Phenyl sulfide (sulfoxide) compound and use thereof

Abstract

The present invention belongs to the field of agricultural acaricides. Specifically, the present invention relates to a phenyl sulfide (sulfoxide) compound and the use thereof. The structure is as shown in general formula I, and the definition of each substituent in the formula is as shown in the description. The compound of general formula I has excellent acaricidal activity and can be used for preventing and controlling various harmful mites.

Description

A phenyl sulfide (sulfoxide) compound and its application Technical Field

[0001] The present invention belongs to the field of agricultural acaricides, and in particular relates to a phenyl sulfide (sulfoxide) compound and application thereof. Background Art

[0002] Patent CN118164880A discloses the following compound KC1, which has a 100% lethality rate against adult Tetranychus cinnabarinus mites at 10 mg / L:

[0003] In the prior art, there are no reports on the compounds represented by the general formula I of the present invention and their acaricidal activity. Moreover, compared with the prior art, the compounds of the present invention have higher acaricidal activity. Summary of the Invention

[0004] The object of the present invention is to provide a phenyl sulfide (sulfoxide) compound with better acaricidal effect, which can be used in the fields of agriculture or forestry to prevent and control pests and mites.

[0005] The technical solutions of the present invention are as follows:

[0006] A phenyl sulfide (sulfoxide) compound, as shown in the general formula I:

[0007] In the general formula I:

[0008] R1 is selected from halogen;

[0009] R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F;

[0010] n is selected from 0 or 1.

[0011] In one possible implementation, in Formula I,

[0012] R1 is selected from chlorine or bromine;

[0013] R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F;

[0014] n is selected from 0 or 1.

[0015] In addition, the present invention provides a method for preparing the above-mentioned phenyl sulfide (sulfoxide) compound, which comprises the following steps:

[0016] Step 1): subjecting compound VIII to a reduction reaction to obtain compound VII;

[0017] Step 2): subjecting compound VII to a rearrangement reaction to obtain compound VI;

[0018] Step 3): subjecting compound VI to a salt-forming reaction to obtain a hydrochloride, hydrobromide, sulfate or fluoroborate salt of compound VI, i.e., a compound of formula V;

[0019] Step 4): subjecting the compound of formula V to a Sandmeyer reaction to obtain a compound of formula IV;

[0020] Step 5): subjecting the compound of formula IV to a sulfonation reaction to obtain a compound of formula III;

[0021] Step 6): subjecting the compound of formula III to a reduction reaction to obtain a compound of formula II;

[0022] Step 7): subjecting the compound of formula II to an alkylation reaction to obtain a compound of formula I-1;

[0023] Step 8): subjecting the compound of formula I-1 to an oxidation reaction to obtain a compound of formula I-2;

[0024] in:

[0025] R1 is selected from halogen;

[0026] R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F;

[0027] X is selected from hydrogen or acetyl;

[0028] Y is selected from HCl, HBr, H2SO4 or HBF4.

[0029] In addition, the present invention provides an intermediate compound for preparing the above-mentioned phenyl sulfide (sulfoxide) compound, and the intermediate compound is shown in the general formula II:

[0030] In the general formula II:

[0031] R1 is selected from halogen;

[0032] X is selected from hydrogen or acetyl.

[0033] In addition, the present invention provides an intermediate compound for preparing the compound of the above-mentioned general formula II, wherein the intermediate compound is shown in the general formula III:

[0034] In the general formula III:

[0035] R1 is selected from halogen.

[0036] In addition, the present invention provides a hydrochloride, hydrobromide, sulfate or fluoroborate compound of compound VI, wherein the salt compound is represented by general formula V:

[0037] In general formula V:

[0038] Y is selected from HCl, HBr, H2SO4 or HBF4.

[0039] In addition, the present invention also provides the use of the compound of formula V for preparing the compound of formula I, the compound of formula II, the compound of formula III or the compound of formula IV.

[0040] In the above technical solution, halogen refers to fluorine, chlorine, bromine or iodine.

[0041] Some of the compounds of formula I of the present invention are shown in Tables 1 to 4, but the present invention is by no means limited to these compounds.

[0042] Table 1

[0043] In the general formula I, when R1=Cl, R2 is a different substituent and n is a different value as shown in Table 1, and the representative compounds are numbered 1.1-1.12.

[0044] Table 2: In general formula I, when R1=F, R2 is a different substituent and n is a different value consistent with Table 1, and the representative compounds are numbered 2.1-2.12, corresponding to 1.1-1.12 in Table 1.

