A pesticide composition containing a biphenyl sulfide compound and application thereof

Abstract

The application belongs to the technical field of pesticides, and relates to a pesticide composition containing a biphenyl sulfide compound and application thereof. The pesticide composition containing the biphenyl sulfide compound comprises active ingredient A and active ingredient B. The active ingredient A is a biphenyl sulfide compound, and the active ingredient B is any one or more than one insecticide and acaricide, such as B1 heterocycle, B2 quinone, B3 phenyl acetonitrile, B4 oxazole, B5 pyrazole amide and the like. The pesticide composition can effectively control various phytophagous mites, shows a synergistic effect within a certain proportion range, can expand the acaricidal spectrum, reduce the use cost, reduce the amount of pesticide, prolong the effective period and delay the development of drug resistance.

Description

Technical Field

[0001] This invention belongs to the field of pesticides, specifically relating to a pesticide composition containing biphenyl sulfide compounds and its application. Background Technology

[0002] Herbivorous mites are significant pests of many agricultural crops worldwide. If not controlled below economic thresholds, they can threaten the production of food, feed, and fiber. In particular, mites belonging to the families Tetranychidae, Trichophyton, Tardiidae, and Eriophyididae are important pests, directly feeding on plants or transmitting plant pathogens and viruses, thus harming crops.

[0003] Spider mites are an important group of agricultural pests, comprising over 100 species. Due to their tiny size and difficulty in identification, coupled with global climate change, pesticide resistance, and changing cropping systems, spider mite damage is becoming increasingly severe. Common hosts for these mites include a wide range of economic crops such as grasses (corn), malvaceaes (cotton, hollyhock), legumes (soybeans, mung beans, red beans, kidney beans, etc.), solanaceae (potatoes, eggplants, tomatoes, peppers, etc.), and cucurbitaceae (cucumbers, pumpkins, tomatoes, watermelons, winter melons, etc.). We found that spider mites are the most prevalent, with the most common being *Tetranychus truncatus*, followed by *Tpueraricola*, *T. kanzawai*, *T. urticae* (red form), and *T. urticae* (green form). These important agricultural pests are particularly prone to developing pesticide resistance due to their short reproductive cycles, high reproductive rates, low mobility, high self-pollination rates, and tendency to develop resistance.

[0004] For a long time, chemical control methods have been the main approach to controlling spider mites in production. The extensive use of chemical insecticides (acaricides) has made spider mites one of the most resistant pests. Rational compounding or mixing of chemical agents has several advantages, including broadening the insecticidal spectrum, improving control efficacy, extending the optimal application period, reducing dosage, minimizing phytotoxicity, reducing residues, and delaying the development of pesticide resistance in mites. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention provides a pesticide composition containing biphenyl sulfide compounds and its application. This pesticide composition can effectively control various agronomic mites, exhibiting a synergistic effect within a certain proportion range. It can broaden the acaricidal spectrum, reduce usage costs, decrease dosage, prolong the duration of effectiveness, and delay the development of resistance.

[0006] A pesticide composition containing a diphenyl sulfide compound, the pesticide composition comprising active ingredient A and active ingredient B, wherein active ingredient A is a diphenyl sulfide compound as shown in formula (I):

[0007] Active ingredient B is selected from one or more of the following acaricides.

[0008] Insecticides and acaricides: B1 heterocyclic compounds, B2 quaternary keto acids, B3 benzoyl acetonitrile compounds, B4 oxazoles, B5 pyrazole amides, B6 bifenhydrazine compounds, B7 antibiotics, B8 organotin compounds, B9 tetrazines, B... 10 Thiazolidinediones, B 11 Sulfites, B 12 Thioureas, B 13 sulfoxides, B 14 Bridged cyclic amines, B 15 Quinoline, B 16 Quinazoline, B 17 Pyridazinones, B 18 Benzoylurea, B 19 Methoxyacrylates, B 20 Benzoate esters, B 21 Pyrazoles, B 22 Pyrroles, B 23 Pyrimidines, B 24 naphthoquinones, B 25 Pyridazines, B 26 Pyrethroids, B 27 Biological products, B 28 Non-systemic organic nitrogen compounds, B 29 Other categories;

[0009] Furthermore, the active ingredient B is selected from:

[0010] B1 heterocyclic compounds: pyridaben, azoxystrobin;

[0011] B2 Quaternary keto acids: Spirodiclofen, Spirodiclofen, Spirodiclofen diester, Quaternary ketoclofen, Quaternary ketoclofen;

[0012] B3 benzoyl acetonitrile derivatives: buflufenicol;

[0013] B4 oxazoles: etoxazole, fluxametamide, isocycloseram;

[0014] B5 pyrazole amides: pyridaben, pyflubumide, etoxazole, cyprodinil;

