Sulfite compound, preparation method therefor, use and composition thereof, and method for preventing and treating pest mites

Abstract

A sulfite compound, a preparation method therefor, a use and composition thereof, and a method for preventing and treating pest mites. The compound has a structure as represented by formula (I). On the basis of the total mass of isomers of two configurations (1S,2S) and (1R,2R) in the compound having the structure as represented by formula (I), the content of a stereoisomer of the (1S,2S) configuration is 60 mol% or more. Compared with propargite, the sulfite compound as represented by formula (I) can achieve a better acaricidal effect at a lower use concentration.

Description

Sulfite compound, preparation method and application thereof, composition thereof, and method for controlling harmful mites

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of Chinese patent application No. 202310804963.6 filed on July 3, 2023, the contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to the technical field of pesticides, and in particular to a sulfite compound, a preparation method and application thereof, a composition thereof, and a method for preventing and controlling harmful mites. Background Art

[0004] In recent years, the prevention and control of agricultural pests has become increasingly difficult. The main reason is that pests have the characteristics of rapid reproduction and strong adaptability, which makes agricultural pests quickly develop resistance to existing acaricides. As a result, the use of chemical acaricides is increasing.

[0005] US3272854A discloses the following sulfite compounds as having certain acaricidal activity: RO-R'-OSOR", where R can be tert-butylphenyl or 2-chlorophenyl; R" can be 2-chloroethyl; and R' can be 1,2-cyclohexyl. When R is 4-tert-butylphenyl, R" is propargyl or 2-chloroethyl, and R' is 1,2-cyclohexyl, the sulfite compound exhibits 100% lethality against mites at 200 ppm. When R" is propargyl, the only commercially available acaricide from this sulfite compound is propargyl.

[0006] There are no reports on photoactive sulfite compounds and their acaricidal activity. Taking propargyl as an example, the molar proportion of its four configurations is close to 25%.

[0007] Propargine, a sulfite acaricide developed in the 1960s, is characterized by its slow development of resistance and remains a widely used acaricide. However, due to its low acaricidal activity, a large dosage per unit area is required. Furthermore, Propargine is less safe for the tender leaves, fruits, and flowers of many crops, making field use prone to phytotoxicity, particularly in hot weather. This significantly limits the scope and duration of Propargine's application.

[0008] Therefore, the market is in urgent need of developing more efficient sulfite compounds that can be used as acaricides.

[0009] Summary of the Invention

[0010] The purpose of the present invention is to overcome the problem that sulfite acaricides in the prior art have low killing activity in controlling pest mites, and to provide a sulfite compound, a preparation method and application thereof, a composition and a method for controlling pest mites.

[0011] The inventors of the present invention have found that increasing the content of the (1S, 2S) stereoisomer in the product is particularly beneficial to improving the acaricidal activity of sulfite acaricides. Therefore, in order to achieve the above-mentioned object, the first aspect of the present invention provides a sulfite compound having a structure shown in formula (I):

[0012] Wherein, based on the total amount of (1S, 2S) configuration and (1R, 2R) configuration isomers in the compound represented by the structure of formula (I), the content of the (1S, 2S) configuration stereoisomer is greater than 60 mol%;

[0013] R1 is selected from 2-propynyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 3,3,3-trifluoropropyl or 2,2,3,3-tetrafluoropropyl;

[0014] R2, R3, R4, R5, and R6 are each independently selected from hydrogen, tert-butyl, fluorine, chlorine, bromine, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, phenyl, phenoxy, benzyloxy, trifluoromethyl, cyano, methylthio, methylsulfinyl, or methylsulfonyl.

[0015] A second aspect of the present invention provides a method for preparing a sulfite compound, the method comprising:

[0016] (1) In the presence of solvent A, the compound represented by formula (II) is subjected to a first coupling reaction with thionyl chloride, followed by post-treatment to obtain a compound represented by formula (III):

[0017] (2) In the presence of solvent B and an alkaline substance, the compound represented by formula (III) is subjected to a second coupling reaction with the alcohol represented by formula (IV), followed by purification to obtain the compound represented by formula (I):

[0018] Among them, the definitions of R1, R2, R3, R4, R5, R6 and C 1 、C 2 The configuration is the same as the definition and configuration described in any one of claims 1 to 3.

[0019] The third aspect of the present invention provides a sulfite compound prepared by the method described in the second aspect of the present invention.

[0020] The fourth aspect of the present invention provides a use of the sulfite compound described in the first aspect or the third aspect of the present invention in controlling pest mites.

[0021] The fifth aspect of the present invention provides a composition comprising at least one of the sulfite compounds described in the first and third aspects of the present invention, and a liquid carrier and / or a solid carrier.

[0022] The sixth aspect of the present invention provides a method for controlling pest mites, characterized in that the method comprises: applying the sulfite compound described in the first or third aspect of the present invention or the composition described in the fifth aspect of the present invention directly or indirectly to the pest mites to be controlled and / or the medium in which they grow.

[0023] Through the above technical solution, compared with vinmant, the sulfite compound represented by formula (I) prepared in the present invention can achieve a better acaricidal effect at a lower usage concentration. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] FIG1 is a chiral HPLC spectrum of (±)-trans-2-(4-tert-butylphenoxy)cyclohexanol;

[0025] Figure 2 is a chiral HPLC spectrum of (1S, 2S) trans-2-(4-(tert-butyl)phenoxy)cyclohexane;

[0026] FIG3 is a chiral HPLC spectrum of (1S, 2S) trans-2-(4-(tert-butyl)phenoxy)cyclohexylprop-2-yn-1-sulfite;

[0027] FIG4 is a chiral HPLC spectrum of chlorpyrifos. DETAILED DESCRIPTION

[0028] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0029] The first aspect of the present invention provides a sulfite compound having a structure shown in formula (I):

[0030] Wherein, based on the total amount of (1S, 2S) configuration and (1R, 2R) configuration isomers in the compound represented by the structure of formula (I), the content of the stereoisomer of the (1S, 2S) configuration is greater than 60 mol%, for example, it can be 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value within any range;

[0031] R1 is selected from 2-propynyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 3,3,3-trifluoropropyl or 2,2,3,3-tetrafluoropropyl;

[0032] R2, R3, R4, R5, and R6 are each independently selected from hydrogen, tert-butyl, fluorine, chlorine, bromine, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, phenyl, phenoxy, benzyloxy, trifluoromethyl, cyano, methylthio, methylsulfinyl, or methylsulfonyl.