[0045] Table 3: In general formula I, when R1=Br, R2 is a different substituent and n is a different value consistent with Table 1, and the representative compounds are numbered 3.1-3.12, corresponding to 1.1-1.12 in Table 1.

[0046] Table 4: In general formula I, when R1=I, R2 is a different substituent and n is a different value consistent with Table 1, and the representative compounds are numbered 4.1-4.12, corresponding to 1.1-1.12 in Table 1.

[0047] Some of the compounds of formula II of the present invention are shown in Table 7, but the present invention is by no means limited to these compounds.

[0048] Table 7

[0049] Some of the compounds of formula III of the present invention are shown in Table 8, but the present invention is by no means limited to these compounds.

[0050] Table 8

[0051] Some of the compounds of formula V of the present invention are shown in Table 9, but the present invention is by no means limited to these compounds.

[0052] Table 9

[0053] The compounds of formula I (including compounds of formula I-1 and formula I-2), compounds of formula II, compounds of formula III and compounds of formula V of the present invention can be prepared according to the following scheme. Unless otherwise specified, the definitions of the groups in the formula are the same as above.

[0054] Step 1): Prepare compound VII from compound VIII

[0055] Compound VIII can be reacted in a suitable solvent, a base, and a reducing agent by conventional methods at a temperature ranging from 40°C to the boiling point of the solvent for 0.5 to 48 hours to obtain a compound of formula VII. Suitable bases include alkali metal hydrides such as lithium, sodium, or potassium, such as sodium hydride and potassium hydride; alkali metal hydroxides such as lithium, sodium, or potassium, such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as lithium, sodium, potassium, or cesium, such as sodium carbonate and cesium carbonate; and organic bases such as triethylamine, sodium tert-butoxide, or potassium tert-butoxide. The reducing agent can be red phosphorus, zinc, iron, copper, nickel, or a mixture of red phosphorus, zinc, iron, copper, and nickel in any proportion; the molar ratio of compound VIII to the reducing agent is 1:1-30 (e.g., 1:1-25, 1:1-20, 1:1-10, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, 1:1-2), more preferably 1:1-20, even more preferably 1:1-10, for example, 1:3-6.

[0056] Step 2): Prepare compound VI from compound VII

[0057] The compound of formula VII is reacted under acidic conditions at a temperature ranging from -5°C to the boiling point of the solvent for 0.5-48 hours to obtain the compound of formula VI. The acid can be an inorganic acid or an organic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid, or methanesulfonic acid. The reaction solvent can be water, chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran, or dioxane.

[0058] Step 3): Prepare the compound of formula V from the compound of formula VI

[0059] The compound of formula VI is reacted under acidic conditions at a temperature ranging from -5°C to the boiling point of the solvent for 0.5-48 hours to produce the compound of formula V. The acid can be hydrochloric acid, hydrobromic acid, sulfuric acid, or fluoroboric acid. The reaction solvent can be water, chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran, or dioxane. Preferably, the molar ratio of the compound of formula VI to the acid is 1:1-10, more preferably 1:2-8, and even more preferably 1:2-6.

[0060] Step 4): Prepare the compound of formula IV from the compound of formula V

[0061] The synthesis of the compound of formula IV can be carried out by diazotizing the compound of formula V under acidic conditions and then adding the corresponding CuX or potassium iodide. Fluoborate is directly diazotized in the presence of fluoroboric acid, and then the diazonium salt is decomposed by heating to obtain the compound of formula IV in which R1 is fluorine. The temperature ranges from -10°C to the boiling point of the solvent. The acid can be an inorganic acid or an organic acid, such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, trifluoroacetic acid, oxalic acid, malonic acid or methanesulfonic acid. The reaction solvent can be water, chloroform, dichloromethane, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane. Preferably, CuX is cuprous chloride or cuprous bromide. Preferably, the molar ratio of the compound of formula V to cuprous chloride, cuprous bromide or potassium iodide is 1:1-10, more preferably 1:2-8, and further preferably 1:2-6.