[0015] B6 biphenylhydrazine derivatives: biphenylhydrazine esters;

[0016] B7 antibiotics: avermectin, methylavermectin benzoate, liuyangmycin, huaguangmycin, mibamectin;

[0017] B8 Organotin compounds: Triazole tin, Benzobutyltin;

[0018] B9 Tetraazine: Tetramethrin, Fluoxetine;

[0019] B 10 Thiazolidinediones: Thiamethoxam;

[0020] B 11 Sulfites: Propylene;

[0021] B 12 Thioureas: difenoconazole, dicofol;

[0022] B 13 Sulfoxides: flupentiofenox;

[0023] B 14 Bridged cyclic amines: acynonapyr;

[0024] B 15 Quinoline derivatives: floctoquin;

[0025] B 16 Quinazoline derivatives: Quinidazole;

[0026] B 17 Pyridazinone derivatives: pyridaben;

[0027] B 18 Benzoylurea derivatives: Lufenuron, Flufenoxuron, Flufenoxuron, Diflubenzuron;

[0028] B 19 Methoxyacrylates: pyrimethanil, fluopyram, pyrimethanil;

[0029] B 20 Benzoate esters: amidoflumet;

[0030] B 21 Pyrazole derivatives: Acetaminophen, vaniliprole, fipronil;

[0031] B 22 Pyrroles: Chlorfenapyr, Brofenoxam;

[0032] B 23 Pyrimidine derivatives: pyrimethanil;

[0033] B 24 Naphthoquinones: Acaricides;

[0034] B 25 Pyridazine derivatives: pyridaben;

[0035] B 26 Pyrethroids: high-efficiency cypermethrin, deltamethrin, cypermethrin, bifenthrin, flufenoxuron, bromofenoxuron;

[0036] B 27Biologically derived substances: matrine, veratrine, azadirachtin, pyrethroids, rotenone, pine mites, olive shark;

[0037] B 28 Non-systemic organic nitrogen compounds: bis(formamidin), monoformamidin;

[0038] B 29 Other classes: at least one of the following insecticides and acaricides: mivorilaner, modoflaner, tigolaner, umifoxolaner, trifluralin, fluazinam, spinosad, and mineral oil.

[0039] Furthermore, the active ingredient B is selected from:

[0040] B1 heterocyclic compounds: azoxystrobin;

[0041] B2 quaternary keto acids: spirotetramat, spirotetramat;

[0042] B3 benzoyl acetonitrile derivatives: buflufenicol;

[0043] B4 oxazoles: etoxazole;

[0044] B5 pyrazole amides: azoxystrobin, etoxazole, cyprodinil;

[0045] B6 biphenylhydrazine derivatives: biphenylhydrazine esters;

[0046] B7 antibiotics: avermectin, methylavermectin benzoate;

[0047] B8 Organotin compounds: Triazole tin;

[0048] B9 Tetraazine: Tetramethrin;

[0049] B 10 Thiazolidinediones: Thiamethoxam;

[0050] B 11 Sulfites: Propylene;

[0051] B 12 Thioureas: Butyl ether urea;

[0052] B 18 Benzoylurea derivatives: Lufenuron, Diflubenzuron;

[0053] B 19 Methoxyacrylates: Fluopyram;

[0054] B 21 Pyrazoles: Acetaminophen;

[0055] B 26 Pyrethroids: cypermethrin, bifenthrin;

[0056] B 29 Other: at least one of the insecticides and acaricides including trifluralin, spinosad, and fluazinam.

[0057] In the pesticide composition of the present invention, the mass ratio of active ingredient A to active ingredient B is not particularly limited, but is preferably 1:100 to 100:1 or any value between the above values;

[0058] Preferably, the mass ratio of active ingredient A to active ingredient B is 1:80 to 80:1;

[0059] More preferably, the mass ratio of active ingredient A to active ingredient B is 1:50 to 50:1;

[0060] More preferably, the mass ratio of active ingredient A to active ingredient B is 1:45 to 45:1.

