Aryl sulfides, processes for their preparation and use

Abstract

Disclosed are aryl sulfides, a method for synthesizing the same, and applications thereof. The aryl sulfides are compounds having a structure as shown in Formula I or agriculturally acceptable salts thereof. The aryl sulfides and the agriculturally acceptable salts thereof exhibit excellent effects on a variety of harmful organisms, particularly on spider mites represented by Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus kanzawai, Panonychus citri, and the like, and can be used for controlling various harmful mites.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of Chinese Patent Application No. 202110180116.8, filed on February 7, 2021, the contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to the field of pesticide technology, specifically to an aryl sulfide, its preparation method and application, agricultural compositions, and methods for controlling invertebrate pests. Background Technology

[0004] JP201142611A discloses the following general formula compounds with acaricidal activity:

[0005]

[0006] Where A is oxygen or sulfur, and R5 is substituted or unsubstituted C. 1-20 Alkyl groups, substituted or unsubstituted amino groups, nitrogen-containing heterocycles, etc.

[0007] Compounds with the following general formula are disclosed in WO2018015852 (CN109803956A) and possess acaricidal activity.

[0008]

[0009] Where R4 represents hydrogen, formyl group, and C. 1-6 Alkyl groups, etc.; R5 and R6 may be the same or different and each represents hydrogen, halogen, or C. 1-6 Alkyl groups, etc.; R7, R8, R9, R 10 R 11 They may be the same or different and each represents hydrogen, halogen, etc.; X represents oxygen or sulfur.

[0010] CN111825585A discloses a compound with the following general formula, which has acaricidal activity.

[0011]

[0012] However, the above compounds still have low killing activity in the control of pests, especially mites. Their acaricidal activity is often unsatisfactory, especially at low application rates, and they are even less effective against resistant spider mites. Therefore, there is still an urgent need in agricultural production for new drugs that are highly effective, low in toxicity, and have excellent killing effects on resistant mites. Summary of the Invention

[0013] The purpose of this invention is to overcome the technical problem that existing compounds have low killing activity in the control of invertebrate pests (especially mites) and to provide an aryl sulfide, its preparation method and application, an agricultural composition, and a method for controlling invertebrate pests.

[0014] The inventors of this invention have unexpectedly discovered that replacing the hydrogen on the nitrogen of the compound previously disclosed by the inventors (aryl sulfide disclosed in CN111825585A) with substituted acyl, alkyl, sulfonyl, or other groups can result in more efficient killing activity against invertebrate pests (especially mites).

[0015] Therefore, in order to achieve the above objectives, a first aspect of the present invention provides an aryl sulfide, which is a compound with the structure shown in Formula I or an agriculturally acceptable salt thereof.

[0016]

[0017] in,

[0018] n is 0 or 1;

[0019] X and Y are each independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy;

[0020] R1 can be fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, or C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkyl sulfonyl, C1-C 10 Haloalkylsulfonyl, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C2-C 10 alkynyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C2-C 10 cyanoalkoxycarbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C1-C 10alkyl sulfinyl or C1-C 10 Halogenated alkyl sulfinyl group;

[0021] R2, R3, R4, and R5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C2-C 10 Cyanoalkyl carbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl;

[0022] R6 is a C1-C6 haloalkyl, C2-C6 alkynyl, C2-C6 alkenyl, C1-C6 alkyl, C3-C6 cycloalkyl, or C3-C6 epoxyalkyl;

[0023] R7 is C1-C 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkyl sulfonyl, C1-C 10 Haloalkylsulfonyl, C1-C 10 Alkyl carbonyl or C1-C 10 Halogenated alkyl carbonyl group.

[0024] A second aspect of the present invention provides a method for preparing aryl sulfides, the method comprising:

[0025] By contacting the compound shown in Formula II with the compound shown in Formula III, the compound shown in Formula I is obtained.

[0026] R7-QIII

[0027] In Formulas II and III, the definitions of n, X, Y, R1, R2, R3, R4, R5, R6 or R7 are the same as those previously defined; Q is a halogen, methanesulfonate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride.

[0028] A third aspect of the present invention provides the application of the aryl sulfides described in the first aspect above in the control of invertebrate pests.

[0029] A fourth aspect of the present invention provides an agricultural composition comprising at least one aryl sulfide as described in the first aspect and at least one liquid or solid carrier.

[0030] The fifth aspect of the present invention provides a method for controlling invertebrate pests, the method comprising applying an insecticidal effective amount of the aryl sulfide described in the first aspect directly or indirectly to the invertebrate pests to be controlled and / or their growth medium.

