A phenyl ether sulfite compound, a preparation method and application thereof

Abstract

The application discloses a phenyl ether sulfite compound and a preparation method and application thereof, and the structure is shown as formula 1. A fluorine-containing organic sulfur compound capable of being used as an active ingredient of a pesticide is prepared by connecting a fluorine-containing group to the end of the phenyl ether sulfite. The prepared phenyl ether sulfite compound can be used for preventing and treating harmful mites, and can further be used for preventing and treating mite eggs. The connected fluorine-containing group can enhance the lipophilicity of the molecule, so that the drug molecule is more easily penetrated into the cells of the insect body, acts on the corresponding target site, and causes death through a series of biochemical reactions. Experiments prove that the phenyl ether sulfite compound prepared by the application has a better killing effect on harmful mites, and a high mite killing effect can be achieved at a low use amount. The phenyl ether sulfite compound prepared by the application also specifically and long-acting inhibits the hatching of mite eggs, and the effect is obviously better than that of the propargite and other reported organic sulfur compounds.

Description

Technical Field

[0001] This invention belongs to the field of pesticide technology, and in particular relates to a phenyl ether sulfite compound, its preparation method and application. Background Technology

[0002] Agricultural mites are primarily phytophagous mites belonging to the order Acari of the class Arachnida. They are common crop pests, widely distributed worldwide, and can damage various crops such as citrus, cotton, apples, flowers, and various vegetables. Once crops are infested with mites, the damage ranges from minor issues like damaged appearance and reduced fruit quality to severe infestations leading to yield reduction or even total crop failure. Therefore, controlling agricultural mites has become a major technical challenge in modern agricultural technology. Agricultural mites are piercing-sucking mites, characterized by their small size, rapid reproduction, and strong adaptability. A single female can sometimes lay nearly a hundred eggs. The eggs hatch into larvae (3 pairs of legs), which gradually develop into nymphs (4 pairs of legs) and then into adults (4 pairs of legs). The adults then lay eggs, which in turn hatch into larvae. In addition, due to the unscientific use of traditional acaricides, mites have become increasingly resistant to them, and sometimes mites will recur after spraying. Some acaricides can only kill mites but cannot effectively inhibit the hatching of mite eggs, making control increasingly difficult. Therefore, when controlling mites, we must kill both mites and eggs at the same time, combining fast-acting and long-lasting effects.

[0003] Currently, the main acaricides used on the market include pyridaben, pyridaben, propargite, triazophos, abamectin, spirodiclofen, spirodiclofen, bifenazate, diflubenzuron, etoxazole, etoxazole-methyl, and cyprodinil. However, with the extension of application time and frequency, resistance to these acaricides is becoming increasingly serious. Even with increasingly higher application concentrations, the acaricide's effectiveness against adults, larvae, and nymphs remains unsatisfactory, and it is also difficult to effectively inhibit mite egg hatching.

[0004] Propargite, also known as acaricide, is an acaricide developed by Uniroyal Corporation of the United States in 1968. It was first officially registered in my country in 1998 by Alex Biochemicals Co., Ltd. Its structural formula is as follows: Figure 1 As shown, this is a broad-spectrum organosulfur acaricide that is highly effective and low in toxicity, acting as a contact pesticide. It has both stomach poison and contact action. Mechanism of action: After application to crops, the pesticide comes into contact with the insects, is absorbed by their cells, and affects mitochondrial magnesium levels. 2+ -ATPase and Na + / K +The transport of ATPase, with its action site at the F0 subunit, causes an imbalance in ion concentrations across the mitochondrial membrane, affecting the normal synthesis of ATP synthase, hindering the function of mitochondria in the nerve cells of pests, impacting their respiration and energy conversion, and ultimately disrupting the respiratory chain of mites, leading to their death. While propargite mites can kill adult and nymphal mites to eliminate or reduce mite damage to crops and thus increase yield, they are ineffective against mite eggs. This allows the eggs to hatch, significantly shortening the residual effect of pesticides, thus increasing the frequency and amount of application, which in turn increases mite resistance, economic costs, and environmental pollution.

[0005] US Patent 2529494A reported the structure of diester sulfite in 1948, namely... Figure 1 Part B has a long-chain alkyl structure, and Part C contains chloroalkyl or similar structures. It was demonstrated that it exhibits high acaricidal activity against the spider mite (Tetranychus telarius) (concentration ratio 1:25600, 100% mortality). British Patent GB977127A, in 1963, also reported the structure of the diester sulfite, namely… Figure 1 Part B has a long-chain alkyl structure, and Part C contains alkyloxy groups, aryl groups, and similar structures. Its inhibitory effect on the pre-germination stage of broadleaf plants and its insecticidal activity against Aedes aegypti larvae were elucidated. Shandong Kangqiao Biotechnology Co., Ltd. applied for a patent in July 2021 for an organosulfur compound and its preparation method and application (CN114315671A), whose structure is an analog of propargite, mainly altering... Figure 1 The structure of Part C in the report shows that the six compounds have a mortality rate of over 80% against Tetranychus carmine at a concentration of 25 ppm, while the efficacy of the control drug propargite is over 60% at the same concentration. The comparison shows that the compounds reported in the patent do not have a significant improvement in efficacy.

[0006] Therefore, in agricultural production, there is an urgent need for novel acaricides that are active against all stages of mites, including adult mites, larvae, nymphs and eggs, have good rapid effect, long-lasting effect, are safe for the environment and crops, and still have acaricidal activity under low temperature conditions in spring and autumn. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a phenyl ether sulfite compound, its preparation method, and its applications.

