 10
  • R 2 , R 3 , R 4 , R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 alkyl , C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 - C 10 alkylsulfonyloxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 2 -C 10 alkenyloxycarbonyl, C 1 -C 10 alkylcarbonyl, aminocarbonyl, C 2 -C 10 cyanoalkylcarbonyl, C 1 -C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl
  • R 6 is C 1 -C 6 haloalkyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 ring oxyalkyl;
  • R 7 is C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, C 1 -C 10 alkylcarbonyl or C 1 -C 10 haloalkylcarbonyl.
  • a second aspect of the present invention provides a method for preparing an aryl sulfide, the method comprising:
  • a third aspect of the present invention provides an application of the aryl sulfide described in the first aspect in controlling invertebrate pests.
  • a fourth aspect of the present invention provides an agricultural composition comprising at least one aryl sulfide according to the aforementioned first aspect and at least one liquid carrier or solid carrier.
  • a fifth aspect of the present invention provides a method for controlling invertebrate pests, the method comprising directly or indirectly applying an insecticidally effective amount of the aryl sulfide described in the first aspect to the invertebrate pests to be controlled and/or or the medium in which it was grown.
  • the present invention has at least the following advantages:
  • the aryl sulfide provided by the present invention has excellent effects on various harmful organisms, especially on the spider mites represented by the two-spotted spider mite, the Kanzawa spider mite, the citrus spider mite, etc. ;
  • the aryl sulfide provided by the present invention has good characteristics in the application of protecting crops, livestock and other pests that are important in agriculture and horticulture.
  • a first aspect of the present invention provides an aryl sulfide, the aryl sulfide is a compound whose structure is shown in formula I or an agriculturally acceptable salt thereof,
  • n 0 or 1
  • X and Y are each independently halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;
  • R 1 is fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 Alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyloxy, C 1 -C 10 Alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 2 -C 10 alkenyloxycarbonyl, C 2 -C 10 alkynyloxy Carbonyl, C 1 -C 10 alkylcarbonyl, aminocarbonyl, C 2 -C 10
  • R 2 , R 3 , R 4 , R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 10 alkyl , C 1 -C 10 haloalkyl, C 1 -C 10 alkoxy, C 1 -C 10 haloalkoxy, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 - C 10 alkylsulfonyloxy, C 1 -C 10 alkylthio, C 1 -C 10 haloalkylthio, C 2 -C 10 alkenyloxycarbonyl, C 1 -C 10 alkylcarbonyl, aminocarbonyl, C 1 -C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C 1
  • R 6 is C 1 -C 6 haloalkyl, C 2 -C 6 alkynyl, C 2 -C 6 alkenyl, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 ring oxyalkyl;
  • R 7 is C 1 -C 10 alkyl, C 1 -C 10 haloalkyl, C 1 -C 10 alkoxycarbonyl, C 1 -C 10 haloalkoxycarbonyl, C 1 -C 10 alkylsulfonyl, C 1 -C 10 haloalkylsulfonyl, C 1 -C 10 alkylcarbonyl or C 1 -C 10 haloalkylcarbonyl.
  • n 0 or 1;
  • X is fluorine, chlorine or methyl;
  • Y is chlorine or methyl;
  • R 1 is C 1 -C 6 alkoxycarbonyl, C 1 -C 6 haloalkoxycarbonyl, C 2 -C 6 alkenyloxycarbonyl, C 2 -C 6 alkynyloxycarbonyl, C 2 -C 6 cyanoalkane Oxycarbonyl, C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkane sulfonyl or C 1 -C 6 haloalkylsulfonyl;
  • R 2 , R 3 , R 4 , R 5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C 1 -C 6 alkyl , C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy or C 1 -C 6 alkoxycarbonyl;
  • R 6 is C 1 -C 4 haloalkyl or C 1 -C 4 alkyl
  • R 7 is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 haloalkylcarbonyl.
  • n is 0 or 1;
  • X is fluorine or methyl
  • Y is chlorine or methyl
  • R 1 is C 1 -C 4 alkoxycarbonyl, C 1 -C 4 haloalkoxycarbonyl, C 2 -C 4 alkenyloxycarbonyl, C 2 -C 4 alkynyloxycarbonyl or C 2 -C 6 cyanoalkane oxycarbonyl;
  • R 2 , R 4 and R 5 are each independently hydrogen
  • R 3 is hydrogen, fluorine, chlorine or cyano
  • R 6 is C 1 -C 4 haloalkyl
  • R 7 is C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl, C 1 -C 6 alkylcarbonyl or C 1 -C 6 haloalkylcarbonyl; wherein the carbonyl group is attached to the nitrogen atom in formula I.
  • n 0 or 1;
  • X is fluorine;
  • Y is chlorine or methyl;
  • R 1 is methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethyl oxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl or cyanoethoxycarbonyl;
  • R 2 , R 4 and R 5 are each independently hydrogen
  • R 3 is hydrogen, fluorine, chlorine or cyano
  • R 6 is 2,2,2-trifluoroethyl
  • R 7 is methyl, ethyl, chloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, pentafluoropropionyl, trichloroacetyl, methanesulfonyl, ethanesulfonyl or trifluoromethanesulfonyl .
  • the aryl sulfide has the structure shown in Table 1, but the compounds included in the derivatives of the present invention are by no means limited to these compounds.
  • the compound number shown in Table 1 refers to the description in the following (Table 1).
  • the present invention in the aryl sulfide and its derivatives, according to the types of substituents, there are geometric isomers of E-type and Z-type, and the present invention includes these E-type, Z-type or Contains a mixture of E-form and Z-form in any proportion.
  • the present invention in the case of optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms, the present invention includes all optical isomers, external isomers racemate or diastereomer.
  • the so-called agriculturally acceptable salts in the compounds of the present invention represented by formula I, when a hydroxyl group, a carboxyl group, or an amino group, etc., are present in the structure, it refers to a salt formed with a metal or an organic base or a salt with a metal or an organic base. Salts formed from inorganic or organic acids, such as potassium, sodium, magnesium, or calcium salts, etc.
  • organic bases include triethylamine or diisopropylamine, examples of inorganic acids such as hydrochloric acid, sulfuric acid, hydrobromic acid, and the like, and examples of organic acids such as formic acid, acetic acid, methanesulfonic acid, fumaric acid, and maleic acid.
  • a second aspect of the present invention provides a method for preparing an aryl sulfide, the method comprising: contacting the compound represented by the formula II with the compound represented by the formula III to obtain the compound represented by the formula I,
  • n X, Y, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 or R 7 are the same as the aforementioned definitions;
  • Q is halogen (may be chlorine, bromine, iodine), mesylate, benzenesulfonate, p-toluenesulfonate, triflate, or substituted anhydride.
  • the present invention has no particular limitation on the halogen, mesylate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride, as long as it can be the compound represented by formula I It is sufficient to provide the R7 group.
  • R 7 -Q can be methyl iodide, ethyl trifluoroacetate, trifluoroacetic anhydride, trifluoroacetyl chloride, ethyl difluoroacetate, difluoroacetic anhydride, ethyl trichloroacetate, trichloroacetic anhydride , Methanesulfonyl chloride, ethylsulfonyl chloride, trifluoromethanesulfonic anhydride.