[0062] Step 5): Prepare the compound of formula III from the compound of formula IV

[0063] The compound of formula IV can be reacted with a sulfonating agent to produce the compound of formula III. The reaction is typically carried out at a temperature of 0-200°C (e.g., 190°C, 170°C, 150°C, 130°C, 110°C, 100°C, 90°C, 80°C, 70°C, 60°C, 50°C, or 30°C). The reaction time is typically 0.5-48 hours. The sulfonating agent can be chlorosulfonic acid, fuming sulfuric acid, concentrated sulfuric acid, sulfur trioxide, or sulfur monochloride. The molar ratio of the compound of formula IV to the sulfonating agent is 1:1-100 (e.g., 1:1-90, 1:1-80, 1:1-70, 1:1-60, 1:1-50, 1:1-40, 1:1-30, 1:1-20, 1:1-10, 1:1-8, 1:1-6, 1:1-4, 1:1-3, or 1:1-2).

[0064] Step 6): Prepare the compound of formula II from the compound of formula III

[0065] The compound of formula III can be reacted with a reducing agent to produce the compound of formula II. The reaction is typically carried out at 0-150°C (e.g., 140°C, 130°C, 120°C, 110°C, 100°C, 90°C, 80°C, 70°C, 60°C, 50°C, 30°C). The reaction time is typically 0.5-48 hours. The reducing agent can be red phosphorus, zinc, iron, copper, nickel, or a mixture of red phosphorus, zinc, iron, copper, and nickel in any proportion. The molar ratio of the compound of formula III to the reducing agent is 1:1-30 (e.g., 1:1-25, 1:1-20, 1:1-10, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, 1:1-2). An appropriate amount of an organic acid or inorganic acid such as formic acid, acetic acid, trifluoroacetic acid, hydrochloric acid, sulfuric acid or nitric acid may be added to the reaction; the molar ratio of the compound of formula III to the acid is 1:1-100 (e.g., 1:1-90, 1:1-80, 1:1-70, 1:1-60, 1:1-50, 1:1-40, 1:1-30, 1:1-20, 1:1-10, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, 1:1-2).

[0066] Preferably, in the reaction of step 6), red phosphorus and iodine are further added.

[0067] More preferably, the molar ratio of the compound of formula III to red phosphorus and iodine is 1:1-10:0.02-0.2, more preferably 1:2-8:0.05-0.15, and further preferably 1:2-6:0.05-0.1.

[0068] The thioacetyl group in the compound of formula II can be subjected to conventional acidic or alkaline hydrolysis to obtain the compound of formula II containing a thiol group.

[0069] Step 7): Prepare the compound of formula I-1 from the compound of formula II

[0070] The compound of formula II can be reacted with a halogenating agent or a sulfonate in a suitable solvent in the presence of a suitable base to produce a compound of formula I-1. The halogenating agent can be trifluoroiodoethane, methyl iodide, or ethyl iodide, and the sulfonate can be 2,2,2-trifluoroethyl methanesulfonate, 2,2,2-trifluoroethyl benzenesulfonate, or ethyl 2,2,2-trifluoro-p-toluenesulfonate. The molar ratio of the compound of formula II to the halogenating agent is 1:1-100 (e.g., 1:1-90, 1:1-80, 1:1-70, 1:1-60, 1:1-50, 1:1-40, 1:1-30, 1:1-20, 1:1-10, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, or 1:1-2). Suitable bases may be the same or different and include organic bases such as trimethylamine, triethylamine, pyridine, DBU, 4-dimethylaminopyridine, N,N-diisopropylethylamine, alkali metal hydrides such as sodium hydride and potassium hydride, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium bicarbonate, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide, and sodium tert-butoxide; the molar ratio of the compound of formula II to the base is 1:1-20 (e.g., 1:1-18, 1:1-16, 1:1-14, 1:1-12, 1:1-10, 1:1-9, 1:1-8, 1:1-7, 1:1-6, 1:1-5, 1:1-4, 1:1-3, 1:1-2). Suitable solvents, which may be the same or different, include aromatic hydrocarbons such as benzene, toluene, and xylene; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; halogenated hydrocarbons such as chloroform and dichloromethane; esters such as methyl acetate and ethyl acetate; ethers such as tetrahydrofuran, dioxane, diethyl ether, 1,2-dimethoxyethane, and 1,4-dioxane; polar solvents such as water, acetonitrile, N,N-dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide; or mixtures thereof. The reaction is typically carried out at a temperature between 0°C and the boiling point of the solvent. The reaction time is typically 0.5 and 48 hours.