[0033] In some embodiments of the present invention, preferably, based on the total amount of (1S, 2S) and (1R, 2R) stereoisomers in the compound represented by formula (I), the content of the (1S, 2S) stereoisomer is greater than 70 mol%.

[0034] R1 is selected from 2-propynyl, 2-fluoroethyl, 2-chloroethyl or 3,3,3-trifluoropropyl;

[0035] R2 and R6 are each independently selected from hydrogen, fluorine, chlorine, bromine, trifluoromethyl, cyano, trifluoromethoxy or 2,2,2-trifluoroethoxy;

[0036] R3 and R5 are both hydrogen;

[0037] R4 is selected from tert-butyl, chloro, trifluoromethoxy, 2,2,2-trifluoroethoxy or phenoxy.

[0038] More preferably, based on the total amount of (1S, 2S) and (1R, 2R) stereoisomers in the compound represented by formula (I), the content of the (1S, 2S) stereoisomer is greater than 80 mol%.

[0039] R1 is selected from 2-propynyl or 2-fluoroethyl;

[0040] R2 and R6 are each independently selected from hydrogen, chlorine or fluorine;

[0041] R4 is selected from tert-butyl, chloro or trifluoromethoxy;

[0042] Wherein, the sulfur atom configuration is selected from R configuration or S configuration, or a mixture thereof.

[0043] According to a preferred embodiment of the present invention, based on the total amount of all isomers in the compound represented by formula (I), C 1 The content of the stereoisomer of S configuration is above 60 mol%, such as 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value within any range; C 2 The content of the stereoisomer having the S configuration is above 60 mol%, such as 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value within any range.

[0044] According to a more preferred embodiment of the present invention, based on the total amount of all isomers in the compound of the structure shown in formula (I), the content of the (1S, 2S) configuration is 60 mol%-100 mol%, for example, it can be 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value in any range; the content of the (1R, 2R) configuration is 0-40 mol%, for example, it can be 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%. %, 35mol%, 40mol%, and any range consisting of any two of the above values ​​and any value in any range; the content of (1R, 2S) configuration is 0-2.5mol%, for example, it can be 0.5mol%, 1mol%, 1.5mol%, 2mol%, 30mol%, 2.5mol%; the content of (1S, 2R) configuration is 0-2.5mol%, for example, it can be 0.5mol%, 1mol%, 1.5mol%, 2mol%, 30mol%, 2.5mol%, and any range consisting of any two of the above values ​​and any value in any range.

[0045] According to another embodiment of the present invention, the present invention relates to a sulfite compound having a structure shown in formula (I):

[0046] Wherein, based on the total amount of all isomers in the compound of the structure shown in formula (I), C 1 The content of the stereoisomer with S configuration is above 60 mol%, such as 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value within any range; C2 The content of the stereoisomer with S configuration is above 60 mol%, such as 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 95 mol%, 100 mol%, and any range consisting of any two of the above values ​​and any value in any range; R1, R2, R3, R4, R5, and R6 are as described above.

[0047] In the present invention, the content of the stereoisomer of the (1S, 2S) configuration can be controlled within the above range by a purification method for photoactive compounds commonly used in the art. Alternatively, the content of the stereoisomer of the (1S, 2S) configuration in the raw material can be controlled to obtain a sulfite compound having a content of the stereoisomer of the (1S, 2S) configuration that satisfies the above range. In order to further improve the yield of the sulfite compound, the second aspect of the present invention provides a method for preparing a sulfite compound, the method comprising:

[0048] (1) In the presence of solvent A, the compound represented by formula (II) is subjected to a first coupling reaction with thionyl chloride, followed by post-treatment to obtain a compound represented by formula (III):

[0049] (2) In the presence of solvent B and an alkaline substance, the compound represented by formula (III) is subjected to a second coupling reaction with the alcohol represented by formula (IV), followed by purification to obtain the compound represented by formula (I):

[0050] Among them, the definitions of R1, R2, R3, R4, R5, R6 and C 1 、C 2 The configuration is the same as the definition and configuration in the first aspect.

[0051] In some embodiments of the present invention, preferably, in step (1), the solvent A is selected from dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, acetone, toluene, or xylene; preferably selected from dichloromethane, 1,2-dichloroethane, or toluene. In some embodiments of the present invention, preferably, the molar ratio of thionyl chloride to the compound represented by formula (II) is 0.2-5:1, preferably 0.7-1.5:1.

[0052] In some embodiments of the present invention, preferably, the reaction temperature of the first coupling reaction is -20°C to 80°C, preferably -10°C to 30°C; the reaction pressure of the first coupling reaction is 0-1 MPa, preferably 0-0.1 MPa; the reaction time of the first coupling reaction is 0.01-10 h, preferably 0.1-2 h.

[0053] In some embodiments of the present invention, preferably, in step (2), the solvent B is selected from dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, acetone, toluene or xylene; preferably selected from dichloromethane, 1,2-dichloroethane or toluene; the alcohol represented by formula (IV) is selected from 2-propynol, 2-fluoroethanol, 2,2-difluoroethanol, 2-chloroethanol, 3,3,3-trifluoropropanol or 2,2,3,3-tetrafluoropropanol; preferably selected from 2-propynol, 2-fluoroethanol or 3,3,3-trifluoropropanol.

[0054] The alkaline substance is selected from an organic base or an inorganic base; preferably selected from at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, triethylamine, diisopropylethylamine and pyridine.

[0055] In some embodiments of the present invention, preferably, the molar ratio of the alkaline substance to the compound represented by formula (III) is 0.2-5:1, preferably 0.7-1.5:1; the molar ratio of the alcohol represented by formula (IV) to the compound represented by formula (III) is 0.2-5:1, preferably 0.7-1.5:1.

[0056] In some embodiments of the present invention, preferably, the reaction temperature of the second coupling reaction is -20°C to 80°C, preferably -10°C to 30°C; the reaction pressure of the second coupling reaction is 0-1 MPa, preferably 0-0.1 MPa; the reaction time of the second coupling reaction is 0.01-10 h, preferably 0.1-1 h.