  • the contacting conditions include: a temperature of -20°C to 210°C, preferably -10°C to 150°C; a time of 1-50 h, preferably 3-25 h.
  • the molar ratio of the compound represented by formula I to the compound represented by formula III may be 1:(1-5), preferably 1:(2-3).
  • the contacting is performed in the presence of a solvent, wherein, relative to 1 g of the compound represented by formula I, the amount of the solvent used is 5-30 mL, preferably 10-20 mL.
  • the solvent is selected from N,N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1,2 - at least one of dichloroethane, trichloromethane, xylene and ethyl acetate.
  • the contacting is performed in the presence of a base, wherein relative to 1 mol of the compound represented by formula I, the amount of the base is 1-5 mol, preferably 2-3 mol.
  • the base is selected from triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine and 1,8 - at least one of diazabicycloundec-7-ene.
  • the post-treatment of the contact is not particularly limited, as long as the requirements of the present invention can be met.
  • it can be carried out in the following manner: adding an extraction solvent and water to the contacted reaction solution, Extraction and separation are performed to obtain an organic phase, and the aqueous phase is discarded; the organic phase is dried and then separated by column chromatography to obtain a purified product (the compound represented by formula I).
  • the extraction solvent is not particularly limited, for example, it can be selected from dichloromethane and/or ethyl acetate.
  • the inventors of the present invention found that the compound represented by the formula I has unexpectedly high acaricidal activity, therefore, the aryl sulfide of the present invention can also be used in agriculture or other fields for preparing acaricides drug.
  • the inventors of the present invention have found that the compound represented by formula I has high activity against the following invertebrate pests (the objects listed below are only used to illustrate the present invention, but not to limit the present invention): Tetranidae (such as Tetranychus cinnabarinus, Panonychus citrus, Tetranychus 2-spotted, Panclaw apple, Tetranychus shinata, Tetranychus hawthorn), Gall mites, Amitidae, Aphididae, Aphididae (such as peach aphid) ), nematodes (such as root-knot nematodes, cyst nematodes, short-bodied nematodes, perforating nematodes, umbrella worms), etc.
  • Tetranidae such as Tetranychus cinnabarinus, Panonychus citrus, Tetranychus 2-spotted, Panclaw apple, Tetranychus shinata, Tetranychus hawt
  • the third aspect of the present invention provides an application of the aryl sulfide according to the aforementioned first aspect in controlling invertebrate pests.
  • the invertebrate pests may be acarid pests and/or nematodes.
  • the aryl sulfide can be used to protect crops, livestock, etc., which are important in agriculture and horticulture, from being harmed or less damaged by mites.
  • the amount of aryl sulfide used varies due to various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the method of application, the application of environment, dosage form, etc.
  • a fourth aspect of the present invention provides an agricultural composition comprising at least one aryl sulfide according to the aforementioned first aspect and at least one liquid carrier or solid carrier.
  • the liquid carrier or solid carrier is not particularly limited, as long as it can meet the requirements of the present invention.
  • the concentration of the aryl sulfide may be 0.5-35 mg/L.
  • the liquid carrier can be water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, etc., such as toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropanol, ethyl acetate, etc.
  • solid carriers may include natural or synthetic clays and silicates
  • solid carriers suitable for powders may include naturally occurring rock powders, chalk, quartz, clay, montmorillonite, silica, silicon Diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, china clay, and synthetic ground minerals (such as finely dispersed silicic acid or alumina).
  • Suitable particulate carriers may include crushed and graded natural rocks such as calcite, marble, pumice, sepiolite and dolomite and synthetic particles made from organic and inorganic powders.
  • the composition may be administered in the form of a formulation.
  • the compound represented by formula I is dissolved or dispersed in a carrier as an active component, or is more easily dispersed when it is configured into a preparation for killing acaricide.
  • the composition can be made into wettable powder, water dispersible granule, suspension, water emulsion, water or emulsifiable concentrate and the like.
  • at least one liquid or solid carrier is added, and when desired a suitable surfactant can also be added.
  • the surfactant can include dodecylbenzene sulfonate, fatty alcohol sulfate, Tween, agricultural milk, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignosulfonate, alkyl naphthalene Sulfonates, etc.
  • a fifth aspect of the present invention provides a method for controlling invertebrate pests, the method comprising directly or indirectly applying an insecticidally effective amount of the aryl sulfide described in the first aspect to the invertebrate pests to be controlled and/or or the medium in which it was grown.
  • the direct or indirect method is not particularly limited, as long as the purpose of preventing and controlling invertebrate pests can be achieved.
  • indirect ways may include adding The substance containing the component of the aryl sulfide treats the place where the invertebrate pests infest (the habitat or the breeding ground of the invertebrate pest, or the plants and soil where the invertebrate pest grows) or treats the component containing the aryl sulfide. Substances process their food chain.
  • the method comprises treating plants grown by invertebrate pests with an insecticidally effective amount of an aryl sulfide according to the aforementioned first aspect.
  • the invertebrate pests are acarid pests and/or nematodes.
  • the acarid pests may include, but are not limited to: Tetranychus (such as Tetranychus cinnabarinus, Panonychus citrus, Tetranychus 2-spotted, Panonychus apple, Tetranychus kanazawa, Tetranychus hawthorn), Gall mites Family, Acaridaceae, Aphididae, Aphididae (such as the green peach aphid), nematodes (such as root-knot nematodes, cyst nematodes, short-bodied nematodes, perforating nematodes, umbrella nematodes) and the like.
  • Tetranychus such as Tetranychus cinnabarinus, Panonychus citrus, Tetranychus 2-spotted, Panonychus apple, Tetranychus kanazawa, Tetranychus hawthorn
  • the plant is a plant of Gymnosperm and/or Angiosperm, preferably at least one of Rutaceae, Solanaceae, Cruciferae, Leguminosae and Rosaceae.
  • the pesticidal effective amount is not particularly limited, for example, it can refer to the dosage of 8 grams to 3 kilograms of the aryl sulfide per hectare, which can provide sufficient control.
  • the pesticidally effective amount may range from 8 grams to 1000 grams per hectare applied, and preferably the effective amount is 15 grams to 300 grams per hectare.
  • the reaction solution was added with dichloromethane (20mL) and water (50mL), and the liquid was extracted and separated, and the aqueous phase was extracted by adding 20mL of dichloromethane again. After the separation, the organic phases were combined, and anhydrous sodium sulfate (5g) was added. After drying, it was concentrated to dryness under reduced pressure, and purified by column chromatography to obtain 2.65 g of white solid.
  • the compounds to be tested are dissolved in acetone and diluted to the desired concentration with 0.1 wt % aqueous Tween 80 solution, and the acetone content does not exceed 5 wt %.
  • Mortality (the number of inoculated insects - the number of live insects after the drug) ⁇ the number of inoculated insects ⁇ 100%.