[0071] Step 8): Prepare the compound of formula I-2 from the compound of formula I-1

[0072] The compound of formula I-1 reacts with an oxidizing agent to produce a compound of formula I-2. The oxidizing agent may be m-chloroperbenzoic acid, hydrogen peroxide or sodium (meta) periodate, etc. The reaction solvent may be water, methanol, ethanol, ether, dichloromethane, chloroform, carbon tetrachloride, hexane, benzene, toluene, ethyl acetate, DMF, tetrahydrofuran or dioxane, etc. The reaction is usually carried out at a temperature of 0-100°C, preferably at 0-30°C. The reaction time is usually 10 minutes to 48 hours. Preferably, the molar ratio of the compound of formula I-1 to the oxidizing agent is 1:1-10, more preferably 1:1-8, further more preferably 1:1-6, for example 1:1-5.

[0073] Because the compounds of Formula I of the present invention possess unexpectedly high acaricidal activity, the technical solutions of the present invention also include the use of the compounds of Formula I in the preparation of acaricides in agriculture or other fields. In particular, the compounds of Formula I are active against important species of the following families (this list is intended to illustrate the present invention only and is in no way limiting): Tetranychus urticae (Tetranychus cinnabarinus, Panonychus malus, Tetranychus citri, Tetranychus kanzawa, Tetranychus chinensis), Tetranychus serratus, Tetranychus chinensis, Tetranychus chinensis, Tetranychus chinensis, etc.), Tetranychus urticae, Tetranychus tarsi, Tetranychus serratus, Tetranychus serratus, etc.

[0074] Due to their positive properties, the above-mentioned compounds can be advantageously used for protecting important agricultural and horticultural crops, domestic and breeding stock, and environments frequented by humans from harmful mites.

[0075] To obtain the desired effect, the amount of compound used will vary depending on various factors, such as the compound used, the crop to be protected, the type of pest, the degree of infestation, climatic conditions, the method of application, the formulation used, etc.

[0076] Doses of 10 g to 5 kg of compound per hectare provide adequate control.

[0077] The present invention also includes an acaricidal composition comprising the compound of formula I as an active ingredient. The weight percentage of the active ingredient in the acaricidal composition is between 0.1% and 99%. The acaricidal composition also includes a carrier acceptable for agriculture, forestry, and hygiene.

[0078] The compositions of the present invention can be applied in the form of formulations. The compound of formula I, as the active ingredient, is dissolved or dispersed in a carrier or formulated into a formulation for easier dispersibility when used as a miticide. For example, these chemical formulations can be formulated as wettable powders, oil suspensions, aqueous suspensions, aqueous emulsions, aqueous solutions, or emulsifiable concentrates. These compositions contain at least one liquid or solid carrier and, if necessary, a suitable surfactant.

[0079] The technical solution of the present invention also includes a method for controlling pest mites: applying the acaricidal composition of the present invention to the pest mites or their growth medium. The effective amount is usually selected to be 10 to 1000 grams per hectare, and preferably 20 to 500 grams per hectare.

[0080] For certain applications, such as in agriculture, one or more other fungicides, insecticides, acaricides, herbicides, plant growth regulators or fertilizers may be added to the acaricide composition of the present invention to produce additional advantages and effects.

[0081] It should be understood that various changes and modifications can be made within the scope of the present invention as defined by the claims. DETAILED DESCRIPTION

[0082] The following specific examples are used to further illustrate the present invention, but the present invention is in no way limited to these examples. (Unless otherwise noted, all raw materials used are commercially available)

[0083] Synthesis Example

[0084] According to the synthetic routes described above, different raw materials can be used to prepare the compounds represented by Formula I, Formula II, Formula III, and Formula V of the present invention, which are further described in detail as follows:

[0085] Example 1: Preparation of Compound 1.1

[0086] (1) Preparation of intermediate 1,2-bis(3-fluorophenyl)hydrazine (VII)

[0087] To a 3L three-necked flask, 819g of 13% sodium hydroxide solution and 1050g of m-fluoronitrobenzene (7.44mol) were added. The mixture was heated to 95°C and stirred. 1858.5g of zinc paste (978.2g of zinc powder + 880.3mL of water, 14.96mol) was added in portions. The temperature was maintained at 95-105°C over a period of 3 hours. The addition was completed after maintaining the temperature at 90-95°C. 912g of zinc paste (480.7g of zinc powder + 431.3mL of water, 7.35mol) was added. After 6 hours of reaction, TLC was used to monitor the reaction. The reaction was stopped, the temperature was lowered to 3-7°C, and the pH was adjusted to 5-6 using 2.8L of concentrated hydrochloric acid. The mixture was filtered under reduced pressure and the filter cake was washed with water until neutral. After drying, 800mL of dichloromethane was added. After stirring at room temperature for 30 minutes, the mixture was filtered and dried to obtain 802.8g of the intermediate in a yield of 98.0%. 1 HNMR(600MHz,Chloroform-d)δ7.22-7.11(m,2H),6.75-6.45(m,6H),5.71(s,2H). ESI-MS:m / z[M+H] + 221.22.