[0031] Compared with the prior art, the present invention has at least the following advantages:

[0032] (1) The aryl sulfides provided by the present invention have shown excellent effects on a variety of harmful organisms, especially on spider mites such as two-spotted spider mite, Kanzawa spider mite, and citrus spider mite;

[0033] (2) The aryl sulfides provided by the present invention have good properties in protecting important crops and livestock from mites in agriculture and horticulture. Detailed Implementation

[0034] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0035] A first aspect of the present invention provides an aryl sulfide, which is a compound with the structure shown in Formula I or an agriculturally acceptable salt thereof.

[0036]

[0037] in,

[0038] n is 0 or 1;

[0039] X and Y are each independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy;

[0040] R1 can be fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, or C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkyl sulfonyl, C1-C 10 Haloalkylsulfonyl, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C2-C 10 alkynyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C2-C 10 cyanoalkoxycarbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C1-C 10 alkyl sulfinyl or C1-C 10 Halogenated alkyl sulfinyl group;

[0041] R2, R3, R4, and R5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl;

[0042] R6 is a C1-C6 haloalkyl, C2-C6 alkynyl, C2-C6 alkenyl, C1-C6 alkyl, C3-C6 cycloalkyl, or C3-C6 epoxyalkyl;

[0043] R7 is C1-C 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkyl sulfonyl, C1-C 10 Haloalkylsulfonyl, C1-C 10 Alkyl carbonyl or C1-C 10 Halogenated alkyl carbonyl group.

[0044] According to some embodiments of the present invention, n is 0 or 1; X is fluorine, chlorine or methyl; Y is chlorine or methyl;

[0045] R1 is C1-C6 alkoxycarbonyl, C1-C6 haloalkoxycarbonyl, C2-C6 alkenoxycarbonyl, C2-C6 alkynoxycarbonyl, C2-C6 cyanoalkoxycarbonyl, C1-C6 alkylthio, C1-C6 haloalkoxythio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl.

[0046] R2, R3, R4, and R5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, or C1-C6 alkoxycarbonyl.

[0047] R6 is a C1-C4 haloalkyl or a C1-C4 alkyl;

[0048] R7 is a C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylcarbonyl, or C1-C6 haloalkylcarbonyl.

[0049] According to some embodiments of the present invention, n is 0 or 1;

[0050] X is either fluorine or methyl;

[0051] Y is either chlorine or methyl;

[0052] R1 is C1-C4 alkoxycarbonyl, C1-C4 haloalkoxycarbonyl, C2-C4 alkenoxycarbonyl, C2-C4 alkynoxycarbonyl or C2-C6 cyanoalkoxycarbonyl;

[0053] R2, R4, and R5 are each hydrogen atoms;

[0054] R3 is hydrogen, fluorine, chlorine, or cyano;

[0055] R6 is a C1-C4 haloalkyl group;

[0056] R7 is a C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl, C1-C6 alkylcarbonyl, or C1-C6 haloalkylcarbonyl; wherein the carbonyl group is attached to a nitrogen atom in Formula I.

[0057] According to some embodiments of the present invention, n is 0 or 1; X is fluorine; Y is chlorine or methyl;

[0058] R1 can be methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethoxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl, or cyanoethoxycarbonyl.

[0059] R2, R4, and R5 are each hydrogen atoms;

[0060] R3 is hydrogen, fluorine, chlorine, or cyano;

[0061] R6 is 2,2,2-trifluoroethyl;

[0062] R7 is methyl, ethyl, chloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, pentafluoropropionyl, trichloroacetyl, methanesulfonyl, ethanesulfonyl, or trifluoromethanesulfonyl.

[0063] In this invention, preferably, the aryl sulfides have the structures shown in Table 1; however, the compounds included in the derivatives of this invention are by no means limited to these compounds. Furthermore, the compound numbers shown in Table 1 refer to the description below (Table 1). In this invention, the aryl sulfides and their derivatives may contain E-type and Z-type geometric isomers depending on the type of substituents; this invention includes these E-type, Z-type, or mixtures containing E-type and Z-type in any proportion. Additionally, in the compounds included in this invention, there may be optical isomers caused by having one or more asymmetric carbon atoms and asymmetric sulfur atoms; this invention includes all optical isomers, racemates, or diastereomers.