[0057] In some embodiments of the present invention, preferably, the post-treatment includes a reduced-pressure rotary evaporation operation.

[0058] In some embodiments of the present invention, preferably, the purification treatment includes extraction, drying, rotary evaporation and column chromatography operations.

[0059] The third aspect of the present invention provides a sulfite compound prepared by the method described in the second aspect of the present invention.

[0060] The fourth aspect of the present invention provides a use of the sulfite compound described in the first aspect or the third aspect of the present invention in controlling pest mites.

[0061] The inventors of the present invention have discovered that the compounds represented by formula (I) have unexpectedly high acaricidal activity. Therefore, the photoactive 2-phenoxycyclohexylsulfite compounds of the present invention can also be used in agriculture or other fields to prepare acaricides. In particular, the inventors of the present invention have discovered that the compounds represented by formula (I) have high activity against the following pest mites: Tetranychus cinnabarinus (e.g., Tetranychus cinnabarinus, Panonychus citri, Tetranychus urticae, Panonychus apicale, Tetranychus kanzawa, Tetranychus chinensis), Tetranychus serratus, Tetranychus serratus, and Tetranychus chinensis, Acaridae, and Tetranychus gracilis.

[0062] In some embodiments of the present invention, preferably, the harmful mite is a pest mite of the family Tetranychus.

[0063] In the present invention, preferably, the photoactive 2-phenoxycyclohexyl sulfite compound can be used to protect important crops and livestock in agriculture and horticulture from or from being harmed by harmful mites.

[0064] In the present invention, in order to obtain the desired effect, in some applications, the amount of the photoactive 2-phenoxycyclohexyl sulfite compound used varies depending on 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, the application formulation, and the like.

[0065] In the present invention, preferably, for certain applications, such as agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers can be added to the agricultural composition of the present invention, thereby producing additional advantages and effects.

[0066] The fifth aspect of the present invention provides a composition comprising at least one of the sulfite compounds described in the first and third aspects of the present invention, and a liquid carrier and / or a solid carrier.

[0067] In some embodiments of the present invention, preferably, the liquid carrier is selected from water, aromatic hydrocarbons, aliphatic hydrocarbons, ketones, and ethers, and is preferably selected from at least one of toluene, xylene, acetone, cyclohexanone, xylene, benzene, cyclohexane, isopropanol, ethylene glycol, sorbitol, methanol, ethanol, butanol, dimethylformamide, N-methylpyrrolidone, decalin, motor oil, petroleum ether, cyclohexanone, methyl oleate, and methylated soybean oil.

[0068] In some embodiments of the present invention, preferably, the solid carrier is selected from powdered or granular silicates, preferably at least one selected from naturally occurring rock powder, chalk, quartz, clay, montmorillonite, white carbon black, diatomaceous earth, pumice, gypsum, talc, bentonite, kaolin, clay, synthetic ground minerals (such as finely dispersed silicic acid or alumina), calcite, marble, pumice, sepiolite and dolomite.

[0069] In some embodiments of the present invention, preferably, the composition can be applied in the form of a preparation. The compound represented by formula (I) is dissolved or dispersed in the carrier as an active ingredient, or is configured into a preparation so that it is easier to disperse when used for acaricide. For example, the composition can be prepared into a dosage form selected from wettable powders, water-dispersible granules, suspensions, aqueous emulsions, aqueous solutions or emulsifiable concentrates. At least one liquid or solid carrier is added to the composition, and when necessary, a suitable surfactant can also be added. The surfactant is selected from dodecylbenzenesulfonate, fatty alcohol sulfate, Tween, agricultural milk, sorbitol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, lignin sulfonate, alkylnaphthalene sulfonate, etc.

[0070] The sixth aspect of the present invention provides a method for controlling pest mites, wherein the method comprises: applying the sulfite compound described in the first or third aspect of the present invention or the composition described in the fifth aspect of the present invention directly or indirectly to the pest mites to be controlled and / or the medium in which they grow.

[0071] In some embodiments of the present invention, preferably, the method comprises: treating plants where harmful mites grow with an acaricidal effective amount of the sulfite compound of the first or third aspect of the present invention or the composition of the fifth aspect of the present invention.

[0072] In the present invention, the plant is a plant of the phylum Gymnosperms and / or Angiosperms, preferably at least one of the family Rutaceae, Solanaceae, Cruciferae and Rosaceae.

[0073] Preferably, the plant can be selected from citrus, apple, pear, cotton, rose, bean, strawberry, pepper, melon, watermelon, eggplant, peanut, wheat and the like.

[0074] In the present invention, the insecticidally effective amount is not particularly limited. For example, a dosage of 30 g to 1 kg of the photoactive 2-phenoxycyclohexyl sulfite compound per hectare can provide sufficient control. Preferably, the insecticidally effective amount can be 50 g to 300 g per hectare.

[0075] The present invention will be described in detail below by way of examples. In the following examples, the conditions for chiral HPLC analysis and detection are all as follows:

[0076] Chromatographic column: CHIRALPAK AY-H 4.6*250mm*5μm; mobile phase: n-hexane:isopropanol = 70:30; detection wavelength 222. Isopropanol raw material was commercially available from Hengxing Reagent Company, brand 20180102; n-hexane raw material was commercially available from Sapry Company, brand 20220107001.

[0077] The raw material of N-chlorosuccinimide is a commercial product with the trademark 20170417 from Shanghai Hushi Company; the raw material of R-(+)-1,1'-binaphthyl-2,2'-diphenylphosphine is a commercial product with the trademark BD01390881 from Shanghai Bid Pharmaceutical Company.

[0078] Preparation Example 1

[0079] According to the reaction scheme shown above, (±)-trans-2-(4-tert-butylphenoxy)cyclohexanol (19.47 g, 78 mmol; prepared according to the method described in Example 1 of CN100376154C, chiral HPLC analysis showed two main chromatographic peaks in roughly equivalent proportions, the analysis results are shown in Figure 1) was added to anhydrous tetrahydrofuran (200 mL), R-(+)-1,1'-binaphthyl-2,2'-diphenylphosphine (19.42 g, 31.2 mmol) was added, the internal temperature was controlled at 10-15°C in a low-temperature cooling bath, and N-chlorosuccinimide (9.37 g, 70.2 mmol) was added. The reaction mixture was stirred for 50 h and then concentrated under reduced pressure to remove the tetrahydrofuran solvent. The crude product was purified by column chromatography. The fraction with an Rf value of 0.184 (5% ethyl acetate in hexanes) was collected. After removal of the solvent, 9.5 g of II-1 was obtained as a white solid with a melting point of 86.8-89.3°C.