[0088] (2) Preparation of intermediate 2,2'-difluoro-[1,1'-biphenyl]-4,4'-diamine (VI)

[0089] Concentrated hydrochloric acid (2173.8 mL, 26.08 mol) and water 1445.5 mL were added to a 5L three-necked flask and stirred at 0°C. Intermediate VII (565.2 g, 2.57 mol) was added in batches within half an hour. After stirring for 5 h, the mixture was moved to room temperature (25°C) and reacted for 3 h. The reaction was completed after TLC monitoring. The reaction solution was moved to 0°C and the pH was adjusted to 10-11 with saturated sodium hydroxide. The mixture was filtered and dried. The obtained solid was recrystallized by adding 650 mL of toluene. After complete precipitation, the solid was filtered and dried to obtain 529.0 g of the intermediate with a yield of 93.6%. 1 HNMR(600MHz,Chloroform-d)δ7.13-7.10(m,2H),6.50-6.43(m,4H),3.79(s,4H).

[0090] (3) Preparation of the intermediate 4,4'-dichloro-2,2'-difluoro-1,1'-biphenyl

[0091] Intermediate VI (68.2 g, 0.31 mol) was added to a 250 mL three-necked flask and dissolved in 300 mL of ethyl acetate. Concentrated hydrochloric acid was added dropwise with stirring at room temperature until the salt was completely formed. The product was filtered and dried to obtain the hydrochloride 9.1. 1 H NMR (600MHz, DMSO-d6) δ9.15 (s, 6H), 7.57-7.38 (m, 2H), 7.25-7.05 (m, 4H).

[0092] To a 1L three-necked flask, add 312mL of concentrated hydrochloric acid and 438mL of water. Add the hydrochloride while stirring at room temperature. Transfer to a -5°C cold trap and add sodium nitrite (51.8g, 0.75mol) dropwise over half an hour. Continue stirring for 2 hours. Then, add the prepared diazonium salt dropwise to a 500mL hydrochloric acid solution of cuprous chloride (110.9g, 1.12mol). Maintain the temperature between -10 and -5°C with vigorous stirring. Continue stirring for 3 hours. After the reaction is complete, add 500mL of ethyl acetate for extraction. The organic layer is extracted with water and saturated sodium chloride, followed by drying over anhydrous magnesium sulfate and concentration to obtain the crude product. Purification by flash column chromatography affords 64.2g of the intermediate 4,4'-dichloro-2,2'-difluoro-1,1'-biphenyl in a yield of 80.1%. 1 H NMR (600MHz, Chloroform-d) δ7.31-7.28(m,2H),7.23(d,2H),7.22-7.19(m,2H).

[0093] (4) Preparation of intermediate 4,4'-dichloro-2',6-difluoro-[1,1'-biphenyl]-3-sulfonyl chloride (8.1)

[0094] Chlorosulfonic acid (3.2 g, 27.49 mmol) was added to DCM (6 mL), and the intermediate 4,4'-dichloro-2,2'-difluoro-1,1'-biphenyl (3.6 g, 13.74 mmol) was added with stirring at room temperature. After completion of the reaction, the reaction solution was added dropwise to water (200 mL) for quenching, and the aqueous phase was extracted with DCM (200 mL). The organic layer was concentrated under vacuum to obtain a white solid (4.2 g, 85.5% yield), which was used directly in the next step without further purification.

[0095] (5) Preparation of intermediate 4,4'-dichloro-2',6-difluoro-[1,1'-biphenyl]-3-thiol (7.1)

[0096] To a reaction flask, intermediate 8.1 (5.6 g, 15.78 mmol), red phosphorus (0.8 g, 26.83 mmol), iodine (0.4 g, 1.58 mol), acetic anhydride (1.6 g, 15.78 mol), and acetic acid (50 mL) were added sequentially and the mixture was heated to reflux for 4 h. After completion of the reaction, as monitored by TLC, the reaction mixture was hot filtered, the mother liquor was concentrated, and the layers were extracted with 200 mL of ethyl acetate and 200 mL of water. The organic layer was concentrated under reduced pressure to yield 5.3 g of a white solid, intermediate 7.2.