[0064] In Table 1, the groups corresponding to the following expressions (e.g., Me, Et, tBu, CF3, Ac) are as follows:

[0065] Me: Methyl; Et: Ethyl; tBu: Tert-Butyl; CF3: Trifluoromethyl; Ac: Acetyl.

[0066] Table 1

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103] In this invention, the term "agriculturally acceptable salt" refers to the salt formed by the presence of hydroxyl, carboxyl, or amino groups in the structure of the compounds of this invention represented by Formula I, when such groups are present in their structure. Examples include salts formed with metals or organic bases, or salts formed with inorganic or organic acids, such as potassium, sodium, magnesium, or calcium salts. Examples of organic bases include triethylamine or diisopropylamine; examples of inorganic acids include hydrochloric acid, sulfuric acid, and hydrobromic acid; and examples of organic acids include formic acid, acetic acid, methanesulfonic acid, fumaric acid, and maleic acid.

[0104] A second aspect of the present invention provides a method for preparing aryl sulfides, the method comprising contacting a compound of formula II with a compound of formula III to obtain a compound of formula I.

[0105] R7-QIII

[0106] In Formulas II and III, the definitions of n, X, Y, R1, R2, R3, R4, R5, R6 or R7 are the same as those mentioned above; Q is a halogen (which can be chlorine, bromine or iodine), methanesulfonate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride.

[0107] The present invention does not particularly limit the halogen, methanesulfonate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted anhydride, as long as it can provide an R7 group for the compound shown in Formula I.

[0108] In this invention, R7-Q can be iodomethane, ethyl trifluoroacetate, trifluoroacetic anhydride, trifluoroacetyl chloride, ethyl difluoroacetate, difluoroacetic anhydride, ethyl trichloroacetate, trichloroacetic anhydride, methanesulfonyl chloride, ethyl sulfonyl chloride, or trifluoromethanesulfonic anhydride.

[0109] According to some embodiments of the present invention, preferably, the contact conditions include: a temperature of -20°C to 210°C, more preferably -10°C to 150°C; and a time of 1-50 hours, more preferably 3-25 hours.

[0110] According to some embodiments of the present invention, the molar ratio of the compound shown in Formula I to the compound shown in Formula III may be 1:(1-5), preferably 1:(2-3).

[0111] According to some embodiments of the present invention, preferably, the contact is carried out in the presence of a solvent, wherein the amount of solvent used is 5-30 mL, preferably 10-20 mL, relative to 1 g of the compound represented by Formula I.

[0112] The solvent is selected from at least one of N,N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1,2-dichloroethane, chloroform, xylene, and ethyl acetate.

[0113] According to some embodiments of the present invention, preferably, the contact is carried out in the presence of a base, wherein the amount of the base is 1-5 mol, preferably 2-3 mol, relative to 1 mol of the compound represented by Formula I.

[0114] The base is selected from at least one of triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine, and 1,8-diazabicycloundec-7-ene.

[0115] In this invention, preferably, there are no particular limitations on the post-treatment of the contact, as long as it meets the requirements of this invention. For example, it can be carried out as follows: adding an extraction solvent and water to the reaction solution after contact, performing extraction and separation to obtain an organic phase, discarding the aqueous phase; the organic phase is dried and then separated by column chromatography to obtain the purified product (the compound shown in Formula I). ​​The extraction solvent is not particularly limited, and can be selected from dichloromethane and / or ethyl acetate.

[0116] In this invention, the inventors discovered that the compound represented by Formula I possesses unexpectedly high acaricidal activity. Therefore, the aryl sulfides of this invention can also be used in agriculture or other fields for the preparation of acaricides. In particular, the inventors have found that the compound represented by Formula I has high activity against the following invertebrate pests (the objects listed below are only for illustrative purposes and are not intended to limit the invention): Tetranychidae (such as Tetranychus carmineus, Tetranychus citrus, Tetranychus two-spotted, Tetranychus maculata, Tetranychus kaempferi, Tetranychus hawthornus), Gallidae, Aphididae, Aphididae, Aphididae (such as Prunus persica), nematodes (such as root-knot nematodes, cyst nematodes, short-bodied nematodes, perforating nematodes, and Scaly-scaly-bladed nematodes), etc.

[0117] Therefore, a third aspect of the present invention provides the application of the aryl sulfides described in the first aspect above in the control of invertebrate pests.

[0118] According to some embodiments of the present invention, the invertebrate pests may be mites and / or nematodes.

[0119] In this invention, preferably, the aryl sulfide can be used to protect important crops and livestock in agriculture and horticulture from or minimize damage by mites.