  • compound 45, 103 and compound 53 disclosed in CN111825585A were selected to carry out the parallel test of killing mites (Tetranychus cinnabarinus), and the test results are shown in Table 2 below:

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Abstract

公开了一种芳基硫化物及其合成方法和应用。该芳基硫化物为结构如式I所示的化合物或其农业上可接受的盐。该芳基硫化物及其农业上可接受的盐对多种有害生物、特别是对以朱砂叶螨、二斑叶螨、神泽氏叶螨、柑桔全爪叶螨等为代表的叶螨类显示出卓越的效果，可用于防治各种害螨。

Description

芳基硫化物及其制备方法和应用
相关申请的交叉引用
本申请要求2021年02月07日提交的中国专利申请202110180116.8的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及农药技术领域，具体涉及一种芳基硫化物及其制备方法和应用、农业用组合物以及防治无脊椎动物害虫的方法。
背景技术
JP201142611A中公开了如下通式化合物具有杀螨活性：
Figure PCTCN2022074734-appb-000001
其中，A为氧或硫，R 5为取代或未经取代的C 1-20烷基、经取代或未经取代的氨基、含氮杂环等。
WO2018015852(CN109803956A)中公开了通式如下的化合物，具有杀螨活性，
Figure PCTCN2022074734-appb-000002
其中R 4表示氢、甲酰基、C 1-6烷基等；R 5、R 6相同或不同且各自表示氢、卤素或C 1-6烷基等；R 7、R 8、R 9、R 10、R 11相同或不同且各自表示氢、卤素等；X表示氧或硫。
CN111825585A中公开了通式如下的化合物，具有杀螨活性，
Figure PCTCN2022074734-appb-000003
但是，以上化合物在有害物特别是螨虫防治时仍然具有较低的杀灭活性，特别是在低使用率下其杀螨活性往往不能令人满意，并且对获得了抗药性的叶螨类防治效果更差，因此农业生产中仍然急需高效低毒，对抗性螨虫具有优良杀灭效果的新药。
发明内容
本发明的目的是为了克服现有技术存在的现有的化合物在无脊椎动物害虫(特别是螨虫)防治中具有较低的杀灭活性的技术问题，提供一种芳基硫化物及其制备方法和应用、农业用 组合物以及防治无脊椎动物害虫的方法。
本发明的发明人意外发现，将本发明的发明人之前公开的化合物(CN111825585A公开的芳基硫化物)氮上的氢用取代酰基、烷基、磺酰基等取代之后，能够对无脊椎动物害虫(特别是螨虫)表现出更高效的杀灭活性。
因此，为了实现上述目的，本发明第一方面提供一种芳基硫化物，该芳基硫化物为结构如式I所示的化合物或其农业上可接受的盐，
Figure PCTCN2022074734-appb-000004
其中，
n为0或1；
X、Y各自独立地为卤素、氰基、C 1-C 3烷基、C 1-C 3卤代烷基、C 1-C 3烷氧基或C 1-C 3卤代烷氧基；
R 1为氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 2-C 10炔氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 2-C 10氰烷氧基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基、C 1-C 10烷基亚磺酰基或C 1-C 10卤代烷基亚磺酰基；
R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 2-C 10氰烷基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基；
R 6为C 1-C 6卤代烷基、C 2-C 6炔基、C 2-C 6烯基、C 1-C 6烷基、C 3-C 6环烷基或C 3-C 6环氧烷基；
R 7为C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷基羰基或C 1-C 10卤代烷基羰基。
本发明第二方面提供一种制备芳基硫化物的方法，该方法包括：
将式II所示的化合物与式III所示的化合物进行接触，获得式I所示的化合物，
Figure PCTCN2022074734-appb-000005
R 7-Q    III
其中，式II和式III中，所涉及的n、X、Y、R 1、R 2、R 3、R 4、R 5、R 6或R 7的定义均与前述定义相同；Q为卤素、甲磺酸酯基、苯磺酸酯基、对甲苯磺酸酯基、三氟甲磺酸酯基或取代酸酐。
本发明第三方面提供一种前述第一方面所述的芳基硫化物在防治无脊椎动物害虫中的 应用。
本发明第四方面提供一种农业用组合物，该组合物包含至少一种前述第一方面所述的芳基硫化物以及至少一种液体载体或固体载体。
本发明第五方面提供一种防治无脊椎动物害虫的方法，该方法包括将杀虫有效量的前述第一方面所述的芳基硫化物直接或间接施于需要控制的无脊椎动物害虫和/或其生长的介质上。
与现有技术相比，本发明至少具有以下优势：
(1)本发明提供的芳基硫化物对多种有害生物、特别是对以二斑叶螨、神泽氏叶螨、柑桔全爪叶螨等为代表的叶螨类显示出卓越的效果；
(2)本发明提供的芳基硫化物在保护农业和园艺业重要的作物、家畜等害螨的伤害的应用上具有良好的特性。
具体实施方式
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。
本发明第一方面提供一种芳基硫化物，该芳基硫化物为结构如式I所示的化合物或其农业上可接受的盐，
Figure PCTCN2022074734-appb-000006
其中，
n为0或1；
X、Y各自独立地为卤素、氰基、C 1-C 3烷基、C 1-C 3卤代烷基、C 1-C 3烷氧基或C 1-C 3卤代烷氧基；
R 1为氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 2-C 10炔氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 2-C 10氰烷氧基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基、C 1-C 10烷基亚磺酰基或C 1-C 10卤代烷基亚磺酰基；
R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基；
R 6为C 1-C 6卤代烷基、C 2-C 6炔基、C 2-C 6烯基、C 1-C 6烷基、C 3-C 6环烷基或C 3-C 6环氧烷基；
R 7为C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷基羰基或C 1-C 10卤代烷基羰基。
根据本发明的一些实施方式，n为0或1；X为氟、氯或甲基；Y为氯或甲基；
R 1为C 1-C 6烷氧基羰基、C 1-C 6卤代烷氧基羰基、C 2-C 6烯氧基羰基、C 2-C 6炔氧基羰基、C 2-C 6氰烷氧基羰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷基磺酰基或C 1-C 6卤代烷基磺酰基；
R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基或C 1-C 6烷氧基羰基；
R 6为C 1-C 4卤代烷基或C 1-C 4烷基；
R 7为C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基羰基或C 1-C 6卤代烷基羰基。
根据本发明的一些实施方式，n为0或1；
X为氟或甲基；
Y为氯或甲基；