[0097] To a reaction flask, add 5.3 g of the white solid (Intermediate 7.2), 50 mL of tetrahydrofuran, and sodium formaldehyde sulfoxylate (1.9 g, 15.78 mmol). Cool to 0-5°C in an ice-water bath. Add aqueous sodium hydroxide (2 g dissolved in 100 mL of water) dropwise, maintaining the temperature at 0-5°C. After the addition is complete, continue stirring the reaction for 30 minutes. After TLC monitoring, add 100 mL of water and 100 mL of ethyl acetate to the reaction mixture, separate the layers, and discard the organic phase. Add concentrated hydrochloric acid (4.4 g, 43.0 mmol) dropwise to the aqueous phase. After the addition is complete, continue stirring for 30 minutes, as solids continue to wash out. Add 200 mL of ethyl acetate and extract. The organic phase is dried over anhydrous magnesium sulfate and concentrated under reduced pressure to yield 3.8 g of a white solid, Intermediate 7.1. Yield: 82.6%.

[0098] (6) Preparation of compound 1.1

[0099] To a reaction flask were added intermediate 7.1 (1.2 g, 3.99 mmol), 10 mL of DMF, potassium carbonate (1.10 g, 7.99 mmol), sodium formaldehyde sulfoxylate (0.2 g, 2.00 mmol), and trifluoroiodoethane (1.3 g, 5.99 mmol). The reaction mixture was heated to 40°C for 5 h. After completion of the reaction, as monitored by TLC, the reaction mixture was concentrated and the residue purified by column chromatography to yield 1.0 g of a white solid, the target compound 1.1, in a 70.5% yield. 1 H NMR (600MHz, Chloroform-d) δ7.65(d,1H),7.33(d,1H),7.29(t,1H),7.27-7.20(m,2H),3.44(q,2H).

[0100] Example 2: Preparation of Compound 1.2

[0101] m-CPBA (0.2 g, 1.01 mmol, 85% purity) was added portionwise to a solution of compound 1.1 (0.2 g, 0.66 mmol) in DCM (10 mL) under ice-cooling conditions. The mixture was stirred for 3 h, and the reaction was monitored for completion by TLC. Saturated aqueous sodium thiosulfate (15 mL) was added, and the organic phase was separated, washed with 10% sodium carbonate solution and brine, dried over MgSO₄, and concentrated in vacuo. Column chromatography afforded 0.2 g of a white solid, compound 1.2, in a 70.5% yield. 1 H NMR (600MHz, Chloroform-d) δ7.99(d,1H),7.34(dd,2H),7.26(ddd,2H),3.79(dq,1H),3.44(dq,1H).

[0102] Example 3: Preparation of Compound 2.1

[0103] (1) Preparation of the intermediate 2,2',4,4'-tetrafluoro-1,1'-biphenyl

[0104] To a 250 mL three-necked flask, intermediate VI (6.9 g, 31.36 mmol) was added and dissolved in 60 mL of ethyl acetate. 40% fluoroboric acid (41.3 g, 188.18 mmol) was added dropwise with stirring at room temperature. After stirring for 30 min, the mixture was filtered and dried to obtain fluoroborate 9.4. 1 HNMR(600MHz,DMSO-d6)δ7.72(s,6H),7.34(t,2H),6.95(d,4H).

[0105] Fluoborate was added to 100 mL of 40% fluoroboric acid and transferred to a -5°C cold trap. Sodium nitrite (5.2 g, 75.36 mmol) was then added dropwise over half an hour. Stirring was continued for 2 hours, and the reaction mixture was filtered to obtain the filter cake, which was diazonium fluoborate. The filter cake was placed in a 250 mL single-necked flask, along with 100 mL of toluene. The mixture was heated to reflux for 72 hours. The reaction was terminated, and extraction was performed with 200 mL of ethyl acetate. The organic layer was extracted once with water and then with saturated sodium chloride. The mixture was dried over anhydrous magnesium sulfate and concentrated to obtain the crude product. Purification by flash column chromatography afforded 1.78 g of the intermediate 2,2',4,4'-tetrafluoro-1,1'-biphenyl, in a yield of 25.1%. 1 H NMR (600MHz, DMSO-d6) δ7.59-7.48(m,2H),7.40(s,2H),7.24(t,2H).