[0080] Chiral HPLC analysis of the above product was performed. The results showed that the peak area of ​​(1S,2S)-trans-2-(4-tert-butylphenoxy)cyclohexanol accounted for 72.1% of the total peak area of ​​the compound's (1S,2S) and (1R,2R) configurations. The chiral HPLC analysis results are shown in Figure 2.

[0081] 1 H NMR (400MHz, CDCl3) δ7.30-7.27(m,2H),6.89-6.87(m,2H),3.98-3.90(m,1H),3.74- 3.65(m,1H),2.58(s,1H),2.18-2.06(m,2H),1.78-1.68(m,2H),1.47-1.26(m,13H).

[0082] 13 C NMR (101MHz, CDCl3) δ155.57,144.03,126.34,115.87,82.34,73.50,34.11,32.04,31.53,29.32,24.04,23.96.

[0083] MS (m / z, ESI): [M+H] +:249.1872; [M+Na] + :271.1692.

[0084] IR(KBr)ν3314.82,3040.60,2942.11,2861.64,1609.16,1578.34,151 1.95,1453.87,1416.50,1385.10,1361.51,1348.48,1291.64,1249.68 ,1203.33,1184.27,1122.77,1074.84,1055.95,1037.33,967.01,951 .89,933.78,870.78,843.31,811.26,730.65,678.11,554.67,470.68.

[0085] [ɑ]D 25 =20.98°(c 0.2,acetone).

[0086] Preparation Example 2

[0087] According to the reaction scheme shown above, referring to the method described in Preparation Example 1, (1S, 2S) configuration-enhanced trans-2-(4-chlorophenoxy)cyclohexanol was prepared.

[0088] Chiral HPLC analysis of the product showed that the peak area of ​​(1S,2S)-trans-2-(4-chlorophenoxy)cyclohexanol accounted for 66.36% of the total peak area of ​​the compound's (1S,2S) configuration and (1R,2R) configuration isomers.

[0089] Preparation Example 3

[0090] According to the reaction scheme shown above, referring to the method described in Preparation Example 1, (1S, 2S) configuration-enhanced trans-2-(4-trifluoromethoxyphenoxy)cyclohexanol was prepared.

[0091] Chiral HPLC analysis of the product showed that the peak area of ​​(1S,2S)-trans-2-(4-trifluoromethoxyphenoxy)cyclohexanol accounted for 68.90% of the total peak area of ​​the compound's (1S,2S) configuration and (1R,2R) configuration isomers.

[0092] 1H NMR(400MHz,Chloroform-d)δ7.17-7.09(m,2H),6.98-6.89(m,2H),3.96(ddd,J=10.5,8.3,4.3Hz,1H),3.72(ddd,J=10.5,8.4,4.6Hz,1H), 2.34(s,1H),2.19-2.05(m,2H),1.76(dq,J=7.6,3.0,2.6Hz,2H),1.39(dddd,J=23.4,10.5,8.7,3.2Hz,1H),1.36(s,1H),1.34-1.22(m,2H).

[0093] 13 C NMR (101MHz, Chloroform-d) δ156.42,143.08,122.49,117.16,82.85,73.37,32.12,29.11,23.94,23.86.

[0094] MS (m / z, ESI): [M+H] + :277.1067.

[0095] [ɑ]D 25 =15.09°(c 0.0108,acetone).

[0096] Example 1

[0097] Preparation of photoactive (1S,2S)-trans-2-(4-(tert-butyl)phenoxy)cyclohexylprop-2-yne-1-sulfite: Toluene (solvent A, 20 mL) and the product II-1 (2 g, 8.1 mmol) obtained in the preparation example were added to a round-bottom flask, and the temperature was cooled to 0°C in an ice bath. Thionyl chloride (1.25 g, 10 mmol) was slowly added, and the reaction was continued in an ice bath for 1 hour. The reaction flask was then subjected to reduced pressure rotary evaporation at room temperature for 20 minutes to obtain a light yellow clear solution.

[0098] To a separate reaction flask, add toluene (solvent B, 20 mL) and triethylamine (alkaline substance, 2.02 g, 20 mmol), add 2-propyn-1-ol (IV-1, 0.68 g, 12 mmol), and slowly add dropwise the light yellow clear solution obtained in the first step under an ice bath. Continue the reaction in an ice bath for 1 hour. Add 100 mL of water and 100 mL of ethyl acetate to the reaction solution, extract and separate the liquids, add 50 mL of ethyl acetate to the aqueous phase again, extract and separate the liquids again, combine the organic phases, add 5 g of anhydrous sodium sulfate to the organic phase, dry for 10 minutes, and then rotary evaporate to dryness. Purify by column chromatography to obtain 0.85 g of a colorless liquid.

[0099] Chiral HPLC analysis revealed four main peaks, indicating the presence of a third chiral center in the compound, namely, the presence of stereoisomers at the sulfur atom. The first peak accounted for 32.33% of the total peak area, the second peak accounted for 38.03%, the third peak accounted for 15.49%, and the fourth peak accounted for 12.22%. The first and second peaks were (1S,2S) isomers, accounting for a combined 70.36% of the peak area, while the third and fourth peaks were (1R,2R) isomers, accounting for 27.71% of the total peak area. Therefore, the (1S,2S) isomer accounted for 71.74% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0100] The results of chiral HPLC analysis are shown in Figure 3.

[0101] 1 H NMR (400MHz, CDCl3) δ7.36-7.27(m,2H),6.93-6.81(m,2H),4.70-4.54(m,2H),4 .53-4.41(m,1H),4.25-4.06(m,1H),2.50(dt,J=8.4,2.5Hz,1H),2.27-2.06(m, 2H),1.75(dd,J=5.7,3.6Hz,2H),1.69-1.32(m,4H),1.29(s,9H).