[0008] The technical solution adopted in this invention is: a phenyl ether sulfite compound, the structure of which is shown in Formula 1.

[0009]

[0010] Among them, R1, R2, R3, R4, and R5 are each independently selected from hydrogen, C1 to C2. 10 Alkyl, halogen, cyano, amino, nitro, hydroxyl, C1-C 10 Alkyloxy group, C1-C 10 Alkyl carbonyl, C1-C 10 Alkyloxycarbonyl, C1-C 10 Alkyl thio, C1-C 10 Haloalkylthio groups, C1-C 10 Haloalkyl, C1-C 10 Haloalkoxy, C3-C8 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsilyl, aryl, aryloxy, arylC1-C6 alkylthio, arylsulfonyl, arylsulfinyl, arylthio, heterocyclic, heterocyclic C1-C6 alkyl or heterocyclicoxy; R1, R2, R3, R4 and R5 are the same, some of the groups are the same or are different groups.

[0011] X is oxygen or methylene thio; Q is hydrogen, methyl or ethyl; W is fluoroethyl or fluoropropyl.

[0012] Preferably, R1 is hydrogen or tert-butyl; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen or tert-butyl or tert-pentyl; R5 is hydrogen; X is oxygen or methylene thio; Q is methyl or ethyl; W is 2-fluoroethyl or 2,2-difluoroethyl or 2,2,2-trifluoroethyl or 2,2,3,3-tetrafluoropropyl.

[0013] Preferably, it is one of formulas A1-A32;

[0014]

[0015]

[0016] A method for preparing phenyl ether sulfite compounds: Compound 2 reacts with epoxide of Formula 3 under the catalysis of a first base to generate compound 4; compound 4 reacts with thionyl chloride to generate compound 5.

[0017] The compound of formula 5 reacts with the alcohol of formula 6 in the presence of a second base to give the compound of formula 1.

[0018]

[0019] Preferably, the compound of formula 2 reacts with the epoxy compound of formula 3 under the catalysis of a base to generate the compound of formula 4, and the reaction temperature is 40-120°C; the first base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; the molar ratio of the compound of formula 2, the epoxy compound of formula 3, and the first base is 1:1-1.5:0.1-0.2;

[0020] Preferably, the solvent is dichloromethane, trichloromethane, water, toluene, xylene, N,N-dimethylformamide, methyl tert-butyl ether, or tetrahydrofuran, and the mass of the solvent is 1 to 3 times that of the compound of Formula 2.

[0021] Preferably, the compound of formula 4 reacts with thionyl chloride to generate the compound of formula 5 at a reaction temperature of -20 to 40°C; the molar ratio of the compound of formula 4 to thionyl chloride is 1:1 to 1.5.

[0022] Preferably, the solvent is dichloromethane, trichloromethane, toluene, or xylene, and its mass is 0.5 to 3 times that of the compound of formula 4.

[0023] Preferably, the compound of formula 5 reacts with the alcohol of formula 6 in the presence of a second base to obtain the compound of formula 1, and the reaction temperature is -10 to 20°C; the second base is one or more of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; the molar ratio of the compound of formula 5, the alcohol of formula 6, and the second base is 1:1 to 1.2:1 to 1.2.

[0024] Preferably, the solvent is dichloromethane, trichloromethane, toluene, xylene, or tetrahydrofuran, and its mass is 1.0 to 3.0 times that of the compound of formula 5.

[0025] Application of phenyl ether sulfite compounds in insecticides.

[0026] Preferably, one or more compounds of Formula 1 are used as the main component of the insecticide; the compounds of Formula 1 include optical isomers, racemates, or diastereomers;

[0027] Preferably, it is used for the control of harmful mites and / or mite eggs;

[0028] Preferably, it is used to control harmful mites of the Tetranychidae, Erythropodidae, Trichodidae, and Trichodidae families; preferably, it can be used to control adult mites, larvae, nymphs, or eggs of piercing-sucking mites.

[0029] Preferably, it can be used for one or more combinations of Tetranychus cinnabarinus, Tetranychus cinnabarinus eggs, Tetranychus two-spotted, Tetranychus two-spotted eggs, Tetranychus citrus, and Tetranychus citrus eggs.

[0030] A method for controlling invertebrate pests, comprising treating one or more of the following: the pest, its food chain, its habitat, its breeding ground, the plants on which the pest grows, and the soil on which the pest grows, with an insecticide containing a phenyl ether sulfite compound.

[0031] Preferably, the effective application amount of compound of formula 1 is 10 to 1000 grams per hectare.

[0032] The advantages and positive effects of this invention are: a new compound has been designed and prepared that can produce a good killing effect on mites and / or mite eggs; when used as an insecticide, it has high acaricidal activity, especially with a long-lasting effect on mite eggs; even when used at low concentrations, this compound has excellent control effects with rapid action and long-lasting effect. Attached Figure Description

[0033] Figure 1 The structural formula of propargite;

[0034] Figure 2 Structural formulas of phenyl ether sulfite compounds. Detailed Implementation

[0035] The embodiments of the present invention will now be described with reference to the accompanying drawings.