[0106] (2) Preparation of intermediate 4'-chloro-2',4,6-trifluoro-[1,1'-biphenyl]-3-sulfonyl chloride (8.2)

[0107] Compound 8.2 was prepared from the intermediate 2,2',4,4'-tetrafluoro-1,1'-biphenyl according to the method described in step (4) of Example 1 in a yield of 98.5%.

[0108] (3) Preparation of intermediate 2',4,4',6-tetrafluoro-[1,1'-biphenyl]-3-thiol (7.3)

[0109] Intermediates 7.4 and 7.3 were prepared from compound 8.2 in 82.5% yield according to the method described in step (5) of Example 1.

[0110] (4) Preparation of compound 2.1

[0111] Compound 2.1 can be prepared from compound 7.3 by the method described in step (6) of Example 1. 1 H NMR (600MHz, Chloroform-d) δ7.59(t,1H),7.32(td,1H),7.05-6.88(m,3H),3.40(q,2H).

[0112] Example 4: Preparation of Compound 2.2

[0113] Compound 2.2 can be prepared from compound 2.1 according to the method described in Example 2. 1HNMR(600MHz,Chloroform-d)δ7.82(t,1H),7.29(td,1H),7.01(t,1H),6.97-6.84(m,1H),3.67-3.47(m,1H).

[0114] Example 5: Preparation of Compound 3.1

[0115] (1) Preparation of the intermediate 4,4'-dibromo-2,2'-difluoro-1,1'-biphenyl

[0116] To a 250 mL three-necked flask, add intermediate VI (6.9 g, 31.36 mmol), dissolve in 60 mL of ethyl acetate, and add 40% hydrobromic acid (25.1 g, 125.45 mmol) dropwise with stirring at room temperature until the salt is completely formed. Filter and wash with water to obtain the hydrobromide intermediate 9.2. 1 H NMR (600MHz, DMSO-d6) δ8.81 (s, 6H), 7.52 (dt, 2H), 7.33-7.18 (m, 4H).

[0117] The hydrobromide intermediate was added to 30 mL of hydrobromic acid and 40 mL of water, transferred to a -5°C cold trap, and a 30 mL aqueous solution of sodium nitrite (4.76 g, 68.99 mmol) was added dropwise. After the addition was complete and stirring continued for 2 hours, the prepared diazonium salt was added dropwise to a 50 mL solution of cuprous bromide (9.0 g, 62.72 mmol) in hydrobromic acid. The temperature was maintained between -10 and -5°C with vigorous stirring. The addition was completed over 3 hours. Stirring was continued for 2 hours until the reaction was complete. Ethyl acetate was added for extraction, and the organic layer was extracted once with water and saturated sodium chloride, dried over anhydrous magnesium sulfate, and concentrated to obtain the crude product. Flash column purification afforded 9.0 g of the intermediate 4,4'-dibromo-2,2'-difluoro-1,1'-biphenyl, with a yield of 82.5%. 1 H NMR (600MHz, Chloroform-d) δ7.39-7.33(m,4H),7.25-7.20(m,2H).

[0118] (2) Preparation of compound 4,4'-dibromo-2',6-difluoro-[1,1'-biphenyl]-3-sulfonyl chloride (8.3)

[0119] Compound 8.3 was prepared from the intermediate 4,4'-dibromo-2,2'-difluoro-1,1'-biphenyl according to the method described in step (4) of Example 1 in a yield of 93.5%.

[0120] (3) Preparation of intermediate 4,4'-dibromo-2',6-difluoro-[1,1'-biphenyl]-3-thiol (7.5)

[0121] Intermediates 7.6 and 7.5 were prepared from compound 8.3 in 85.6% yield according to the method described in step (5) of Example 1.

[0122] (4) Preparation of compound 3.1

[0123] Compound 3.1 can be prepared from compound 7.5 by the method described in step (6) of Example 1. 1 H NMR (600MHz, Chloroform-d) δ7.67-7.63(m,1H),7.49(d,1H),7.41-7.35(m,2H),7.25-7.20(m,1H),3.53-3.36(m,2H).

[0124] Example 6: Preparation of Compound 3.2

[0125] Compound 3.2 can be prepared from compound 3.1 according to the method described in Example 2. 1 HNMR(600MHz,Chloroform-d)δ7.98(d,1H),7.50(d,1H),7.41(ddd,2H),7.29-7.26(m,1H),3.81(dq,1H),3.41(dq,1H).