[0120] In this invention, to achieve the desired effect, the amount of aryl sulfide used in some applications varies due to various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infection, the application method, the application environment, and the application formulation.

[0121] In this invention, preferably, for certain applications, such as in agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers may be added to the acaricide composition of this invention, thereby producing additional advantages and effects.

[0122] A fourth aspect of this invention provides an agricultural composition comprising at least one aryl sulfide as described in the first aspect and at least one liquid or solid carrier. The liquid or solid carrier is not particularly limited, as long as it meets the requirements of this invention. Taking a liquid composition as an example, the concentration of the aryl sulfide in the composition can be 0.5-35 mg / L.

[0123] In this invention, the liquid carrier can be water, various aromatic hydrocarbons, aliphatic hydrocarbons, ketones, ethers, etc., such as toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropanol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, naphthane, engine oil, petroleum ether, cyclohexanone, methyl oleate, methyl soybean oil, etc., one or more of these. The solid carrier can include natural or synthetic clays and silicates. Solid carriers suitable for powders can include naturally formed rock powders, chalk, quartz, clay, montmorillonite, silica, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, clay, and synthetic ground minerals (such as micro-dispersed silica or alumina). Suitable particulate carriers can include crushed and graded natural rocks such as calcite, marble, pumice, sepiolite, and dolomite, as well as synthetic particles made from organic and inorganic powders.

[0124] In this invention, preferably, the composition can be applied in the form of a formulation. The compound represented by Formula I is dissolved or dispersed in a carrier as an active ingredient, or formulated to facilitate dispersion for use as a mite control. For example, the composition can be formulated as a wettable powder, water-dispersible granules, suspension, emulsion, aqueous solution, or emulsifiable concentrate. At least one liquid or solid carrier is added to the composition, and a suitable surfactant may be added when necessary. The surfactant may include dodecylbenzene sulfonate, fatty alcohol sulfate, Tween, agricultural emulsions, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignin sulfonate, alkylnaphthalene sulfonate, etc.

[0125] The fifth aspect of this invention provides a method for controlling invertebrate pests. This method includes applying an insecticidal effective amount of the aryl sulfide described in the first aspect directly or indirectly to the invertebrate pest to be controlled and / or its growth medium. There is no particular limitation on whether the method is direct or indirect, as long as it achieves the purpose of controlling invertebrate pests. For example, a direct method may include directly contacting the substance containing the aryl sulfide with the invertebrate pest (including the invertebrate pest directly consuming the substance containing the aryl sulfide, or the invertebrate pest's body surface directly contacting the substance containing the aryl sulfide, etc.). An indirect method may include treating the invertebrate pest's habitat (its habitat or breeding ground, or the plants or soil where the invertebrate pest grows) with the substance containing the aryl sulfide, or treating the food chain with the substance containing the aryl sulfide.

[0126] According to a preferred embodiment of the present invention, the method includes treating plants in which invertebrate pests grow with an insecticidal amount of the aryl sulfide described in the first aspect above.

[0127] In this invention, preferably, the invertebrate pests are mites and / or nematodes. As mentioned above, the mites may include, but are not limited to: spider mites (such as *Tetranychus carmineus*, *Tetranychus citrus*, *Tetranychus two-spotted*, *Tetranychus maculata*, *Tetranychus scabra*, *Tetranychus hawthornensis*), gall mites, tromites, fine-toothed mites, aphids (such as peach aphids), and nematodes (such as root-knot nematodes, cyst nematodes, short-bodied nematodes, perforating nematodes, and *Tetranychus scabra*).

[0128] In this invention, the plant is a plant belonging to the phylum Gymnosperms and / or phylum Angiosperms, preferably at least one of the following: Rutaceae, Solanaceae, Brassicaceae, Fabaceae, and Rosaceae.

[0129] In this invention, there is no particular limitation on the effective insecticidal amount. For example, it can refer to a dosage of 8 grams to 3 kilograms of the aryl sulfide per hectare that can provide sufficient control. Preferably, the effective insecticidal amount can be 8 grams to 1000 grams per hectare, and more preferably, 15 grams to 300 grams per hectare.

[0130] It should be clearly stated that various changes and modifications can be made within the scope defined by the claims of this invention.