[0036] This invention relates to a phenyl ether sulfite compound, its preparation method, and its application. Addressing the problems of existing acaricides such as poor activity against adults, larvae, and nymphs, difficulty in effectively inhibiting mite egg hatching, and severe resistance, a novel phenyl ether sulfite compound was designed and prepared. Starting from the compound's structure and mechanism of action, [the invention further details the design and preparation of this compound]. Figure 1 The structure of Part B is designed as an alkane with less steric hindrance, and a highly lipophilic fluorinated alkyl group is introduced into the terminal Part C of the sulfite ester to enhance the molecule's permeability to cell membranes, etc. This allows for effective killing of adult mites, nymphs, and larvae at low doses, as well as more effective inhibition of mite egg hatching and a longer duration of efficacy. The specific structure of the phenyl ether sulfite ester compound is shown in Formula 1:

[0037]

[0038] Among them, R1, R2, R3, R4, and R5 are each independently selected from hydrogen, C1 to C2. 10 Alkyl, halogen, cyano, amino, nitro, hydroxyl, C1-C 10 Alkyloxy group, C1-C 10 Alkyl carbonyl, C1-C 10 Alkyloxycarbonyl, C1-C 10 Alkyl thio, C1-C 10 Haloalkylthio groups, C1-C 10 Haloalkyl, C1-C10 Haloalkoxy, C3-C8 cycloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsilyl, aryl, aryloxy, arylC1-C6 alkylthio, arylsulfonyl, arylsulfinyl, arylthio, heterocyclic, heterocyclic C1-C6 alkyl or heterocyclicoxy; R1, R2, R3, R4 and R5 are the same, some of which are the same or different groups; X is oxygen or methylene thio; Q is hydrogen, methyl or ethyl; W is fluoroethyl or fluoropropyl.

[0039] In some embodiments of the present invention, the preferred groups are: R1 is hydrogen or tert-butyl; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen or tert-butyl or tert-amyl; R5 is hydrogen; X is oxygen or methylene thio; Q is methyl or ethyl; W is 2-fluoroethyl or 2,2-difluoroethyl or 2,2,2-trifluoroethyl or 2,2,3,3-tetrafluoropropyl.

[0040] Specifically, according to the structural formula of compound 1, each group can be shown in Table 1.

[0041] Table 1. Phenyl ether sulfite compounds

[0042]

[0043] In the table, Me represents methyl, Et represents ethyl, and tBu represents tert-butyl.

[0044] Among the compounds included in the phenyl ether sulfite class, where geometric isomers of R-type and S-type exist depending on the type of substituents, this invention includes these R-type, S-type, or mixtures containing S-type and R-type in any proportion. Furthermore, among the compounds included in this invention, where optical isomers exist due to having one or more asymmetric carbon atoms and asymmetric sulfur atoms, this invention includes all optical isomers, racemates, or diastereomers.

[0045] The phenyl ether sulfite compounds shown in Formula 1 can be prepared via the following synthetic route:

[0046]

[0047] In the first step of the reaction, compound 2 reacts with epoxide compound 3 in a solvent under the catalysis of the first base to generate compound 4.

[0048] In the second step, compound 4 further reacts with thionyl chloride in a solvent to generate compound 5.

[0049] In the third step, the compound of formula 5 reacts with the alcohol compound of formula 6 in the presence of the second base to generate the compound of formula 1.

[0050] The specific preparation process is as follows:

[0051] In the first step, compound 2 reacts with epoxide of formula 3 in a solvent under the catalysis of the first base to generate compound 4; the reaction temperature is 40–120 °C; the first base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; the solvent is dichloromethane, chloroform, water, toluene, xylene, N,N-dimethylformamide, methyl tert-butyl ether, or tetrahydrofuran, with a mass of 1.0–3.0 times that of compound 2; the molar ratio of compound 2, epoxide of formula 3, and the first base is 1.0:(1.0–1.5):(0.1–0.2);

[0052] In the second step, compound 4 further reacts with thionyl chloride in a solvent to generate compound 5; the reaction temperature is -20 to 40 °C; the solvent is dichloromethane, trichloromethane, toluene, or xylene, with a mass of 0.5 to 3.0 times that of compound 4; the molar ratio of compound 4 to thionyl chloride is 1.0:(1.0 to 1.5);

[0053] In the third step, the compound of formula 5 reacts with the alcohol of formula 6 in the presence of a second base to generate the compound of formula 1 at a reaction temperature of -10 to 20°C. The second base is one or more of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide. The solvent is dichloromethane, trichloromethane, toluene, xylene, or tetrahydrofuran, with a mass of 1.0 to 3.0 times that of the compound of formula 5. The molar ratio of the compound of formula 5, the alcohol of formula 6, and the second base is 1.0:(1.0 to 1.2):(1.0 to 1.2).

[0054] In some embodiments of the present invention, the preferred groups are: R1 is hydrogen or tert-butyl; R2 is hydrogen; R3 is hydrogen; R4 is hydrogen or tert-butyl or tert-amyl; R5 is hydrogen; X is oxygen or methylene thio; Q is methyl or ethyl; W is 2-fluoroethyl or 2,2-difluoroethyl or 2,2,2-trifluoroethyl or 2,2,3,3-tetrafluoropropyl.

[0055] Compound of Formula 1 can be used to prepare insecticides, and is especially suitable as an acaricide. It has a highly active killing effect on harmful mites such as Tetranychus cinnabarinus, Tetranychus citrus, Tetranychus two-spotted, Tetranychus maculata, Tetranychus kaempferi, Tetranychus hawthorn, Erythropodidae, Aphididae, and Aphididae.