R 1为C 1-C 4烷氧基羰基、C 1-C 4卤代烷氧基羰基、C 2-C 4烯氧基羰基、C 2-C 4炔氧基羰基或C 2-C 6氰烷氧基羰基；
R 2、R 4和R 5各自独立的为氢；
R 3为氢、氟、氯或氰基；
R 6为C 1-C 4卤代烷基；
R 7为C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷基磺酰基、C 1-C 4卤代烷基磺酰基、C 1-C 6烷基羰基或C 1-C 6卤代烷基羰基；其中，羰基与式I中的氮原子相连。
根据本发明的一些实施方式，n为0或1；X为氟；Y为氯或甲基；
R 1为甲氧基羰基、乙氧基羰基、丙氧基羰基，丁氧基羰基、异丙氧基羰基、环丙氧基羰基、叔丁氧基羰基、氟乙氧基羰基、二氟乙氧基羰基、三氟乙氧基羰基、烯丙氧基羰基、炔丙氧基羰基、五氟丙氧基羰基或氰乙氧基羰基；
R 2、R 4和R 5各自独立的为氢；
R 3为氢、氟、氯或氰基；
R 6为2,2,2-三氟乙基；
R 7为甲基、乙基、氯乙酰基、氟乙酰基、二氟乙酰基、三氟乙酰基、五氟丙酰基、三氯乙酰基、甲磺酰基、乙磺酰基或三氟甲磺酰基。
本发明中，优选地，所述芳基硫化物具有表1所示的结构，但是本发明衍生物所包括的化合物绝非仅限定于这些化合物。另外，表1所示的化合物编号参照下文(表1)中的记载。本发明中，所述芳基硫化物及其衍生物中，根据取代基的种类存在E-型和Z-型的几何异构体的情况，本发明包括这些E-型、Z-型或者以任意比例含有E-型和Z-型的混合物。另外，在本发明包括的化合物中，存在由具有1个或2个以上的不对称碳原子和不对称硫原子而引起的光学异构体的情况，本发明包括所有的光学异构体、外消旋体或非对映体。
表1中：以下表述(例如Me、Et、tBu、CF 3、Ac)对应的基团如下所述：
Me：甲基；Et：乙基；tBu：叔丁基；CF 3：三氟甲基；Ac：乙酰基。
表1
Figure PCTCN2022074734-appb-000007
Figure PCTCN2022074734-appb-000008
Figure PCTCN2022074734-appb-000009
Figure PCTCN2022074734-appb-000010
Figure PCTCN2022074734-appb-000011
Figure PCTCN2022074734-appb-000012
Figure PCTCN2022074734-appb-000013
Figure PCTCN2022074734-appb-000014
Figure PCTCN2022074734-appb-000015
Figure PCTCN2022074734-appb-000016
Figure PCTCN2022074734-appb-000017
Figure PCTCN2022074734-appb-000018
Figure PCTCN2022074734-appb-000019
Figure PCTCN2022074734-appb-000020
Figure PCTCN2022074734-appb-000021
Figure PCTCN2022074734-appb-000022
Figure PCTCN2022074734-appb-000023
Figure PCTCN2022074734-appb-000024
Figure PCTCN2022074734-appb-000025
Figure PCTCN2022074734-appb-000026
Figure PCTCN2022074734-appb-000027
Figure PCTCN2022074734-appb-000028
Figure PCTCN2022074734-appb-000029
Figure PCTCN2022074734-appb-000030
Figure PCTCN2022074734-appb-000031
Figure PCTCN2022074734-appb-000032
Figure PCTCN2022074734-appb-000033
Figure PCTCN2022074734-appb-000034
Figure PCTCN2022074734-appb-000035
Figure PCTCN2022074734-appb-000036
Figure PCTCN2022074734-appb-000037
Figure PCTCN2022074734-appb-000038
Figure PCTCN2022074734-appb-000039
Figure PCTCN2022074734-appb-000040
Figure PCTCN2022074734-appb-000041
Figure PCTCN2022074734-appb-000042
本发明中，所谓农业上可接受的盐，在式I表示的本发明化合物中，当羟基、羧基、或氨基等存在于其结构中时，是指它们与金属或有机碱形成的盐或与无机酸或有机酸形成的盐，例如钾盐、钠盐、镁盐、或钙盐等。作为有机碱，例如三乙胺或二异丙胺等，作为无机酸，例如盐酸、硫酸、氢溴酸等，作为有机酸，例如甲酸、乙酸、甲磺酸、富马酸、马来酸等。
本发明第二方面提供一种制备芳基硫化物的方法，该方法包括，将式II所示的化合物与式III所示的化合物进行接触，获得式I所示的化合物，
Figure PCTCN2022074734-appb-000043
R 7-Q    III
其中，式II和式III中，所涉及的n、X、Y、R 1、R 2、R 3、R 4、R 5、R 6或R 7的定义均与前述的定义相同；Q为卤素(可以为氯、溴、碘)、甲磺酸酯基、苯磺酸酯基、对甲苯磺酸酯基、三氟甲磺酸酯基或取代酸酐。
本发明对所述卤素、甲磺酸酯基、苯磺酸酯基、对甲苯磺酸酯基、三氟甲磺酸酯基或取代酸酐没有特别的限定，只要能够为式I所示的化合物提供R 7基团即可。
本发明中，R 7-Q可以为碘甲烷、三氟乙酸乙酯、三氟乙酸酐、三氟乙酰氯、二氟乙酸乙酯、二氟乙酸酐、三氯乙酸乙酯、三氯乙酸酐、甲基磺酰氯，乙基磺酰氯、三氟甲磺酸酐。
根据本发明的一些实施方式，优选地，所述接触的条件包括：温度为-20℃至210℃，优选为-10℃至150℃；时间为1-50h，优选为3-25h。
根据本发明的一些实施方式，式I所示的化合物与式III所示的化合物的摩尔比可以为1：(1-5)，优选为1：(2-3)。
根据本发明的一些实施方式，优选地，所述接触在溶剂的存在下进行，其中，相对于1g式I所示的化合物，所述溶剂的用量为5-30mL，优选为10-20mL。
其中，所述溶剂选自N,N-二甲基甲酰胺、二氯甲烷、乙腈、丙酮、四氢呋喃、N-甲基吡咯烷酮、水、甲醇、乙醇、二甲基亚砜、甲苯、1,2-二氯乙烷、三氯甲烷、二甲苯和乙酸乙酯中的至少一种。
根据本发明的一些实施方式，优选地，所述接触在碱的存在下进行，其中相对于1mol式I所示的化合物，所述碱的用量为1-5mol，优选为2-3mol。
所述碱选自三乙胺、二异丙基乙基胺、氢化钠、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸铯、碳酸氢钠、碳酸氢钾、吡啶和1,8-二氮杂二环十一碳-7-烯中的至少一种。
本发明中，优选地情况下，对所述接触的后处理没有特别的限定，只要能够满足本发明的需求即可，例如可以通过如下方式进行：向接触后的反应液加入萃取溶剂和水，进行萃取分液，得到有机相，弃去水相；有机相经干燥后进行柱层析分离得到纯化产物(式I所示的化合物)。其中，对所述萃取溶剂没有特别的限定，例如可以选自二氯甲烷和/或乙酸乙酯。
本发明中，本发明的发明人发现，式I所示的化合物具有意想不到的高杀螨活性，因此，本发明的芳基硫化物还可以应用在农业或者其他领域中用作制备杀螨剂药物。尤其是，本发 明的发明人研究发现，式I所示的化合物对下述无脊椎动物害虫具有高活性(下述所列对象仅用来说明本发明，但非用来限定本发明)：叶螨科(如朱砂叶螨、柑橘全爪螨、二斑叶螨、苹果全爪螨、神泽叶螨、山楂叶螨)、瘿螨科、走螨科、细须螨科、蚜科(如桃蚜)、线虫(如根结线虫、胞囊线虫、短体线虫、穿孔线虫、伞滑刃线虫)等。