[0126] Biological activity assay

[0127] Example 7: Determination of activity against adult Tetranychus cinnabarinus

[0128] The greenhouse mite killing activity of the compound of the present invention and the control compound KC1 was determined as follows:

[0129] According to the solubility of the test compound, dissolve it in acetone or dimethyl sulfoxide, and prepare 50 ml of the test solution of the required concentration with 0.1% Tween 80 solution. The content of acetone or dimethyl sulfoxide in the solution shall not exceed 10%.

[0130] Two true-leaf bean seedlings were inoculated with adult Tetranychus cinnabarinus mites and the base population was investigated. The entire plant was then sprayed with a handheld sprayer. Each treatment was repeated three times. After treatment, the seedlings were placed in a standard observation room. After 72 hours, the number of surviving mites was investigated and the mortality rate was calculated.

[0131] The test results are as follows:

[0132] When the concentration of the drug solution was 10 mg / L, the lethality of compounds 1.1, 1.2, 2.1, 2.2, 3.1, 3.2 and the control compound KC1 to Tetranychus cinnabarinus was 100%.

[0133] When the concentration of the drug solution was 1.25 mg / L, the lethality of compounds 1.1, 1.2, 2.1, 2.2, 3.1 and 3.2 to Tetranychus cinnabarinus was not less than 90%, while the lethality of the control compound KC1 to Tetranychus cinnabarinus was 0.

Claims

1. A phenyl sulfide (sulfoxide) compound, characterized in that: The compound is shown in the general formula I: In the general formula I: R1 is selected from halogen; R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F; n is selected from 0 or 1.

2. The compound according to claim 1, characterized in that: In the general formula I, R1 is selected from chlorine or bromine; R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F; n is selected from 0 or 1.

3. A method for preparing a phenyl sulfide (sulfoxide) compound as claimed in any one of claims 1 or 2, comprising the steps of: Step 1): subjecting compound VIII to a reduction reaction to obtain compound VII; Step 2): subjecting compound VII to a rearrangement reaction to obtain compound VI; Step 3): subjecting compound VI to a salt-forming reaction to obtain a hydrochloride, hydrobromide, sulfate or fluoroborate salt of compound VI, i.e., a compound of formula V; Step 4): subjecting the compound of formula V to a Sandmeyer reaction to obtain a compound of formula IV; Step 5): subjecting the compound of formula IV to a sulfonation reaction to obtain a compound of formula III; Step 6): subjecting the compound of formula III to a reduction reaction to obtain a compound of formula II; Step 7): subjecting the compound of formula II to an alkylation reaction to obtain a compound of formula I-1; Step 8): subjecting the compound of formula I-1 to an oxidation reaction to obtain a compound of formula I-2; in: R1 is selected from halogen; R2 is selected from -CF3, -CHF2, -CH2F, -CH2CF3, -CH2CHF2 or -CH2CH2F; X is selected from hydrogen or acetyl; Y is selected from HCl, HBr, H2SO4 or HBF4.

4. A compound which is an intermediate for preparing the phenyl sulfide (sulfoxide) compound according to any one of claims 1 to 2, characterized in that: The compound has the structure shown in the following general formula II: In the general formula II: R1 is selected from halogen; X is selected from hydrogen or acetyl.

5. A compound which is an intermediate for preparing the compound according to claim 4, characterized in that: The compound has the structure shown in the following general formula III: In the general formula III: R1 is selected from halogen.

6. A compound, characterized in that The compound is a hydrochloride, hydrobromide, sulfate or fluoroborate compound of compound VI according to claim 3, and the salt compound has a structure shown in the following general formula V: In general formula V: Y is selected from HCl, HBr, H2SO4 or HBF4.

7. Use of the compound of formula V according to claim 6 for preparing a compound of formula I, a compound of formula II, a compound of formula III or a compound of formula IV.

8. Use of the compound of general formula I according to claim 1 as a miticide in the field of agriculture or forestry.

9. A mite-killing composition, characterized in that: The composition comprises the compound of general formula I according to claim 1 and an agriculturally acceptable carrier, wherein the weight percentage of the active component in the composition is 0.1-99%.

10. A method for controlling agricultural or forestry pests, characterized by: An effective amount of the composition according to claim 9 is applied to the pest mites to be controlled or their growth medium.

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