[0131] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0132] Preparation Example:

[0133] Preparation Example 1

[0134] Preparation of methyl 2-((N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamido)methyl)benzoate (compound 35)

[0135]

[0136] Methyl 2-((((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (0.5 g, 1.29 mmol) was added to a round-bottom flask, followed by dichloromethane (10 mL) and triethylamine (0.26 g, 2.58 mmol), and then acetyl chloride (0.15 g, 1.935 mmol) was added dropwise. After stirring the reaction solution at room temperature for 4 hours, dichloromethane (30 mL) and water (50 mL) were added. After extraction and separation, the organic phase was dried with anhydrous sodium sulfate (5 g), concentrated under reduced pressure to dryness, and purified by silica gel column chromatography to obtain 0.36 g of white solid.

[0137] 1 H-NMR (400MHz, CDCl3): 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);

[0138] MS (m / z, ESI): 452.3 (m+Na).

[0139] Preparation Example 2

[0140] Preparation of methyl 2-((2-chloro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamido)methyl)benzoate (compound 37)

[0141]

[0142] Prepared according to the method described in Preparation Example 1;

[0143] 1 H-NMR (400MHz, CDCl3): 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);

[0144] MS(m / z,ESI):464.3(m+H).

[0145] Preparation Example 3

[0146] Preparation of methyl 2-((N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)isobutyramido)methyl)benzoate (compound 1877)

[0147]

[0148] Prepared according to the method described in Preparation Example 1;

[0149] 1 H-NMR (400MHz, CDCl3): 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 = 1 4.8Hz,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);

[0150] MS (m / z, ESI): 458.3 (m+H), 480.3 (m+Na).

[0151] Preparation Example 4

[0152] Preparation of methyl 2-((2-chloro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)propamido)methyl)benzoate (compound 57)

[0153]

[0154] Prepared according to the method described in Preparation Example 1;

[0155] 1 H-NMR (400MHz, CDCl3): 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);

[0156] MS(m / z,ESI):478.2(m+H),500.2(m+Na).

[0157] Preparation Example 5

[0158] Preparation of methyl 2-((N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)propamido)methyl)benzoate (compound 53)

[0159]

[0160] Prepared according to the method described in Preparation Example 1;

[0161] 1 H-NMR (400MHz, CDCl3): 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=14.8 Hz,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);

[0162] MS (m / z, ESI): 444.2 (m+H), 466.2 (m+Na).

[0163] Preparation Example 6

[0164] Preparation of methyl 2-((N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)benzamido)methyl)benzoate (compound 1845)

[0165]

[0166] It was prepared according to the method described in Preparation Example 1.

[0167] 1 H-NMR (400MHz, CDCl3): 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);

[0168] MS (m / z, ESI): 514.3 (m+Na).

[0169] Preparation Example 7

[0170] Preparation of methyl 2-(((2,2,2-trifluoro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamido)methyl)benzoate (compound 45)

[0171]

[0172] Methyl 2-((((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (2.5 g, 6.45 mmol) was added to a round-bottom flask, followed by dichloromethane (15 mL) and potassium carbonate (1.34 g, 9.68 mmol). Trifluoroacetic anhydride (1.63 g, 7.74 mmol) was slowly added dropwise at room temperature. The reaction mixture was stirred at room temperature for 3.5 hours. Dichloromethane (20 mL) and water (50 mL) were added to the reaction mixture, and the mixture was extracted. The aqueous phase was extracted again with 20 mL of dichloromethane. The organic phases were combined, dried with anhydrous sodium sulfate (5 g), and concentrated to dryness under reduced pressure. The solution was purified by column chromatography to obtain 2.65 g of white solid.

[0173] 1 H-NMR (400MHz, CDCl3): 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);

[0174] MS (m / z, ESI): 484.2 (m+H), 506.2 (m+Na).

[0175] Preparation Example 8

[0176] Preparation of methyl 2-((2,2-difluoro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamyl)methyl)benzoate (compound 43)

[0177]

[0178] Prepared according to the method described in Preparation Example 7;

[0179] 1H NMR (400MHz, CDCl3): 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);

[0180] MS (m / z, ESI): 466.1 (m+H), 488.1 (m+Na).

[0181] Preparation Example 9

[0182] Preparation of methyl 2-((2,2,2-trichloro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamyl)methyl)benzoate (compound 47)

[0183]

[0184] Prepared according to the method described in Preparation Example 7;

[0185] 1 H NMR (400MHz, CDCl3): 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);

[0186] MS (m / z, ESI): 532.1 (m+H), 556.0 (m+Na).