[0102] 13 C NMR (101MHz, CDCl3) δ155.17,155.11,144.24,144.08,126.36,115.88,115.63,78.56,77.94,77.61,76.30,76 .05,75.70,75.66,48.21,48.10,48.13,34.12,31.52,31.25,31.15,29.72,29.35,23.47,23.18,22.91,22.68.

[0103] MS (m / z, ESI): [M+Na] + :373.1438.

[0104] IR(KBr)ν3286.81,3038.75,2945.13,2865.89,2130.36,1607.23,158 0.10,1509.57,1454.26,1362.49,1290.49,1237.57,1201.72,1183.1 1,1115.90,1053.62,1038.36,977.85,918.81,901.19,869.75,851.5 2,829.82,810.25,772.73,729.79,679.76,610.16,549.59,523.40cm -1 .

[0105] [ɑ] D 26.4 =-2.2°(c 0.01,acetone).

[0106] Example 2

[0107] Preparation of optically active (1S,2S)-trans-2-(4-(tert-butyl)phenoxy)cyclohexyl-2-fluoroethyl-sulfite:

[0108] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(tert-butyl)phenoxy)cyclohexyl-2-fluoroethyl-sulfite (Compound I-2) was prepared as a colorless liquid.

[0109] Chiral HPLC analysis revealed three main peaks, with the first peak accounting for 52.53% of the total area, the second peak accounting for 16.49%, and the third peak accounting for 13.18%. The first peak represents the (1S,2S) isomer, accounting for a combined 52.53% of the peak area, while the third and fourth peaks represent the (1R,2R) isomers, accounting for a combined 29.67% of the peak area. Therefore, the (1S,2S) isomer accounts for 63.91% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0110] 1H NMR(400MHz,Chloroform-d)δ7.32-7.25(m,2H),6.92-6.81(m,2H),4.68-4.57(m,1H),4.60-4.46(m,1H),4.51-4.37(m,1H),4.37- 4.20(m,1H),4.24-4.06(m,2H),2.19-2.09(m,2H),1.79-1.71(m,2H),1.68-1.55(m,2H),1.50-1.38(m,1H),1.29(d,J=4.0Hz,10H).

[0111] 13 C NMR(101MHz,Chloroform-d)δ155.16,144.26,144.14,126.37,126.35,115.93,115.71,82.59,82 .53,80.82,59.46,59.26,34.12,31.51,31.38,31.33,29.79,29.55,23.48,23.31,22.94,22.82.

[0112] MS (m / z, ESI): [M+Na] + :370.1075.

[0113] [ɑ]D 25 =0.297°(c 0.00673,acetone).

[0114] Example 3

[0115] Preparation of Photoactive (1S,2S)-trans-2-(4-(tert-butyl)phenoxy)cyclohexyl-3,3,3-trifluoropropyl-sulfite:

[0116] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(tert-butyl)phenoxy)cyclohexyl-3,3,3-trifluoropropyl-sulfite (Compound I-3) was prepared as a colorless liquid.

[0117] Chiral HPLC analysis revealed four main peaks. The first and second peaks were baseline-inseparable, accounting for 68.01% of the total area. The third peak accounted for 15.78% of the total area, and the fourth peak accounted for 11.68% of the total area. The first and second peaks represented the (1S,2S) isomer, accounting for 68.01% of the total peak area, while the third and fourth peaks represented the (1R,2R) isomer, accounting for 27.46% of the total peak area. Therefore, the (1S,2S) isomer accounted for 71.24% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0118] 1 H NMR(400MHz,Chloroform-d)δ7.33-7.25(m,2H),6.94-6.80(m,2H),4.50-4.21(m,2H),4.24-4.11(m,1H),4.14-4.00(m,1H),2.56-2.3 3(m,2H),2.23-2.10(m,1H),1.78(d,J=12.1Hz,2H),1.70-1.55(m,1H),1.52-1.35(m,1H),1.39-1.30(m,1H),1.29(s,9H),1.28(s,2H).

[0119] MS (m / z, ESI): [M+Na] + :431.1493.

[0120] [ɑ]D 25 =-0.321°(c 0.00623,acetone).

[0121] Example 4

[0122] Preparation of optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexylprop-2-yn-1-sulfite:

[0123] According to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexylprop-2-yn-1-sulfite (Compound I-4) was prepared as a colorless liquid.

[0124] Chiral HPLC analysis revealed four main peaks, with the first peak accounting for 54.70% of the total area, the second peak accounting for 21.75%, the third peak accounting for 16.19%, and the fourth peak accounting for 5.76%. The first and second peaks represent the (1S,2S) isomer, accounting for a combined 76.45% of the peak area, while the third and fourth peaks represent the (1R,2R) isomer, accounting for a combined 21.95% of the peak area. Therefore, the (1S,2S) isomer accounts for 77.69% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0125] 1 H NMR(400MHz,Chloroform-d)δ7.27-7.18(m,2H),6.92-6.82(m,2H),4.69-4.53(m,2H),4.48(ddd,J=9.9,7.8,4.5Hz,1H),4.21-4.0 9(m,1H),2.51(dt,J=7.6,2.5Hz,1H),2.15(ddt,J=17.4,9.6,3.9Hz,2H),1.84-1.71(m,2H),1.74-1.47(m,1H),1.51-1.20(m,3H).

[0126] 13 C NMR(101MHz,Chloroform-d)δ156.07,129.52,129.48,126.23,117.68,117.47,79.00,78 .38,76.19,75.83,75.74,48.34,48.20,31.14,29.57,29.22,23.39,23.11,22.88,22.64.

[0127] MS (m / z, ESI): [M+Na] + :351.0448.

[0128] [ɑ]D 25 =-1.435°(c 0.0119,acetone).

[0129] Example 5

[0130] Preparation of optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2-fluoroethyl sulfite:

[0131] According to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2-fluoroethyl sulfite (Compound I-5) was prepared as a colorless liquid.

[0132] Chiral HPLC analysis revealed three main peaks, with the first peak accounting for 36.04% of the total area, the second peak accounting for 10.08%, and the third peak accounting for 47.73%. This indicates that the first peak represents the (1S,2S) isomer, while the second peak represents the (1R,2R) isomer. Therefore, the (1S,2S) isomer accounts for 78.14% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0133] 1 H NMR(400MHz,Chloroform-d)δ7.26-7.18(m,2H),6.91-6.82(m,2H),4.70-4.58(m,1H),4.62-4.39(m,2H),4.3 5-4.18(m,1H),4.22-4.05(m,2H),2.35-2.08(m,2H),1.83-1.70(m,2H),1.70-1.55(m,1H),1.59-1.22(m,3H).