因此，本发明第三方面提供一种前述第一方面所述的芳基硫化物在防治无脊椎动物害虫中的应用。
根据本发明一些实施方式，所述无脊椎动物害虫可以为螨科害虫和/或线虫。
本发明中，优选地，所述芳基硫化物可以用于保护农业和园艺业中重要的作物、家畜等不受或少受害螨的伤害。
本发明中，为获得理想效果，在一些应用中，芳基硫化物的用量因各种因素而改变，例如所用化合物、预保护的作物、有害生物的类型、感染程度、施药方法、施药环境、施用剂型等因素。
本发明中，优选地，对于某些应用，例如在农业上可在本发明的杀螨组合物中加入一种或多种其他的杀虫剂、杀螨剂、杀菌剂、除草剂、植物生长调节剂或肥料等，由此可产生附加的优点和效果。
本发明第四方面提供一种农业用组合物，该组合物包含至少一种前述第一方面所述的芳基硫化物以及至少一种液体载体或固体载体。其中，对所述液体载体或固体载体没有特别的限定，只要能够满足本发明的需求即可。以液态形式的组合物为例，所述组合物中，所述芳基硫化物的浓度可以为0.5-35mg/L。
本发明中，液体载体可以为水、各种芳烃、脂肪烃、酮类、醚类等，如甲苯、二甲苯、丙酮、环已酮、二甲苯、苯、环己烷、异丙醇、乙二醇、山梨醇、甲醇、乙醇、丁醇、二甲基甲酰胺、N-甲基吡咯烷酮、萘烷、机油、石油醚、环己酮、油酸甲酯、甲基化大豆油等中的一种或几种；固体载体可以包括天然的或合成的粘土和硅酸盐，适用于粉剂的固体载体可以包括天然形成的岩石粉末、白垩、石英、粘土、蒙脱土、白炭黑、硅藻土、浮石、石膏、滑石、膨润土、高岭土、陶土及合成的磨碎的矿物质(如微分散的硅酸或氧化铝)。适合的颗粒载体可以包括破碎的和分级的天然岩石例如方解石、大理石、浮石、海泡石和白云石及由有机物和无机物的粉末制成的合成颗粒。
本发明中，优选地，所述组合物可以以制剂的形式施用。其中，式I所示的化合物作为活性组分溶解或分散于载体中，或配置成制剂以便进行杀螨使用时更易于分散。例如：所述组合物可以被制成可湿性粉剂、水分散粒剂、悬浮剂、水乳剂、水剂或乳油等。在所述组合物中，至少加入一种液体或固体载体，并且当需要时还可以加入适当的表面活性剂。其中，表面活性剂可以包括十二烷基苯磺酸盐、脂肪醇硫酸盐、吐温、农乳、山梨醇聚氧乙烯醚、脂肪醇聚氧乙烯醚、木质素磺酸盐、烷基萘磺酸盐等。
本发明第五方面提供一种防治无脊椎动物害虫的方法，该方法包括将杀虫有效量的前述第一方面所述的芳基硫化物直接或间接施于需要控制的无脊椎动物害虫和/或其生长的介质上。其中，对于直接或间接的方式没有特别的限定，只要能够达到防治无脊椎动物害虫的目的即可，例如直接的方式可以包括直接将含有所述芳基硫化物的成分的物质与无脊椎动物害虫接触(包括无脊椎动物害虫直接食用含有所述芳基硫化物的成分的物质、无脊椎动物害虫身体表面与含有所述芳基硫化物的成分的物质直接接触等)；间接的方式可以包括将含有所述芳基硫化物的成分的物质处理无脊椎动物害虫出没的场所(其栖息地或其繁殖地或无脊椎动物害虫生长的植物、土壤)或者将含有所述芳基硫化物的成分的物质处理其食物链。
根据本发明优选的实施方式，所述方法包括用杀虫有效量的前述第一方面所述的芳基硫化物处理无脊椎动物害虫生长的植物。
本发明中，优选地，所述无脊椎动物害虫为螨科害虫和/或线虫。如前所述，所述螨科害虫可以包括但不限于：叶螨科(如朱砂叶螨、柑橘全爪螨、二斑叶螨、苹果全爪螨、神泽叶螨、山楂叶螨)、瘿螨科、走螨科、细须螨科、蚜科(如桃蚜)、线虫(如根结线虫、胞囊 线虫、短体线虫、穿孔线虫、伞滑刃线虫)等。
本发明中，所述植物为裸子植物门和/或被子植物门的植物，优选为芸香科植物、茄科植物、十字花科植物、豆科植物和蔷薇科植物中的至少一种。
本发明中，对杀虫有效量没有特别的限定，例如可以指每公顷施用8克到3公斤的所述芳基硫化物的剂量，便能够提供充分的防治。优选地，杀虫有效量可以为每公顷施用8克到1000克，优选有效量为每公顷施用15克到300克。
应当明确的是，在本发明的权利要求所限定的范围内，可进行各种变换和改动。
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
制备实施例：
制备实施例1
2-((N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰氨基)甲基)苯甲酸甲酯(化合物35)的制备
Figure PCTCN2022074734-appb-000044
将2-((((2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)氨基)甲基)苯甲酸甲酯(0.5g，1.29mmol)加入到圆底烧瓶中，依次加入二氯甲烷(10mL)和三乙胺(0.26g，2.58mmol)，然后滴加乙酰氯(0.15g，1.935mmol)，反应液室温搅拌4小时后加入二氯甲烷(30mL)和水(50mL)，萃取分液后有机相加入无水硫酸钠(5g)干燥，减压浓缩至干，硅胶柱层析纯化得白色固体0.36g；
1H-NMR(400MHz,CDCl 3):δ＝7.79(d,J＝8.0Hz,1H),7.44-7.50(m,2H),7.27-7.31(m,1H),7.07(d,J＝7.6Hz,1H),6.99(d,J＝10.4Hz,1H),5.59(d,J＝10.8Hz,1H),5.04(d,J＝15.2Hz,1H),3.75(s,3H),3.10-3.19(m,2H),2.42(s,3H),1.91(s,3H)；
MS(m/z,ESI):452.3(m+Na)。
制备实施例2
2-((2-氯-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰氨基)甲基)苯甲酸甲酯(化合物37)的制备
Figure PCTCN2022074734-appb-000045
按照制备实施例1所述方法制备得到；
1H-NMR(400MHz,CDCl 3):δ＝7.81(d,J＝7.6Hz,1H),7.47(d,J＝3.6Hz,2H),7.30-7.34(m,1H),7.07(d,J＝7.6Hz,1H),7.01(d,J＝10.4Hz,1H),5.67(d,J＝14.8Hz,1H),5.02(d,J＝15.2Hz,1H),3.86(d,J＝8.0Hz,2H),3.75(s,3H),3.07-3.21(m,2H),2.44(s,3H)；
MS(m/z,ESI):464.3(m+H)。
制备实施例3
2-((N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)异丁酰胺基)甲基)苯甲酸 甲酯(化合物1877)的制备
Figure PCTCN2022074734-appb-000046
按照制备实施例1所述方法制备得到；
1H-NMR(400MHz,CDCl 3):δ＝7.70(d,J＝7.6Hz,1H),7.36(s,2H),7.22(s,1H),6.92(d,J＝8.8Hz,2H),5.59(d,J＝14.8Hz,1H),4.84(d,J＝15.2Hz,1H),3.69(s,3H),2.96-3.10(m,2H),2.31-2.34(m,4H),0.99(t,J＝7.2Hz,6H)；
MS(m/z,ESI):458.3(m+H),480.3(m+Na)。
制备实施例4
2-((2-氯-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)丙酰胺基)甲基)苯甲酸甲酯(化合物57)的制备
Figure PCTCN2022074734-appb-000047
按照制备实施例1所述方法制备得到；
1H-NMR(400MHz,CDCl 3):δ＝7.83(d,J＝7.2Hz,1H),7.47(s,2H),7.32(s,1H),7.16(d,J＝6.8Hz,1H),7.01(d,J＝10.8Hz,1H),5.72(d,J＝15.2Hz,1H),4.93(d,J＝14.8Hz,1H),4.15(d,J＝6.0Hz,1H),3.77(s,3H),3.05-3.21(m,2H),2.43(s,3H),1.60-1.64(m,3H)；
MS(m/z,ESI):478.2(m+H),500.2(m+Na).