[0056] One or more compounds of the phenyl ether sulfite class are used as active ingredients in insecticides that kill piercing-sucking mites at various stages of their development (adults, larvae, nymphs, and their eggs). The dosage of the compound varies depending on various factors to achieve the desired effect, such as the compound used, the crop being protected, the type of pest, the degree of infestation, the application method, the application environment, and the formulation.

[0057] One or more different compounds of Formula 1 are dissolved or dispersed in a carrier, or formulated into a preparation for use as an acaricide, making it easier to disperse upon application. The weight percentage of the active ingredient in the composition is 1% to 99%. For example, these active substances can be formulated as wettable powders, water-dispersible granules, microemulsions, emulsions, or emulsifiable concentrates. In these compositions, at least one liquid or solid carrier is added, and a suitable surfactant may be added if necessary. The acaricide composition is applied to the mites or their growth medium. The pests, their food chain, their habitats or breeding grounds, or the plants and soil on which the pests grow are treated with a formulation comprising an insecticidal effective amount of a compound of Formula 1. A commonly chosen effective amount is 10 to 1000 grams per hectare, preferably 10 to 300 grams per hectare.

[0058] In some embodiments of the present invention, for certain applications, such as agriculture, one or more other insecticides, acaricides, fungicides, herbicides, plant growth regulators or fertilizers may be added to the acaricide composition of the present invention, thereby producing additional advantages and effects.

[0059] Phenyl ether sulfite compounds are prepared by attaching a fluorine-containing group to the end of a phenyl ether sulfite ester, resulting in fluorinated organosulfur compounds that can be used as insecticide active ingredients. The fluorine-containing group enhances the lipophilicity of the molecule, allowing the drug molecule to penetrate more easily into the insect cells and act on the corresponding target sites, leading to the death of the insect through a series of biochemical reactions. These compounds have excellent acaricidal effects, especially against the eggs, larvae, nymphs, and adults of Tetranychus carmine and Tetranychus two-spotted. They are effective even at low concentrations and specifically and persistently inhibit the hatching of mite eggs, showing significantly better efficacy than propargite and other previously reported organosulfur compounds.

[0060] The present invention will now be described with reference to the accompanying drawings. Experimental methods not specifically described in terms of operation steps are performed in accordance with the corresponding product manuals. Unless otherwise specified, the instruments, reagents, and consumables used in the embodiments can be purchased from commercial companies.

[0061] Example 1: Preparation of 1-(4-(tert-butyl)phenoxy)propyl-2-(2,2-difluoroethyl)sulfite (Compound A2)

[0062] Step 1 reaction: Preparation of 1-(4-tert-butylphenoxy)-2-propanol

[0063]

[0064] Toluene (200 mL), p-tert-butylphenol (150.22 g, 1.00 mol), and sodium hydroxide (4.00 g, 0.10 mol) were added to a 500 mL round-bottom flask. After purging with nitrogen three times, the mixture was stirred and heated to 50-60 °C under a nitrogen atmosphere. 1,2-epoxypropane (63.89 g, 1.10 mol) was added dropwise, and the reaction was allowed to proceed for 10 hours. After the gas phase analysis showed that the reaction was satisfactory, the system was cooled to 30 °C, 200 mL of water was added, and dilute hydrochloric acid was added dropwise to adjust the pH of the system to neutral. After extraction and separation, the aqueous phase was extracted once with 50 mL of toluene. The organic phases were combined after separation, dried with anhydrous magnesium sulfate, filtered, and then evaporated under reduced pressure to remove the solvent, yielding 211 g of a colorless viscous liquid product with a purity of 96%.

[0065] Steps 2 and 3: Preparation of 1-(4-(tert-butyl)phenoxy)propyl-2-(2,2-difluoroethyl)sulfite (Compound A2)

[0066]

[0067] Toluene (100 mL) and thionyl chloride (89.23 g, 0.75 mol) were added to a 500 mL round-bottom flask. The reaction system was cooled to -5 °C, and 1-(4-tert-butylphenoxy)-2-propanol (104.15 g, 0.50 mol) was added dropwise with stirring. The reaction temperature was kept below 10 °C. After the addition was complete, the reaction was continued for 10 hours. After the gas phase detection was qualified, the excess thionyl chloride was removed by vacuum distillation to obtain a crude toluene solution of 1-(4-(tert-butyl)phenoxy)propyl-2-yl-(O)-sulfinyl chloride.

[0068] In another 500 mL round-bottom flask, toluene (200 mL), triethylamine (55.65 g, 0.55 mol), and 2,2-difluoroethanol (45.13 g, 0.55 mol) were added. The reaction system was cooled to -5 °C, and the crude toluene solution of 1-(4-(tert-butyl)phenoxy)propyl-2-(O)-sulfinyl chloride was slowly added dropwise with stirring. After the addition was complete, the reaction was allowed to proceed at room temperature for 1 hour. After the gas phase analysis showed that the reaction solution was qualified, the reaction solution was poured into 500 mL of ice water, and the pH was adjusted to neutral with glacial acetic acid. After separation, the aqueous phase was extracted once with 50 mL of toluene. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and purified by rotary evaporation under reduced pressure and column chromatography to obtain 155 g of a colorless viscous oily liquid, with a yield of 91%.