[0134] 13 C NMR(101MHz,Chloroform-d)δ156.23,156.12,129.51,129.48,126.39,126.25,117.72,117.52,82.52,82.47,80.8 1,80.76,79.16,78.67,76.09,75.84,59.48,59.45,59.24,31.32,31.25,29.67,29.38,23.42,23.21,22.92,22.75.

[0135] MS (m / z, ESI): [M+Na] + :359.0509.

[0136] [ɑ]D 25 =3.886°(c 0.00875,acetone).

[0137] Example 6

[0138] Preparation of optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-3,3,3-trifluoropropyl-sulfite:

[0139] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-3,3,3-trifluoropropyl-sulfite (Compound I-6) was prepared as a colorless liquid.

[0140] Example 7

[0141] Preparation of optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2,2,2-trifluoroethyl-sulfite:

[0142] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2,2,2-trifluoroethyl-sulfite (Compound I-7) was prepared as a colorless liquid.

[0143] Chiral HPLC analysis revealed four main peaks, with the first peak accounting for 22.48% of the total area, the second peak accounting for 8.08%, the third peak accounting for 28.09%, and the fourth peak accounting for 9.38%. The first and third peaks represent the (1S,2S) isomer, accounting for a combined 50.57% of the peak area, while the third and fourth peaks represent the (1R,2R) isomer, accounting for a combined 17.46% of the peak area. Therefore, the (1S,2S) isomer accounts for 74.33% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0144] 1 H NMR(400MHz,Chloroform-d)δ7.29-7.17(m,2H),6.93-6.77(m,2H),4.49(dtd,J=10.3,8.3,4.7Hz,1H),4.42-4.25(m,1H),4.15( dddd,J=16.8,9.7,8.4,4.4Hz,2H),2.20-1.96(m,2H),1.78(tdt,J=11.7,7.6,4.8Hz,2H),1.72-1.49(m,1H),1.49-1.13(m,3H).

[0145] 13C NMR(101MHz,Chloroform-d)δ155.96,155.86,129.58,129.55,126.65,126.47,117.70,117.43,79.1 7,78.67,77.17,76.90,56.63,56.44,56.26,56.07,31.36,29.73,29.43,23.53,23.34,22.96,22.80.

[0146] MS (m / z, ESI): [M+Na] + :395.0317.

[0147] [ɑ]D 25 =3.586°(c 0.00725,acetone).

[0148] Example 8

[0149] Preparation of optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2,2,3,3-tetrafluoropropyl-sulfite:

[0150] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(chloro)phenoxy)cyclohexyl-2,2,3,3-tetrafluoropropyl-sulfite (Compound I-8) was prepared as a colorless liquid.

[0151] Chiral HPLC analysis showed that the product had three main peaks, with the first peak accounting for 38.08% of the total area, the second peak accounting for 47.75% of the total area, and the third peak accounting for 10.24% of the total area. This means that the first peak is the (1S,2S) isomer and the third peak is the (1R,2R) isomer. Therefore, the (1S,2S) isomer accounts for 78.81% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0152] 1 HNMR(400MHz,Chloroform-d)δ7.40-7.08(m,2H),6.93-6.70(m,2H),5.85(tdt,J=53.0,31.5,4.3Hz,1H),4.6 4-4.28(m,2H),4.24-4.02(m,2H),2.28-2.05(m,2H),1.89-1.72(m,2H),1.72-1.52(m,1H),1.52-1.17(m,3H).

[0153] 13C NMR(101MHz,Chloroform-d)δ155.94,155.83,129.57,129.54,126.63,126.45,117.67,117.3 8,79.13,78.78,55.87,55.59,55.29,31.44,31.34,29.77,29.45,23.55,23.39,22.98,22.84.

[0154] MS (m / z, ESI): [M+Na] + :427.0391.

[0155] [ɑ]D 25 =0.855°(c 0.00509,acetone).

[0156] Example 9

[0157] Preparation of optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexylprop-2-yn-1-sulfite:

[0158] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexylprop-2-yn-1-sulfite (Compound I-9) was prepared as a colorless liquid.

[0159] Chiral HPLC analysis revealed four main peaks, with the first peak accounting for 46.63% of the total area, the second peak accounting for 29.74%, the third peak accounting for 12.15%, and the fourth peak accounting for 7.15%. The first and second peaks represent the (1S,2S) isomer, accounting for a combined 76.38% of the peak area, while the third and fourth peaks represent the (1R,2R) isomer, accounting for a combined 19.30% of the peak area. Therefore, the (1S,2S) isomer accounts for 79.83% of the total peak area of ​​the compound's (1S,2S) and (1R,2R) isomers.

[0160] 1 H NMR(400MHz,Chloroform-d)δ7.18-7.00(m,2H),6.99-6.82(m,2H),4.72-4.28(m,3H),4.24-4. 05(m,1H),2.51(dt,J=9.3,2.5Hz,1H),2.34-1.99(m,2H),1.84-1.70(m,2H),1.70-1.20(m,4H).

[0161] 13C NMR(101MHz,Chloroform-d)δ156.01,155.97,143.27,143.13,122.56,122.53,117.19,116.95,79.1 7,78.52,76.19,75.82,75.67,48.39,48.20,31.21,31.14,29.58,29.22,23.39,23.10,22.88,22.62.

[0162] MS (m / z, ESI): [M+Na] + :401.0666.

[0163] [ɑ]D 25 =0.942°(c 0.00905,acetone).

[0164] Example 10

[0165] Preparation of optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-2-fluoroethyl sulfite:

[0166] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-2-fluoroethyl sulfite (Compound I-10) was prepared as a colorless liquid.

[0167] Chiral HPLC analysis revealed three main peaks, with the first peak accounting for 57.57% of the total area, the second peak accounting for 19.97%, and the third peak accounting for 10.78%. The first peak represents the (1S,2S) isomer, while the second and third peaks represent the (1R,2R) isomers, with a combined peak area of ​​20.75%. Therefore, the (1S,2S) isomer accounts for 65.93% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0168] 1 H NMR(400MHz,Chloroform-d)δ7.12-6.96(m,2H),6.96-6.77(m,2H),4.59-4.49(m,1H),4.49-4.3 0(m,2H),4.29-3.97(m,3H),2.08(dd,J=13.8,5.3Hz,2H),1.78-1.64(m,2H),1.64-1.13(m,4H).