制备实施例5
2-((N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)丙酰胺基)甲基)苯甲酸甲酯(化合物53)的制备
Figure PCTCN2022074734-appb-000048
按照制备实施例1所述方法制备得到；
1H-NMR(400MHz,CDCl 3):δ＝7.78(d,J＝7.6Hz,1H),7.46-7.48(m,2H),7.29-7.31(m,1H),6.97-7.03(m,2H),5.62(d,J＝14.8Hz,1H),5.00(d,J＝14.8Hz,1H),3.74(s,3H),3.08-3.16(m,2H),2.42(s,3H),2.08(q,J＝6.8Hz,2H),1.09(t,J＝6.8Hz,3H)；
MS(m/z,ESI):444.2(m+H),466.2(m+Na)。
制备实施例6
2-((N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)苯甲酰胺基)甲基)苯甲酸甲酯(化合物1845)的制备
Figure PCTCN2022074734-appb-000049
按照制备实施例1所述方法制备得到。
1H-NMR(400MHz,CDCl 3):δ＝7.84(d,J＝8.0Hz,1H),7.61(d,J＝7.6Hz,1H),7.50(t,J＝7.2Hz,1H),7.32-7.35(m,3H),7.17-7.21(m,3H),6.95(d,J＝6.4Hz,1H),6.79(d,J＝10.8Hz,1H),5.76(s,1H),5.26(s,1H),3.81(s,3H),2.91(s,2H),2.31(s,3H)；
MS(m/z,ESI):514.3(m+Na)。
制备实施例7
2-(((2,2,2-三氟-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰胺基)甲基)苯甲酸甲酯(化合物45)的制备
Figure PCTCN2022074734-appb-000050
将2-((((2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)氨基)甲基)苯甲酸甲酯(2.5g，6.45mmol)加入到圆底烧瓶中，依次加入二氯甲烷(15mL)和碳酸钾(1.34g，9.68mmol)，室温下缓慢滴加三氟乙酸酐(1.63g，7.74mmol)。反应液继续室温下搅拌反应3.5小时。反应液加入二氯甲烷(20mL)和水(50mL)，萃取分液，水相再次加入20mL二氯甲烷萃取，分液后合并有机相，加入无水硫酸钠(5g)干燥后减压浓缩至干，柱层析纯化得到白色固体2.65g。
1H-NMR(400MHz,CDCl 3):δ＝7.84(d,J＝8.0Hz,1H),7.47(t,J＝7.2Hz,1H),7.34-7.39(m,2H),6.94-7.01(m,2H),5.74(d,J＝14.4Hz,1H),5.00(d,J＝14.4Hz,1H),3.75(s,3H),2.98-3.15(m,2H),2.43(s,3H)；
MS(m/z,ESI):484.2(m+H),506.2(m+Na)。
制备实施例8
2-((2,2-二氟-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰胺基)甲基)苯甲酸甲酯(化合物43)的制备
Figure PCTCN2022074734-appb-000051
按照制备实施例7所述方法制备得到；
1H NMR(400MHz,CDCl 3):δ＝7.84(t,J＝8.5Hz,1H),7.46(dd,J＝17.9,9.1Hz,2H),7.42–7.32(m,1H),7.01(d,J＝9.9Hz,2H),5.87–5.58(m,2H),5.02(dd,J＝14.3,9.4Hz,1H),3.76(t,J＝7.1Hz,3H),3.11(dt,J＝24.0,7.5Hz,2H),2.44(d,J＝9.9Hz,3H)；
MS(m/z,ESI):466.1(m+H),488.1(m+Na)。
制备实施例9
2-((2,2,2-三氯-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰胺基)甲基) 苯甲酸甲酯(化合物47)的制备
Figure PCTCN2022074734-appb-000052
按照制备实施例7所述方法制备得到；
1H NMR(400MHz,CDCl 3):δ＝7.84(d,J＝7.7Hz,1H),7.46(dd,J＝13.7,6.7Hz,2H),7.34(t,J＝8.2Hz,1H),7.09(d,J＝6.6Hz,1H),6.95(d,J＝10.5Hz,1H),5.84(s,1H),4.92(s,1H),3.77(s,3H),3.04(s,2H),2.37(d,J＝38.1Hz,3H)；
MS(m/z,ESI):532.1(m+H),556.0(m+Na)。
制备实施例10
(2-氟-4-甲基-5-(2,2,2-三氟乙基)硫代苯基)(甲基)氨基)苯甲酸甲酯(化合物1)的制备
Figure PCTCN2022074734-appb-000053
将2-((((2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)氨基)甲基)苯甲酸甲酯(1g，2.58mmol)加入到50mL圆底烧瓶中，加入DMF(10mL)，然后依次加入碳酸钾(0.72g，5.22mmol)，碘甲烷(0.732g，5.16mmol)，反应液加热到42摄氏度下搅拌反应24小时。反应液加入50mL乙酸乙酯和100mL水，萃取分液后水相再次加入50mL乙酸乙酯，萃取分液后合并有机相，分两批加入100mL水洗涤。分液后有机相加入无水硫酸钠(5g)干燥，减压浓缩至干后柱层析纯化，得到180mg淡黄色油状液体；
1H NMR(400MHz,CDCl3)δ＝8.00–7.66(m,1H),7.57(s,1H),7.46(d,J＝6.3Hz,1H),7.38–7.01(m,1H),7.06(d,J＝8.6Hz,1H),6.87(d,J＝13.3Hz,1H),4.64(s,2H),3.91(dd,J＝51.8,23.7Hz,3H),3.45–2.98(m,2H),2.80(s,3H),2.59–2.13(m,3H)；
MS(m/z,ESI):402.1(m+H)，424.1(m+Na)。
制备实施例11
2-((乙基(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)氨基)甲基)苯甲酸甲酯(化合物3)的制备
Figure PCTCN2022074734-appb-000054
按照制备实施例10所述方法制备得到；
1H NMR(400MHz,CDCl 3):δ＝7.83(d,J＝7.7Hz,1H),7.52(d,J＝7.7Hz,1H),7.42(t,J＝7.6Hz,1H),7.29(d,J＝7.6Hz,1H),7.00(d,J＝8.8Hz,1H),6.86(d,J＝13.4Hz,1H),4.65(s,2H),3.87(d,J＝0.6Hz,3H),3.36–2.97(m,4H),2.35(s,3H),1.08(t,J＝7.0Hz,3H)；
MS(m/z,ESI):416.4(m+H)。
制备实施例12
2-((2-氟-4-甲基-5-(2,2,2-三氟乙基硫代)苯基)-(丙基)氨基)甲基苯甲酸酯(化合物5)的制备
Figure PCTCN2022074734-appb-000055
按照制备实施例10所述方法制备得到；
1H-NMR(400MHz,CDCl 3):δ＝7.76(d,J＝7.6Hz,1H),7.43(d,J＝7.6Hz,1H),7.30-7.35(m,1H),7.20-7.22(m,1H),6.90(d,J＝8.8Hz,1H),6.77(d,J＝13.6Hz,1H),4.60(s,2H),3.82(s,3H),3.01-3.09(m,4H),2.27(s,3H),1.44-1.50(m,2H),0.78(t,J＝7.2Hz,3H)；
MS(m/z,ESI):430.3(m+H)。
制备实施例13
2-((2,2,2-三氟-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰胺基)甲基)苯甲酸乙酯(化合物103)的制备
Figure PCTCN2022074734-appb-000056
按照制备实施例7所述方法制备得到，白色固体；
1H NMR(400MHz,CDCl 3)δ7.84(d,J＝7.7Hz,1H),7.47(t,J＝7.5Hz,1H),7.36(dd,J＝17.2,8.2Hz,2H),6.97(dd,J＝13.1,8.9Hz,2H),5.74(d,J＝14.4Hz,1H),5.02(d,J＝14.4Hz,1H),4.41–4.01(m,2H),3.07(tdd,J＝15.4,9.6,6.0Hz,2H),2.42(s,3H),1.32(t,J＝7.1Hz,3H).