[0069] Example 2: Preparation of 1-(4-(tert-butyl)phenoxy)but-2-(2-fluoroethyl)sulfite (Compound A5)

[0070] Step 1 reaction: Preparation of 1-(4-tert-butylphenoxy)-2-butanol

[0071]

[0072] Toluene (200 mL), p-tert-butylphenol (150.22 g, 1.00 mol), and potassium hydroxide (6.60 g, 0.10 mol) were added to a 500 mL round-bottom flask. After purging with nitrogen three times, the mixture was stirred and heated to 80-90 °C under a nitrogen atmosphere. 1,2-epoxybutane (79.32 g, 1.10 mol) was added dropwise, and the reaction was allowed to proceed for 8 hours. After the gas phase analysis showed that the reaction was satisfactory, the system was cooled to 30 °C, 200 mL of water was added, and dilute hydrochloric acid was added dropwise to adjust the pH of the system to neutral. After extraction and separation, the aqueous phase was extracted once with 50 mL of toluene. The organic phases were combined after separation, dried with anhydrous magnesium sulfate, filtered, and then evaporated under reduced pressure to remove the solvent, yielding 228 g of a colorless viscous liquid product with a purity of 96%.

[0073] Steps 2 and 3: Preparation of 1-(4-(tert-butyl)phenoxy)but-2-(2-fluoroethyl)sulfite (Compound A5)

[0074]

[0075] Toluene (100 mL) and thionyl chloride (89.23 g, 0.75 mol) were added to a 500 mL round-bottom flask. The reaction system was cooled to -5 °C, and 1-(4-tert-butylphenoxy)-2-butanol (111.16 g, 0.50 mol) was added dropwise with stirring. The reaction temperature was kept below 10 °C. After the addition was complete, the reaction was continued for 15 hours. After the gas phase detection was qualified, the excess thionyl chloride was removed by vacuum distillation to obtain a crude toluene solution of 1-(4-(tert-butyl)phenoxy)but-2-yl-(O)-sulfinyl chloride.

[0076] In another 500 mL round-bottom flask, toluene (200 mL), triethylamine (55.65 g, 0.55 mol), and 2-fluoroethanol (35.23 g, 0.55 mol) were added. The reaction system was cooled to -10 °C, and the crude toluene solution of 1-(4-(tert-butyl)phenoxy)but-2-(O)-sulfinyl chloride was slowly added dropwise with stirring. After the addition was complete, the reaction was allowed to proceed at room temperature for 1 hour. After the gas phase analysis showed that the reaction solution was qualified, it was poured into 500 mL of ice water, and the pH was adjusted to neutral with glacial acetic acid. After separation, the aqueous phase was extracted once with 50 mL of toluene. The organic phases were combined, dried over anhydrous magnesium sulfate, filtered, and purified by rotary evaporation under reduced pressure and column chromatography to obtain 153 g of a colorless viscous oily liquid, with a yield of 92%.

[0077] Example 3: Preparation of 1-(4-(tert-butyl)benzylthio)propyl-2-(2-fluoroethyl)sulfite (Compound A9)

[0078] Step 1 reaction: Preparation of 1-(4-tert-butylbenzylthio)-2-propanol

[0079]

[0080] It was prepared according to the method described in the first step of Example 1.

[0081] Steps 2 and 3: Preparation of 1-(4-(tert-butyl)benzylthio)propyl-2-(2-fluoroethyl)sulfite (Compound A9)

[0082]

[0083] It was prepared according to the method described in steps two and three of Example 1.

[0084] Example 4: Preparation of 1-(4-(tert-butyl)benzylthio)but-2-(2,2-difluoroethyl)sulfite (Compound A14)

[0085] Step 1 reaction: Preparation of 1-(4-tert-butylbenzylthio)-2-butanol

[0086]

[0087] It was prepared according to the method described in the first step of Example 2.

[0088] Steps 2 and 3: Preparation of 1-(4-(tert-butyl)benzylthio)but-2-(2,2-difluoroethyl)sulfite (compound A14)

[0089]

[0090] It was prepared according to the method described in steps two and three of Example 2.

[0091] Example 5: Preparation of 1-(4-(tert-amyl)phenoxy)propyl-2-(2,2,3,3-tetrafluoropropyl)sulfite (Compound A20)

[0092] Step 1 reaction: Preparation of 1-(4-tert-pentylphenoxy)-2-propanol

[0093]

[0094] It was prepared according to the method described in the first step of Example 1.

[0095] Steps 2 and 3: Preparation of 1-(4-(tert-amyl)phenoxy)propyl-2-yl-(2,2,3,3-tetrafluoropropyl)sulfite (compound A20)

[0096]

[0097] It was prepared according to the method described in steps two and three of Example 1.

[0098] Example 6: Preparation of 1-(4-(tert-amyl)phenoxy)but-2-yl-(2,2,3,3-tetrafluoropropyl)sulfite (Compound A24)

[0099] Step 1 reaction: Preparation of 1-(4-tert-pentylphenoxy)-2-butanol

[0100]

[0101] It was prepared according to the method described in the first step of Example 2.

[0102] Steps 2 and 3: Preparation of 1-(4-(tert-amyl)phenoxy)but-2-yl-(2,2,3,3-tetrafluoropropyl)sulfite (compound A24)

[0103]

[0104] It was prepared according to the method described in steps two and three of Example 2.

[0105] Example 7: Preparation of 1-(1-(tert-butyl)phenoxy)propyl-2-(2,2-difluoroethyl)sulfite (Compound A26)

[0106] Step 1 reaction: Preparation of 1-(1-tert-butylphenoxy)-2-propanol

[0107]

[0108] It was prepared according to the method described in the first step of Example 1.