[0187] Preparation Example 10

[0188] Preparation of methyl (2-fluoro-4-methyl-5-(2,2,2-trifluoroethyl)thiophenyl)(methyl)amino)benzoate (compound 1)

[0189]

[0190] Methyl 2-((((2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (1 g, 2.58 mmol) was added to a 50 mL round-bottom flask, followed by 10 mL of DMF, then potassium carbonate (0.72 g, 5.22 mmol) and methyl iodoform (0.732 g, 5.16 mmol). The reaction mixture was heated to 42 °C and stirred for 24 hours. 50 mL of ethyl acetate and 100 mL of water were added to the reaction mixture. After extraction and separation, 50 mL of ethyl acetate was added to the aqueous phase, and the mixture was extracted and separated again. The organic phases were combined and washed in two batches with 100 mL of water. After separation, the organic phase was dried with anhydrous sodium sulfate (5 g), concentrated under reduced pressure to dryness, and purified by column chromatography to obtain 180 mg of a pale yellow oily liquid.

[0191] 1 H 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);

[0192] MS (m / z, ESI): 402.1 (m+H), 424.1 (m+Na).

[0193] Preparation Example 11

[0194] Preparation of methyl 2-((ethyl(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)amino)methyl)benzoate (compound 3)

[0195]

[0196] It was prepared according to the method described in Preparation Example 10;

[0197] 1H NMR (400MHz, CDCl3): 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);

[0198] MS(m / z,ESI):416.4(m+H).

[0199] Preparation Example 12

[0200] Preparation of 2-((2-fluoro-4-methyl-5-(2,2,2-trifluoroethylthio)phenyl)-(propyl)amino)methylbenzoate (compound 5)

[0201]

[0202] It was prepared according to the method described in Preparation Example 10;

[0203] 1 H-NMR (400MHz, CDCl3): 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);

[0204] MS(m / z,ESI):430.3(m+H).

[0205] Preparation Example 13

[0206] Preparation of ethyl 2-((2,2,2-trifluoro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamyl)methyl)benzoate (compound 103)

[0207]

[0208] A white solid was prepared according to the method described in Preparation Example 7.

[0209] 1 H NMR (400MHz, CDCl3) 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).

[0210] MS(m / z,ESI): 520.1(m+Na).

[0211] Preparation Example 14

[0212] Preparation of methyl 5-fluoro-2-(((2,2,2-trifluoro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamido)methyl)benzoate (compound 1511)

[0213]

[0214] A white solid was prepared according to the method described in Preparation Example 7.

[0215] 1 H NMR (400MHz, CDCl3) 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).

[0216] Preparation Example 15

[0217] Preparation of 2-(((2,2,2-trifluoro-N-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)acetamido)methyl)benzoate trifluoroethyl ester (compound 393)

[0218]

[0219] A white solid was prepared according to the method described in Preparation Example 7.

[0220] 1H NMR (400MHz, CDCl3) 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).

[0221] MS(m / z,ESI):574.15(m+Na).

[0222] Preparation Example 16

[0223] Preparation of methyl 2-((N-(4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)-2,2,2-trifluoroacetamido)methyl)benzoate (compound 799)

[0224]

[0225] 1 H NMR (400MHz, CDCl3) 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=8.0H z,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).

[0226] MS (m / z, ESI): 526.08 (m+Na).

[0227] Preparation Example 17

[0228] Preparation of ethyl methyl 2-((N-(4-chloro-2-fluoro-5-((2,2,2-trifluoroethyl)thio)phenyl)-2,2,2-trifluoroacetamido)methyl)benzoate (compound 857)

[0229] A white solid was prepared according to the method described in Preparation Example 7.

[0230]

[0231] 1H NMR (400MHz, CDCl3) 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=7.6H z,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).

[0232] MS(m / z,ESI):540.01(m+Na).

[0233] Formulation Example 1:

[0234] Preparation of 20% Compound 45 Emulsifiable Concentrate

[0235] Take 20 parts by weight of compound 45 and dissolve it in 24 parts by weight of N-methylpyrrolidone. Then add 12 parts by weight of 500# (calcium dodecylbenzenesulfonate) and 6 parts by weight of 33# (triphenylethylphenol polyoxyethylene ether), stir well, add 7.2 parts by weight of methyl oleate 680, continue to stir well, and then add methyl naphthalene to fill the remaining amount to 100 parts by weight. After stirring well, a 20% compound 45 emulsifiable concentrate formulation is obtained.