[0169] 13C NMR(101MHz,Chloroform-d)δ155.09,121.51,116.20,115.97,81.47,81.41,79. 70,58.47,58.39,58.26,58.18,30.29,28.64,28.35,22.38,22.17,21.89,21.71.

[0170] MS (m / z, ESI): [M+Na] + :409.0731

[0171] [ɑ]D 25 =2.842°(c 0.00633,acetone).

[0172] Example 11

[0173] Preparation of optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-3,3,3-trifluoropropyl sulfite:

[0174] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-3,3,3-trifluoropropyl sulfite (Compound I-11) was prepared as a colorless liquid.

[0175] Chiral HPLC analysis revealed three main peaks, with the first peak accounting for 60.64% of the total area, the second for 21.29%, and the third for 13.97%. The first peak represents the (1S,2S) isomer, while the second and third peaks represent the (1R,2R) isomers, accounting for a combined 35.26% of the total peak area. Therefore, the (1S,2S) isomer accounts for 63.23% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0176] 1 H NMR(400MHz,Chloroform-d)δ7.13(d,J=8.7Hz,2H),6.96-6.84(m,2H),4.48-4.22(m,2H),4.20-4.11(m,1H),4 .08(ddt,J=13.3,11.1,4.2Hz,1H),2.56-2.36(m,2H),2.20-2.08(m,2H),1.81-1.74(m,2H),1.63-1.26(m,4H).

[0177] 13C NMR (101MHz, Chloroform-d) δ155.98,122.54,117.24,116.97,53.25,31.48,31.37,29.73,29.57,23.45,23.37,22.90.

[0178] MS (m / z, ESI): [M+Na] + :459.0702

[0179] [ɑ]D 25 =1.028°(c 0.00583,acetone).

[0180] Example 12

[0181] Preparation of optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-2,2,2-trifluoroethyl sulfite:

[0182] Referring to the method described in Example 1, optically active (1S,2S)-trans-2-(4-(trifluoromethoxy)phenoxy)cyclohexyl-2,2,2-trifluoroethyl sulfite (Compound I-12) was prepared as a colorless liquid.

[0183] Chiral HPLC analysis revealed three main peaks, with the first peak accounting for 38.49% of the total area, the second peak accounting for 49.28%, and the third peak accounting for 9.90%. This indicates that the first peak represents the (1S,2S) isomer, while the third peak represents the (1R,2R) isomer. Therefore, the (1S,2S) isomer accounts for 79.54% of the total peak area of ​​the (1S,2S) and (1R,2R) isomers.

[0184] 1 H NMR(400MHz,Chloroform-d)δ7.18-7.09(m,2H),6.95-6.87(m,2H),4.56-4.45(m,1H),4.41-4.27(m,1H),4.2 5-4.14(m,1H),4.18-4.08(m,1H),2.26-2.08(m,2H),1.85-1.72(m,2H),1.71-1.53(m,1H),1.53-1.23(m,3H).

[0185] 13C NMR(101MHz,Chloroform-d)δ155.84,155.75,122.61,122.59,119.27,117.22,116.92 ,79.32,78.80,56.61,56.46,56.24,31.37,29.75,29.45,23.53,23.34,22.97,22.81.

[0186] MS (m / z, ESI): [M+Na] + :445.0536.

[0187] [ɑ]D 25 =5.251°(c 0.00895,acetone).

[0188] Comparative Example 1

[0189] Preparation of 2-(4-(tert-butyl)phenoxy)cyclohexylprop-2-yn-1-sulfite (propargyl):

[0190] Following the method described in Example 1, 2-(4-(tert-butyl)phenoxy)cyclohexan-1-ol was used in place of the (1S,2S)-2-(4-(tert-butyl)phenoxy)cyclohexan-1-ol starting material to obtain the target compound, 2-(4-(tert-butyl)phenoxy)cyclohexylprop-2-yn-1-ylsulfite (propargyl). Chiral HPLC analysis showed four major peaks at 4.47 min, 4.85 min, 5.16 min, and 6.78 min, with peak area percentages of 22.10%, 25.06%, 26.02%, and 21.76%, respectively. The chiral HPLC results are shown in Figure 4.

[0191] 1 H NMR (600MHz, CDCl3) δ7.37-7.25(m,2H),6.94-6.73(m,2H),4.60(dtd,J=25.2,15.5,2.4Hz,2H),4.52-4.38(m, 1H),4.23-4.02(m,1H),2.49(dt,J=12.7,2.5Hz,1H),2.28-1.99(m,2H),1.85-1.68(m,2H),1.70-1.29(m,13H).

[0192] 13C NMR (151MHz, CDCl3) δ155.22,144.16,126.45,115.93,115.67,78.68,78.06,77.73,77.67,76.37,76. 12,75.78,75.74,48.28,48.16,34.22,34.16,31.56,31.49,29.79,29.43,23.55,23.27,22.99,22.76.

[0193] IR(KBr)ν3290.56,2949.16,2866.22,2129.41,1608.63,1579.70,1510.26,1454.33,1363.67,1290.38,1240.23,1203 .58,1184.29,1114.86,1055.06,1039.63,923.90,902.69,869.90,852.54,831.32,810.10,775.38,742.59,551.64cm -1 .

[0194] MS (m / z, ESI): [M+Na] + :373.1438.

[0195] Application Examples

[0196] Activity test of Tetranychus cinnabarinus:

[0197] The test compound was dissolved in acetone and diluted to the desired concentration with a 0.1 wt % Tween 80 aqueous solution, with the acetone content not exceeding 5 wt %.

[0198] Bean seedlings grown to two true leaves were inoculated with adult Tetranychus cinnabarinus mites (T. cinnabarinus). The population was then assessed and the entire plant was sprayed with a handheld sprayer (1.5 mL). Each treatment was repeated three times. After treatment, the seedlings were observed in a constant temperature observation room. After 72 hours, the number of live mites was assessed and mortality was calculated. 40-80 T. cinnabarinus mites were inoculated at each inoculation.