[0109] Steps 2 and 3: Preparation of 1-(1-(tert-butyl)phenoxy)propyl-2-(2,2-difluoroethyl)sulfite (compound A26)

[0110]

[0111] It was prepared according to the method described in steps two and three of Example 1.

[0112] Example 8: Preparation of 1-(1-(tert-butyl)phenoxy)but-2-(2-fluoroethyl)sulfite (Compound A29)

[0113] Step 1 reaction: Preparation of 1-(1-tert-butylphenoxy)-2-propanol

[0114]

[0115] It was prepared according to the method described in the first step of Example 2.

[0116] Steps 2 and 3: Preparation of 1-(1-(tert-butyl)phenoxy)but-2-yl-(2-fluoroethyl)sulfite (Compound A29)

[0117]

[0118] It was prepared according to the method described in steps two and three of Example 2.

[0119] Compounds A1-A32 can all be obtained from raw materials containing the groups shown in Table 1. These raw materials are all commercially available compounds and were prepared according to the method of Example 1 or Example 2. The properties, NMR characterization data and high-resolution mass spectrometry characterization data of compounds A1-A32 listed in Table 1 are shown in Table 2.

[0120] Table 2. Properties, NMR and high-resolution mass spectrometry data of phenyl ether sulfites.

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127]

[0128] Example 9: Preparation of formulations of phenyl ether sulfite compounds

[0129] Formulation 1: Preparation of 30% Compound 2 emulsifiable concentrate

[0130] Dissolve 30 parts of compound 2 in 13 parts of methyl oleate, then add 14 parts of calcium dodecylbenzenesulfonate and 7 parts of tristyrenephenol polyoxyethylene ether polyoxypropylene ether, and finally add methylnaphthalene to bring the total to 100 parts. Stir and mix thoroughly to obtain a 30% emulsifiable concentrate of compound 2.

[0131] Formulation 2: Preparation of 40% Compound 5 emulsifiable concentrate

[0132] 40 parts of compound 5 were dissolved in 13 parts of methyl oleate, and then 14 parts of calcium dodecylbenzenesulfonate and 7 parts of tristyrenephenol polyoxyethylene ether polyoxypropylene ether were added. Methylnaphthalene was then added to bring the total volume to 100 parts. The mixture was stirred until homogeneous to obtain an emulsion containing 40% compound 5.

[0133] Formulation 3: Preparation of 25% Compound 31 emulsifiable concentrate

[0134] 25 parts of compound 31 were dissolved in 13 parts of methyl oleate, and 14 parts of calcium dodecylbenzenesulfonate and 7 parts of tristyrenephenol polyoxyethylene ether polyoxypropylene ether were added respectively. Then, methylnaphthalene was added to bring the total to 100 parts. The mixture was stirred until homogeneous to obtain an emulsion containing 25% compound 31.

[0135] Preparations numbered 1-32 were prepared according to the above preparation steps, and then used for biological experiments on killing mites and their eggs.

[0136] Example 10: Biological experiment on the killing effect of Tetranychus cinnabarinus and its eggs.

[0137] The formulations 1-32 prepared in Example 9 were subjected to Tetranychus cinnabarinus tests. Meanwhile, other compound formulations involved in existing patent documents and the commonly used insecticide propargite were used as comparative examples and subjected to Tetranychus cinnabarinus tests under the same conditions.

[0138] The specific steps of the Tetranychus carmineus test are as follows: Dissolve the test compound in acetone and dilute it to the required concentration with 0.1% Tween 80 solution. The acetone content should not exceed 5%. Remove one true leaf from a bean seedling that has grown to two true leaves. Inoculate with Tetranychus carmineus and investigate the initial population. Spray the entire plant with a handheld sprayer. Repeat each treatment three times. After treatment, observe in a constant temperature observation room. Investigate the number of live mites after 72 hours and calculate the mortality rate.

[0139] Each inoculation involves 100 to 200 Tetranychus carmineus mites.

[0140] Mortality rate = (Number of inoculated worms - Number of surviving worms after treatment) ÷ Number of inoculated worms × 100%.

[0141] The killing effects of each compound formulation on Tetranychus cinnabarinus are shown in Table 3.

[0142] Table 3 shows the bioactivity data of the prepared phenyl ether sulfite compounds 1-32 against the spider mite *Tetranychus cinnabarinus*.

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150] As shown in Table 3, compound A1-A32 showed a mortality rate of over 90% against Tetranychus cinnabarinus at 10 ppm (10 mg / L), which was significantly better than the control drug propargite.

[0151] To further verify the killing effect of the above compounds on Tetranychus cinnabarinus eggs, an egg test was conducted on Tetranychus cinnabarinus eggs. The specific steps are as follows:

[0152] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% Tween 80 solution. The acetone content should not exceed 5%. One true leaf was removed from the bean seedlings that had grown to two true leaves. After inoculating with spider mite eggs, the initial population was investigated. The whole plant was sprayed with a handheld sprayer. Each treatment was repeated 3 times. After treatment, the plants were placed in a constant temperature observation room to observe the hatching of mite eggs and record the hatching rate.

[0153] The number of Tetranychus cinnabarinus eggs inoculated each time was 100–200. The hatching status of the mite eggs is shown in Table 4, where the experimental insects were Tetranychus cinnabarinus eggs, and the concentration was 10 ppm.

[0154] Table 4 shows the bioactivity data of the prepared phenyl ether sulfite compounds 1-32 against the eggs of the spider mite *Tetranychus cinnabarinus*.