[0236] Application Example 1

[0237] Cinnabar Tetranychus activity test

[0238] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% by weight Tween 80 aqueous solution, with the acetone content not exceeding 5% by weight.

[0239] Remove one true leaf from bean seedlings that have grown to two true leaves. Inoculate with Tetranychus carmineus and assess the initial mite population. Spray the entire plant with a handheld sprayer. Repeat each treatment three times (approximately 0.5g of the preparation). Observe the plants in a constant-temperature observation room after treatment. After 72 hours, assess the number of live mites and calculate the mortality rate. The experiment was repeated three times, with 50-150 Tetranychus carmineus mites inoculated each time.

[0240] Mortality rate = (Number of inoculated worms - Number of surviving worms after treatment) ÷ Number of inoculated worms × 100%.

[0241] In this test, the following compounds showed a lethality of over 90% at 25 ppm (25 mg / L):

[0242] 1, 3, 5, 37, 43, 45, 47, 57, 103, 393, 799, 857, 1511.

[0243] In this test, the following compounds showed a lethality of over 90% at 6.25 ppm (6.25 mg / L):

[0244] 1, 43, 45, 47, 103, 393, 799, 857, 1511.

[0245] In this test, the following compounds showed a lethality of over 80% at 1.56 ppm (1.56 mg / L):

[0246] 45, 103, 393, 799, 857, 1511.

[0247] Following the above method, parallel experiments were conducted on compounds 45, 103, and compound 53 disclosed in CN111825585A to kill mites (Tetranychus cinnabarinus). The results are shown in Table 2 below:

[0248] Table 2

[0249]

[0250] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An aryl sulfide, characterized in that, The aryl sulfide is a compound with the structure shown in Formula I or an agriculturally acceptable salt thereof. I， in, n is 0 or 1; X and Y are each independently a halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy or C1-C3 haloalkoxy; R1 can be fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, or C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkyl sulfonyl, C1-C 10 Haloalkylsulfonyl, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C2-C 10 alkynyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C2-C 10 cyanoalkoxycarbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl, C1-C 10 alkyl sulfinyl or C1-C 10 Halogenated alkyl sulfinyl group; R2, R3, R4, and R5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, and C1-C. 10 Alkyl, C1-C 10 Haloalkyl, C1-C 10 Alkoxy, C1-C 10 Halogenated alkoxy groups, C1-C 10 alkoxycarbonyl, C1-C 10 Haloalkoxycarbonyl, C1-C 10 Alkylsulfonyloxy, C1-C 10 Alkylthio, C1-C 10 Haloalkylthio group, C2-C 10 Alkenyloxycarbonyl, C1-C 10 Alkyl carbonyl, amino carbonyl, C1-C 10 N-alkylcarbonyl, N,N-dimethylcarbonyl, N,N-dimethylthiocarbonyl, C1-C 10 N-alkylthiocarbonyl, 2-oxopropoxycarbonyl; R6 is a C1-C6 haloalkyl, C2-C6 alkynyl, C2-C6 alkenyl, C1-C6 alkyl, C3-C6 cycloalkyl, or C3-C6 epoxyalkyl; R7 is C1-C 10 Halogenated alkyl carbonyl; wherein the carbonyl group is bonded to a nitrogen atom in Formula I.

2. The aryl sulfide according to claim 1, wherein, n is 0 or 1; X is fluorine, chlorine, or methyl; Y is either chlorine or methyl; R1 is a C1-C6 alkoxycarbonyl, C1-C6 haloalkoxycarbonyl, C2-C6 alkenoxycarbonyl, C2-C6 alkynoxycarbonyl, C 2- C6 cyanoalkoxycarbonyl, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; R2, R3, R4, and R5 are each independently hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, amino, hydroxymethyl, carboxyl, hydroxyl, mercapto, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, or C1-C6 alkoxycarbonyl. R6 is a C1-C4 haloalkyl or a C1-C4 alkyl; R7 is a C1-C6 haloalkyl carbonyl group; wherein the carbonyl group is attached to a nitrogen atom in Formula I.

3. The aryl sulfide according to claim 1 or 2, wherein, n is 0 or 1; X is either fluorine or methyl; Y is either chlorine or methyl; R1 is a C1-C4 alkoxycarbonyl, C1-C4 haloalkoxycarbonyl, C2-C4 alkenoxycarbonyl, C2-C4 alkynoxycarbonyl, or C 2- C6 cyanoalkoxycarbonyl; R2, R4, and R5 are each hydrogen atoms; R3 is hydrogen, fluorine, chlorine, or cyano; R6 is a C1-C4 haloalkyl group; R7 is a C1-C6 haloalkyl carbonyl group; wherein the carbonyl group is attached to a nitrogen atom in Formula I.