[0199] Among them, mortality rate (%) = (number of inoculated insects - number of live insects after medication) ÷ number of inoculated insects × 100%.

[0200] Among them, compounds I-1, I-2, I-3, I-4, I-9, I-10, and I-11 were significantly more active against adult Tetranychus cinnabarinus than propargyl. The mortality rates of compounds I-1, I-2, I-3, I-4, I-5, I-9, I-10, I-11, and propargyl at different concentrations against Tetranychus cinnabarinus are shown in Table 1:

[0201] Table 1

[0202] As shown in the table above, the photoactive product I-1 of the present invention exhibits significantly superior lethal activity against Tetranychus cinnabarinus compared to the racemic propargyl. The development of the photoactive product I-1 can significantly reduce pesticide usage, achieving the goal of reducing pesticide use and increasing its effectiveness, with significant economic and social benefits.

[0203] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A sulfite compound having a structure shown in formula (I): in, Based on the total amount of (1S, 2S) configuration and (1R, 2R) configuration isomers in the compound of the structure represented by formula (I), the content of the stereoisomer of the (1S, 2S) configuration is greater than 60 mol%; R1 is selected from 2-propynyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 3,3,3-trifluoropropyl or 2,2,3,3-tetrafluoropropyl; R2, R3, R4, R5, R6 are each independently selected from hydrogen, tert-butyl, fluorine, chlorine, bromine, trifluoromethoxy, 2,2,2-trifluoroethoxy, methoxy, ethoxy, propoxy, phenyl, phenoxy, benzyloxy, trifluoromethyl, cyano, methylthio, methylsulfinyl or methylsulfonyl.

2. The sulfite compound according to claim 1, wherein Based on the total amount of (1S, 2S) configuration and (1R, 2R) configuration isomers in the compound of the structure represented by formula (I), the content of the stereoisomer of the (1S, 2S) configuration is greater than 70 mol%; R1 is selected from 2-propynyl, 2-fluoroethyl, 2-chloroethyl or 3,3,3-trifluoropropyl; R2 and R6 are each independently selected from hydrogen, fluorine, chlorine, bromine, trifluoromethyl, cyano, trifluoromethoxy or 2,2,2-trifluoroethoxy; R3 and R5 are both hydrogen; R4 is selected from tert-butyl, chloro, trifluoromethoxy, 2,2,2-trifluoroethoxy or phenoxy.

3. The sulfite compound according to claim 1 or 2, wherein Based on the total amount of (1S, 2S) configuration and (1R, 2R) configuration isomers in the compound of the structure represented by formula (I), the content of the stereoisomer of the (1S, 2S) configuration is greater than 80 mol%; R1 is selected from 2-propynyl or 2-fluoroethyl; R2, R6 are each independently selected from hydrogen, chlorine or fluorine; R4 is selected from tert-butyl, chloro or trifluoromethoxy.

4. A method for preparing a sulfite compound, the method comprising: (1) In the presence of solvent A, the compound represented by formula (II) is subjected to a first coupling reaction with thionyl chloride, and then subjected to post-treatment to obtain a compound represented by formula (III): (2) In the presence of solvent B and an alkaline substance, the compound represented by formula (III) is subjected to a second coupling reaction with the alcohol represented by formula (IV), and then subjected to purification treatment to obtain the compound represented by formula (I): Among them, the definitions of R1, R2, R3, R4, R5, R6 and C 1 , C 2 The configuration is the same as the definition and configuration described in any one of claims 1 to 3.

5. The method according to claim 4, wherein: In step (1), the solvent A is selected from at least one of dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, acetone, toluene and xylene, preferably selected from at least one of dichloromethane, 1,2-dichloroethane and toluene; and / or, the molar ratio of thionyl chloride to the compound represented by formula (II) is 0.2-5:1, preferably 0.7-1.5:1; and / or, the reaction temperature of the first coupling reaction is -20°C to 80°C, preferably -10°C to 30°C; and / or, the reaction pressure of the first coupling reaction is 0-1 MPaG, preferably 0-0.1 MPaG; and / or, the reaction time of the first coupling reaction is 0.01-10 h, preferably 0.1-2 h; And / or, in step (2), the solvent B is selected from at least one of dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, N,N-dimethylformamide, acetone, toluene and xylene, preferably selected from at least one of dichloromethane, 1,2-dichloroethane and toluene; and / or, the alcohol represented by formula (IV) is at least one selected from 2-propynol, 2-fluoroethanol, 2,2-difluoroethanol, 2-chloroethanol, 3,3,3-trifluoropropanol and 2,2,3,3-tetrafluoropropanol, preferably at least one selected from 2-propynol, 2-fluoroethanol and 3,3,3-trifluoropropanol; and / or, the alkaline substance is selected from an organic base or an inorganic base, preferably at least one selected from sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, triethylamine, diisopropylethylamine and pyridine; and / or, the molar ratio of the alkaline substance to the compound represented by formula (III) is 0.2-5:1, preferably 0.7-1.5:1; and / or, the molar ratio of the alcohol represented by formula (IV) to the compound represented by formula (III) is 0.2-5:1, preferably 0.7-1.5:1; and / or, the reaction temperature of the second coupling reaction is -20°C to 80°C, preferably -10°C to 30°C; And / or, the reaction pressure of the second coupling reaction is 0-1 MPaG, preferably 0-0.1 MPaG; and / or, the reaction time of the second coupling reaction is 0.01-10 h, preferably 0.1-1 h.

6. A sulfite compound prepared by the method according to claim 4 or 5.

7. Use of the sulfite compound according to any one of claims 1 to 3 and 6 in controlling harmful mites.

8. A composition, wherein include: At least one of the sulfite compounds according to any one of claims 1 to 3 and 6, and a liquid carrier and / or a solid carrier.

9. A method for controlling harmful mites, characterized in that: The method comprises: applying the sulfite compound described in any one of claims 1 to 3 and 6 or the composition described in claim 8 directly or indirectly to the harmful mites to be controlled and / or the medium where they grow.

10. The method according to claim 9, wherein: The method comprises: treating plants where harmful mites grow with an acaricidal effective amount of the sulfite compound described in any one of claims 1 to 3 and 6 or the composition described in claim 8.

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