[0155]

[0156] After application, compound A1-A32 maintained its inhibitory effect on Tetranychus cinnabarinus eggs for up to 28 days at a treatment concentration of 10 ppm (10 mg / L), and significantly reduced the hatching rate of the eggs.

[0157] Example 11: Biological experiment on the killing effect of two-spotted spider mites and their eggs

[0158] The formulations 1-32 prepared in Example 9 were then used in experiments on the two-spotted spider mite (Tetranychus urticae Koch), and the specific steps are as follows:

[0159] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% Tween 80 solution, with the acetone content not exceeding 5%. One true leaf was removed from the bean seedlings that had grown to two true leaves. The seedlings were inoculated with two-spotted spider mites, and the initial population was investigated. The entire plant was sprayed with a handheld sprayer. Each treatment was repeated 3 times. The seedlings were observed in a constant temperature observation room after treatment. The number of live mites was investigated after 72 hours, and the mortality rate was calculated.

[0160] Each inoculation involves 100 to 200 two-spotted spider mites.

[0161] Mortality rate = (Number of inoculated worms - Number of surviving worms after treatment) ÷ Number of inoculated worms × 100%.

[0162] The killing effect of each formulation on the two-spotted spider mite is shown in Table 5.

[0163] Table 5 shows the bioactivity data of the prepared phenyl ether sulfite compounds 1-32 against the two-spotted spider mite.

[0164]

[0165] As can be seen from the data in Table 5, compound A1-A32 showed a mortality rate of over 90% against two-spotted spider mites at a treatment concentration of 10 ppm (10 mg / L).

[0166] Next, conduct an egg test for the two-spotted spider mite (Tetranychus urticae Koch). The specific steps are as follows:

[0167] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% Tween 80 solution. The acetone content should not exceed 5%. One true leaf was removed from the bean seedlings that had grown to two true leaves. After inoculating with two-spotted spider mite eggs, the initial population was investigated. The whole plant was sprayed with a handheld sprayer. Each treatment was repeated 3 times. After treatment, the plants were placed in a constant temperature observation room to observe the hatching of mite eggs and record the hatching rate.

[0168] The number of two-spotted spider mite eggs inoculated each time was 100-200. The hatching status of the mite eggs is shown in Table 6, where the experimental insects were two-spotted spider mite eggs, the experimental concentration was 10 ppm, and the hatching rate of the mite eggs was detected.

[0169] Table 6 shows the bioactivity data of the prepared phenyl ether sulfite compounds 1-32 against Tetranychus tinctoria eggs.

[0170]

[0171]

[0172] The data in the table show that after application, compound A1-A32 maintained its inhibitory effect on mite eggs for up to 28 days at a treatment concentration of 10 ppm (10 mg / L), and the hatching rate of mite eggs was significantly reduced.

[0173] Example 12: Biological experiment on the killing of citrus red spider mite and its eggs

[0174] The formulations 1-32 prepared in Example 9 were then used in the Panonychus citri McGregor test, and the specific steps are as follows:

[0175] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% Tween 80 solution, with the acetone content not exceeding 5%. One true leaf was removed from the bean seedlings that had grown to two true leaves. After inoculating with citrus parsnip, the initial population was investigated. The whole plant was sprayed with a handheld sprayer. Each treatment was repeated 3 times. After treatment, the plants were observed in a constant temperature observation room. The number of live mites was investigated after 72 hours, and the mortality rate was calculated.

[0176] The number of citrus psyllid mites inoculated each time is 100 to 200.

[0177] Mortality rate = (Number of inoculated worms - Number of surviving worms after treatment) ÷ Number of inoculated worms × 100%.

[0178] The killing effect of each formulation on citrus red spider mite is shown in Table 7.

[0179] Table 7. Bioactivity data of the prepared phenyl ether sulfite compounds A1-A32 against *Pachycercus citrinum*.

[0180]

[0181]

[0182] As can be seen from the data in Table 7, compound 1-32 showed a mortality rate of over 90% against Panonychuscitri McGregor at 10 ppm (10 mg / L).

[0183] Next, conduct an egg test for the citrus red spider mite (Panonychus citri McGregor). The specific steps are as follows:

[0184] The test compound was dissolved in acetone and diluted to the required concentration with 0.1% Tween 80 solution. The acetone content should not exceed 5%. One true leaf was removed from the bean seedlings that had grown to two true leaves. After inoculating with eggs of the citrus paronychia mite, the initial population was investigated. The whole plant was sprayed with a handheld sprayer. Each treatment was repeated 3 times. After treatment, the plants were placed in a constant temperature observation room to observe the hatching of mite eggs and record the hatching rate.

[0185] Each inoculation involves 100–200 citrus psyllid eggs. Egg hatching is shown in Table 8.

[0186] Table 8. Bioactivity test data of the prepared phenyl ether sulfite compounds 1-32 against the eggs of *Paecilomyces citrus*.

[0187]

[0188]

[0189] The data in the table show that after application, compound 1-32 has a residual effect on mite eggs for up to 28 days at 10 ppm (10 mg / L), and the hatching rate of mite eggs is very low.

[0190] Example 13: Field fruit tree trial

[0191] Field trials on fruit trees in citrus-producing areas of southern my country at various developmental stages (adults, nymphs, larvae, and eggs) of the citrus mite.

[0192] As is well known, the citrus red mite is one of the most serious pests that occur in citrus producing areas in my country. It is figuratively called "the number one pest of citrus". The citrus red mite is distributed in most citrus producing areas, but the infestation is more serious in citrus producing areas with less sunshine in Yunnan, Guizhou, Sichuan, northwestern Hubei and western Hunan.