4. The aryl sulfide according to claim 3, wherein, n is 0 or 1; X is fluorine; Y is either chlorine or methyl; R1 can be methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethoxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl, or cyanoethoxycarbonyl. R2, R4, and R5 are each hydrogen atoms; R3 is hydrogen, fluorine, chlorine, or cyano; R6 is 2,2,2-trifluoroethyl; R7 is chloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, pentafluoropropionyl, or trichloroacetyl; wherein the carbonyl group is bonded to the nitrogen atom in Formula I.

5. The aryl sulfide according to claim 4, wherein, n is 0; X is fluorine; Y represents a methyl group; R1 can be methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isopropoxycarbonyl, cyclopropoxycarbonyl, tert-butoxycarbonyl, fluoroethoxycarbonyl, difluoroethoxycarbonyl, trifluoroethoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl, pentafluoropropoxycarbonyl, or cyanoethoxycarbonyl. R2, R4, and R5 are each hydrogen atoms; R3 is hydrogen; R6 is 2,2,2-trifluoroethyl; R7 is trifluoroacetyl.

6. A method for preparing aryl sulfides, characterized in that, The method includes: By contacting the compound shown in Formula II with the compound shown in Formula III, the compound shown in Formula I is obtained. II, R7-QIII In Formulas II and III, the definitions of n, X, Y, R1, R2, R3, R4, R5, R6 or R7 are the same as those in any one of claims 1-3; Q is a halogen, methanesulfonate group, benzenesulfonate group, p-toluenesulfonate group, trifluoromethanesulfonate group or substituted acid anhydride.

7. The method according to claim 6, wherein, The contact conditions include: a temperature of -20°C to 210°C; and a contact time of 1-50 hours. And / or, the molar ratio of the compound shown in Formula I to the compound shown in Formula III is 1:(1-5); And / or, the contact is carried out in the presence of a solvent, wherein the amount of solvent is 5-30 mL relative to 1 g of the compound shown in Formula I; The solvent is selected from at least one of N,N-dimethylformamide, dichloromethane, acetonitrile, acetone, tetrahydrofuran, N-methylpyrrolidone, water, methanol, ethanol, dimethyl sulfoxide, toluene, 1,2-dichloroethane, chloroform, xylene, and ethyl acetate. And / or, the contact is carried out in the presence of a base, wherein the amount of base used is 1-5 mol relative to 1 mol of the compound represented by Formula I; The base is selected from at least one of triethylamine, diisopropylethylamine, sodium hydride, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, pyridine, and 1,8-diazabicycloundec-7-ene.

8. The method according to claim 7, wherein, The contact conditions include: a temperature of -10°C to 150°C; and a contact time of 3-25 hours. And / or, the molar ratio of the compound shown in Formula I to the compound shown in Formula III is 1:(2-3); And / or, the contact is carried out in the presence of a solvent, wherein the amount of solvent is 10-20 mL relative to 1 g of the compound shown in Formula I; And / or, the contact is carried out in the presence of a base, wherein the amount of base is 2-3 mol relative to 1 mol of the compound represented by Formula I.

9. The use of an aryl sulfide according to any one of claims 1-5 in the preparation of an agent for controlling invertebrate pests.

10. The application according to claim 9, wherein the invertebrate pest is a mite and / or a nematode.

11. An agricultural composition, characterized in that, The composition comprises at least one aryl sulfide as described in any one of claims 1-4 and at least one liquid or solid carrier.

12. A method for controlling invertebrate pests for non-therapeutic purposes, characterized in that, The method comprises applying, directly or indirectly, an insecticidal effective amount of the aryl sulfide according to any one of claims 1-5 to the invertebrate pests to be controlled and / or their growth medium.

13. The method according to claim 12, wherein, The method comprises treating plants infested with invertebrate pests with an insecticidal amount of the aryl sulfide according to any one of claims 1-3.

14. The method according to claim 13, wherein, The invertebrate pests mentioned are mites and / or nematodes.

15. The method according to claim 13, wherein, The plants are plants belonging to the phylum Gymnosperms and / or phylum Angiosperms.

16. The method according to claim 15, wherein, The plant is at least one of the following: Rutaceae, Solanaceae, Brassicaceae, Fabaceae, and Rosaceae.

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