MS(m/z,ESI):520.1(m+Na)。
制备实施例14
5-氟-2-(((2,2,2-三氟-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫基)苯基)乙酰胺基)甲基)苯甲酸甲酯(化合物1511)的制备
Figure PCTCN2022074734-appb-000057
按照制备实施例7所述方法制备得到，白色固体；
1H NMR(400MHz,CDCl 3)δ7.54(dd,J＝9.2,2.8Hz,1H),7.41(dd,J＝8.5,5.4Hz,1H),7.24–7.10(m,1H),7.00(dd,J＝8.7,6.0Hz,2H),5.62(d,J＝14.4Hz,1H),5.07(d,J＝14.5Hz,1H),3.75(s,3H),3.34–3.01(m,2H),2.45(s,3H)。
制备实施例15
2-(((2,2,2-三氟-N-(2-氟-4-甲基-5-((2,2,2-三氟乙基)硫代)苯基)乙酰胺基)甲基)苯甲酸三氟乙酯(化合物393)的制备
Figure PCTCN2022074734-appb-000058
按照制备实施例7所述方法制备得到，白色固体；
1H NMR(400MHz,CDCl 3)δ7.92(d,J＝7.8Hz,1H),7.55(t,J＝7.1Hz,1H),7.51–7.36(m,2H),7.07–6.95(m,2H),5.68(d,J＝14.7Hz,1H),5.07(d,J＝14.7Hz,1H),4.55(pd,J＝9.1,4.2Hz,2H),3.25–2.93(m,2H),2.41(d,J＝14.6Hz,3H).
MS(m/z,ESI):574.15(m+Na)。
制备实施例16
甲基2-((N-(4-氯-2-氟-5-((2,2,2-三氟乙基)硫基)苯基)-2,2,2-三氟乙酰氨基)甲基)苯甲酸甲酯(化合物799)的制备
Figure PCTCN2022074734-appb-000059
1H NMR(400MHz,CDCl 3)δ7.86(d,J＝7.8Hz,1H),7.50(t,J＝7.5Hz,1H),7.39(dd,J＝13.1,7.0Hz,2H),7.25(d,J＝8.0Hz,1H),7.08(d,J＝7.6Hz,1H),5.68(d,J＝14.4Hz,1H),5.07(d,J＝14.3Hz,1H),3.76(s,3H),3.24(q,J＝9.5Hz,2H).
MS(m/z,ESI):526.08(m+Na)。
制备实施例17
甲基2-((N-(4-氯-2-氟-5-((2,2,2-三氟乙基)硫基)苯基)-2,2,2-三氟乙酰氨基)甲基)苯甲酸乙酯(化合物857)的制备
按照制备实施例7所述方法制备得到，白色固体；
Figure PCTCN2022074734-appb-000060
1H NMR(400MHz,CDCl 3)δ7.86(d,J＝7.9Hz,1H),7.50(t,J＝7.5Hz,1H),7.45–7.35(m,2H),7.25(d,J＝10.2Hz,1H),7.08(d,J＝7.6Hz,1H),5.69(d,J＝14.4Hz,1H),5.09(d,J＝14.3Hz,1H),4.29–4.04(m,2H),3.23(tt,J＝9.5,4.7Hz,2H),1.32(t,J＝7.1Hz,3H).