[0193] Taking compounds 2, 4, 5, 9, 12, 13, 16, 20, 24, 27, 29, and 32 as examples, field fruit tree trials were conducted in a portion of the citrus planting experimental area in Yunnan. The dosage of compounds 2, 4, 5, 9, 12, 13, 16, 20, 24, 27, 29, and 32 was 80g (the effective components of compounds 2, 4, 5, 9, 12, 13, 16, 20, 24, 27, 29, and 32) / hm². 2 .

[0194] Within one day after spraying, the number of adult, nymphal, and larval citrus parsnipal mites decreased significantly. After three days, the control effect reached over 90%. Continued observation showed that the inhibitory effect on mite egg hatching lasted for more than 28 days. After four weeks, a very small number of mite eggs hatched, with a hatching rate of less than 5%.

[0195] Using propargite, spirodiclofen, diflubenzuron, etoxazole, etoxazole-propargyl, and cyprodinil as control pesticides, and sprayed at the same effective dosage, the control efficacy of propargite, spirodiclofen, diflubenzuron, etoxazole, etoxazole-propargyl, and cyprodinil were 12%, 23%, 38%, 46%, 51%, and 57%, respectively. The duration of inhibition of mite egg hatching was less than 3 days for all of them. It is evident that, under the same pesticide dosage, the difenosulfite compounds used in this example, when used as insecticides, have significantly higher killing efficacy than propargite, spirodiclofen, diflubenzuron, etoxazole, etoxazole-propargyl, and cyprodinil, achieving high killing efficacy at low concentrations while providing long-lasting inhibition of mite egg hatching.

[0196] The embodiments of the present invention have been described in detail above, but the content described is only a preferred embodiment of the present invention and should not be considered as limiting the scope of the present invention. All equivalent changes and improvements made within the scope of the present invention should still fall within the patent coverage of the present invention.

Claims

1. A phenyl ether sulfite compound, characterized in that: The structure is shown in Equation 1. Formula 1; Specifically, it is one of formulas A3-A32; 。 2. A method for preparing the phenyl ether sulfite compound of claim 1, characterized in that: Compound 2 reacts with epoxide of formula 3 under the catalysis of the first base to generate compound 4; compound 4 reacts with thionyl chloride to generate compound 5; compound 5 reacts with alcohol of formula 6 in the presence of the second base to give compound 1. Formula 2; Formula 3; Equation 4; Formula 5; Formula 6; Among them, R1, R2, R3, R4, R5, X, Q and W correspond to the corresponding groups in the compounds of formula A3-A32.

3. The method for preparing phenyl ether sulfite compounds according to claim 2, characterized in that: Compound 2 reacts with epoxide of formula 3 under the catalysis of a base to generate compound 4. The reaction temperature is 40~120℃. The first base is one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide. The molar ratio of compound 2, epoxide of formula 3, and the first base is 1:1~1.5:0.1~0.

2. The solvent is dichloromethane, trichloromethane, water, toluene, xylene, N,N-dimethylformamide, methyl tert-butyl ether, or tetrahydrofuran, and the mass of the solvent is 1 to 3 times that of the compound of formula 2.

4. The method for preparing phenyl ether sulfite compounds according to claim 3, characterized in that: The compound of formula 4 reacts with thionyl chloride to form the compound of formula 5 at a reaction temperature of -20 to 40 °C; the molar ratio of the compound of formula 4 to thionyl chloride is 1:1 to 1.

5. The solvent is dichloromethane, trichloromethane, toluene, or xylene, and its mass is 0.5 to 3 times that of the compound of formula 4.

5. The method for preparing phenyl ether sulfite compounds according to claim 4, characterized in that: Compound of Formula 5 reacts with alcohol of Formula 6 in the presence of a second base to yield compound of Formula 1 at a reaction temperature of -10 to 20 °C; the second base is one or more of pyridine, dimethylaminopyridine, triethylamine, diisopropylethylamine, sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide; the molar ratio of compound of Formula 5, alcohol of Formula 6, and the second base is 1:1 to 1.2:1 to 1.

2. The solvent is dichloromethane, trichloromethane, toluene, xylene, or tetrahydrofuran, and its mass is 1.0 to 3.0 times that of the compound of formula 5.

6. The application of the phenyl ether sulfite compound according to claim 1 in insecticides, characterized in that: Used to control harmful mites and / or mite eggs.

7. The application according to claim 6, characterized in that: One or more compounds of Formula 1 are used as the main component of insecticides.

8. The application according to claim 7, characterized in that: Used to control harmful mites belonging to the families Tetranychidae, Erythropodidae, Triplophyta, or Triplophyta.

9. The application according to claim 7, characterized in that: Used for the control of adult mites, larvae, nymphs, or eggs of piercing-sucking mites.

10. The application according to claim 7, characterized in that: It is used for one or more of the following: Tetranychus cinnabarinus, Tetranychus cinnabarinus eggs, Tetranychus two-spotted, Tetranychus two-spotted, Toxocara citrinum, and Toxocara citrinum eggs.

11. A method for controlling invertebrate pests, characterized in that: Treat one or more of the following: pests, their food chain, their habitat, their breeding grounds, the plants on which the pests grow, and the soil on which the pests grow, with an insecticide containing the phenyl ether sulfite compound of claim 1; the pests being mites and / or mite eggs. The effective application rate of compound Formula 1 is 10 to 1000 grams per hectare.

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