MS(m/z,ESI):540.01(m+Na)。
制剂实施例1：
20％化合物45乳油制剂的配制
取20重量份化合物45溶于24重量份N-甲基吡咯烷酮中，然后分别加入12重量份500#(十二烷基苯磺酸钙)、6重量份33#(三苯乙基酚聚氧乙烯醚)，搅拌均匀，加入7.2重量份油酸甲酯680，继续搅拌均匀后加入用甲基萘填充剩余量至100重量份，搅拌均匀后得20％化合物45乳油制剂。
用途实施例1
朱砂叶螨活性试验
将待测化合物用丙酮溶解，并用0.1重量％的吐温80水溶液稀释至所需浓度，丙酮含量不超过5重量％。
将生长至两片真叶的菜豆苗去掉一片真叶，接种朱砂叶螨后调查基数，用手持喷雾器进行整株喷雾处理，每处理重复3次(制剂施用量约为0.5g)，处理后于恒温观察室观察，72小时后调查活螨数量，计算死亡率。实验重复3次，每次接种朱砂叶螨的数量为50-150只。
死亡率＝(接种虫数－药后活虫数)÷接种虫数×100％。
在该试验中，以下化合物在25ppm(25mg/L)下显示出超过90％的致死率：
1，3，5，37，43，45，47，57，103，393,799,857，1511。
在该试验中，以下化合物在6.25ppm(6.25mg/L)下显示出超过90％的致死率：
1，43，45，47，103，393,799,857，1511。
在该试验中，以下化合物在1.56ppm(1.56mg/L)下显示出超过80％的致死率：
45，103，393,799,857，1511。
按照上述方法，选取化合物45、103与CN111825585A中公开的化合物53进行杀螨(朱砂叶螨)的平行试验，试验结果见下表2：
表2
Figure PCTCN2022074734-appb-000061
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。

Claims (10)

  1. 一种芳基硫化物，其特征在于，该芳基硫化物为结构如式I所示的化合物或其农业上可接受的盐，
    Figure PCTCN2022074734-appb-100001
    其中，
    n为0或1；
    X、Y各自独立地为卤素、氰基、C 1-C 3烷基、C 1-C 3卤代烷基、C 1-C 3烷氧基或C 1-C 3卤代烷氧基；
    R 1为氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 2-C 10炔氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 2-C 10氰烷氧基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基、C 1-C 10烷基亚磺酰基或C 1-C 10卤代烷基亚磺酰基；
    R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基、C 1-C 10卤代烷氧基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰氧基、C 1-C 10烷硫基、C 1-C 10卤代烷硫基、C 2-C 10烯氧基羰基、C 1-C 10烷基羰基、氨基羰基、C 1-C 10N-烷基羰基、N,N-二甲基羰基、N,N-二甲基硫代羰基、C 1-C 10N-烷基硫代羰基、2-氧代丙氧基羰基；
    R 6为C 1-C 6卤代烷基、C 2-C 6炔基、C 2-C 6烯基、C 1-C 6烷基、C 3-C 6环烷基或C 3-C 6环氧烷基；
    R 7为C 1-C 10烷基、C 1-C 10卤代烷基、C 1-C 10烷氧基羰基、C 1-C 10卤代烷氧基羰基、C 1-C 10烷基磺酰基、C 1-C 10卤代烷基磺酰基、C 1-C 10烷基羰基或C 1-C 10卤代烷基羰基。
  2. 根据权利要求1所述的芳基硫化物，其中，n为0或1；
    X为氟、氯或甲基；
    Y为氯或甲基；
    R 1为C 1-C 6烷氧基羰基、C 1-C 6卤代烷氧基羰基、C 2-C 6烯氧基羰基、C 2-C 6炔氧基羰基、C 2-C 6氰烷氧基羰基、C 1-C 6烷硫基、C 1-C 6卤代烷硫基、C 1-C 6烷基亚磺酰基、C 1-C 6卤代烷基亚磺酰基、C 1-C 6烷基磺酰基或C 1-C 6卤代烷基磺酰基；
    R 2、R 3、R 4、R 5各自独立的为氢、氟、氯、溴、碘、氰基、硝基、氨基、羟甲基、羧基、羟基、巯基、C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷氧基、C 1-C 6卤代烷氧基或C 1-C 6烷氧基羰基；
    R 6为C 1-C 4卤代烷基或C 1-C 4烷基；
    R 7为C 1-C 6烷基、C 1-C 6卤代烷基、C 1-C 6烷基磺酰基、C 1-C 6卤代烷基磺酰基、C 1-C 6烷基羰基或C 1-C 6卤代烷基羰基。
  3. 根据权利要求1或2所述的芳基硫化物，其中，n为0或1；
    X为氟或甲基；
    Y为氯或甲基；
    R 1为C 1-C 4烷氧基羰基、C 1-C 4卤代烷氧基羰基、C 2-C 4烯氧基羰基、C 2-C 4炔氧基羰基或C 2-C 6氰烷氧基羰基；
    R 2、R 4和R 5各自独立的为氢；
    R 3为氢、氟、氯或氰基；
    R 6为C 1-C 4卤代烷基；
    R 7为C 1-C 4烷基、C 1-C 4卤代烷基、C 1-C 4烷基磺酰基、C 1-C 4卤代烷基磺酰基、C 1-C 6烷基羰基或C 1-C 6卤代烷基羰基；其中，羰基与式I中的氮原子相连；
    优选地，n为0或1；
    X为氟；
    Y为氯或甲基；
    R 1为甲氧基羰基、乙氧基羰基、丙氧基羰基，丁氧基羰基、异丙氧基羰基、环丙氧基羰基、叔丁氧基羰基、氟乙氧基羰基、二氟乙氧基羰基、三氟乙氧基羰基、烯丙氧基羰基、炔丙氧基羰基、五氟丙氧基羰基或氰乙氧基羰基；
    R 2、R 4和R 5各自独立的为氢；
    R 3为氢、氟、氯或氰基；
    R 6为2,2,2-三氟乙基；
    R 7为甲基、乙基、氯乙酰基、氟乙酰基、二氟乙酰基、三氟乙酰基、五氟丙酰基、三氯乙酰基、甲磺酰基、乙磺酰基或三氟甲磺酰基。
  4. 一种制备芳基硫化物的方法，其特征在于，该方法包括：
    将式II所示的化合物与式III所示的化合物进行接触，获得式I所示的化合物，
    Figure PCTCN2022074734-appb-100002
    R 7-Q III
    其中，式II和式III中，所涉及的n、X、Y、R 1、R 2、R 3、R 4、R 5、R 6或R 7的定义均与权利要求1-3中任意一项的定义相同；Q为卤素、甲磺酸酯基、苯磺酸酯基、对甲苯磺酸酯基、三氟甲磺酸酯基或取代酸酐。
  5. 根据权利要求4所述的方法，其中，所述接触的条件包括：温度为-20℃至210℃，优选为-10℃至150℃；时间为1-50h，优选为3-25h；
    和/或，式I所示的化合物与式III所示的化合物的摩尔比为1：(1-5)，优选为1：(2-3)；
    和/或，所述接触在溶剂的存在下进行，优选地，相对于1g式I所示的化合物，所述溶剂的用量为5-30mL，优选为10-20mL；
    其中，所述溶剂选自N,N-二甲基甲酰胺、二氯甲烷、乙腈、丙酮、四氢呋喃、N-甲基吡咯烷酮、水、甲醇、乙醇、二甲基亚砜、甲苯、1,2-二氯乙烷、三氯甲烷、二甲苯和乙酸乙酯中的至少一种；
    和/或，所述接触在碱的存在下进行，优选地，相对于1mol式I所示的化合物，所述碱的用量为1-5mol，优选为2-3mol；
    其中，所述碱选自三乙胺、二异丙基乙基胺、氢化钠、氢氧化钠、氢氧化钾、碳酸钠、碳酸钾、碳酸铯、碳酸氢钠、碳酸氢钾、吡啶和1,8-二氮杂二环十一碳-7-烯中的至少一种。
  6. 一种权利要求1-3中任意一项所述的芳基硫化物在防治无脊椎动物害虫中的应用。
  7. 根据权利要求6所述的应用，所述无脊椎动物害虫为螨科害虫和/或线虫。
  8. 一种农业用组合物，其特征在于，该组合物包含至少一种权利要求1-3中任意一项 所述的芳基硫化物以及至少一种液体载体或固体载体。
  9. 一种防治无脊椎动物害虫的方法，其特征在于，该方法包括将杀虫有效量的权利要求1-3中任意一项所述的芳基硫化物直接或间接施于需要控制的无脊椎动物害虫和/或其生长的介质上。
  10. 根据权利要求9所述的方法，其中，所述方法包括用杀虫有效量的权利要求1-3中任意一项所述的芳基硫化物处理无脊椎动物害虫生长的植物；
    和/或，所述无脊椎动物害虫为螨科害虫和/或线虫；
    和/或，所述植物为裸子植物门和/或被子植物门的植物，优选为芸香科植物、茄科植物、十字花科植物、豆科植物、和蔷薇科植物中的至少一种。
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