[0061] In one specific embodiment, the present invention also provides for a particular combination of active ingredient A and active ingredient B as follows:

[0062]

[0063]

[0064] Furthermore, a specific combination of active ingredient A and active ingredient B:

[0065] Component A Component B Typical mass ratio Equation (I) Azoxystrobin 25:1～1:24 Equation (I) etoxazole 15:1～1:32 Equation (I) Avermectin 15:1～1:15 Equation (I) methylavermectin benzoate 50:1～5:1 Equation (I) Tetramethrin 15:1～1:27 Equation (I) propargite 20:1～1:20 Equation (I) Butyl ether urea 18:1～1:18 Equation (I) Diflubenzuron 20:1～1:20 Equation (I) Trifluoroacetate 15:1～1:20 Equation (I) Fluazinam 15:1～1:15

[0066] Furthermore, a specific combination of active ingredient A and active ingredient B:

[0067] Component A Component B Typical mass ratio Equation (I) Azoxystrobin 25:1～1:14 Equation (I) etoxazole 15:1～1:7 Equation (I) Tetramethrin 15:1～1:20 Equation (I) Avermectin 15:1～1:10 Equation (I) methylavermectin benzoate 50:1～5:1 Equation (I) propargite 14:1～1:20 Equation (I) Butyl ether urea 18:1～1:18 Equation (I) Diflubenzuron 20:1～1:20 Equation (I) Trifluoroacetate 15:1～1:20 Equation (I) Fluazinam 6:1～1:15

[0068] Furthermore, based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1 to 95 wt%.

[0069] Furthermore, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1 to 90 wt%.

[0070] In a preferred embodiment, the sum of the contents of the compound of formula (I) and pyrimethanil in the pesticide composition is:

[0071]

[0072]

[0073] Furthermore, the sum of the contents of the compound of formula (I) and pyrimethanil in the pesticide composition is:

[0074]

[0075]

[0076] Furthermore, in addition to the active ingredient, the pesticide composition also includes agriculturally acceptable auxiliary ingredients, which are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

[0077] The wetting agent is selected from one or more of the following: alkylbenzene sulfonates, alkylnaphthalene sulfonates, lignin sulfonates, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate, α-olefin sulfonates, alkylphenol polyoxyethylene ethers, castor oil polyoxyethylene ethers, alkylphenol ethoxylates, fatty alcohol ethoxylates, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, soapberry powder, soapberry powder, SOPA, detergents, emulsifiers 2000 series, and wetting and penetrating agents F; and / or

[0078] The dispersant is selected from one or more of the following: lignin sulfonates, alkyl naphthalene sulfonates formaldehyde condensates, naphthalene sulfonates, tristyrylphenol ethoxylate phosphates, fatty alcohol ethoxylates, alkylphenol polyoxyethylene ethers, alkylphenol polyoxyethylene ether methyl ether condensates sulfates, fatty amine polyoxyethylene ethers, glycerol fatty acid ester polyoxyethylene ethers, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers, and EO-PO graft copolymers; and / or

[0079] The emulsifier is selected from one or more of the following: calcium dodecylbenzenesulfonate, alkylphenol formaldehyde resin polyoxyethylene ether, phenethylphenol polyoxyethylene polyoxypropylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrene-phenol polyoxyethylene ether, castor oil polyoxyethylene ether, and alkylphenol ether phosphate; and / or

[0080] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose, and silica; and / or

[0081] The disintegrant is selected from one or more of sodium sulfate, ammonium sulfate, aluminum chloride, sodium chloride, ammonium chloride, bentonite, glucose, sucrose, starch, cellulose, urea, sodium carbonate, sodium bicarbonate, citric acid, and tartaric acid; and / or

[0082] Antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0083] Defoamer selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10One or more of the fatty alcohols; and / or

[0084] The solvent is selected from one or more of benzene, toluene, xylene, mesitylene, methanol, ethanol, isopropanol, n-butanol, dimethyl sulfoxide, dimethylformamide, cyclohexanone, hydrocarbon carbonates, diesel oil, solvent oil, vegetable oil, vegetable oil derivatives, and water; and / or

[0085] The preservative is selected from one or more of propionic acid, sodium propionate, sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, methyl p-hydroxybenzoate, Kathon, and 1,2-benzisothiazolin-3-one; and / or

[0086] The stabilizer is selected from one or more of the following: disodium hydrogen phosphate, oxalic acid, succinic acid, adipic acid, borax, 2,6-di-tert-butyl-p-cresol, triethanolamine oleate, epoxidized vegetable oil, kaolin, bentonite, attapulgite, silica, talc, montmorillonite, and starch; and / or

[0087] Synergists are selected from synergistic phosphorus, synergistic ether; and / or

[0088] The carrier is selected from one or more of the following: ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils, and vegetable oil derivatives.

[0089] The carrier can be a solid carrier or a liquid carrier;

[0090] The solid carrier includes: minerals, plant materials, synthetic fillers, and inorganic salts;

[0091] The minerals mentioned include silicates, carbonates, sulfates, and oxides.

[0092] The silicates are selected from at least one of kaolin, sepiolite, pearl clay, montmorillonite, mica, vermiculite, pyrophyllite, and talc; the carbonates are selected from calcium carbonate or dolomite; the sulfates are selected from at least one of ammonium sulfate, sodium sulfate, and calcium sulfate; the oxides are selected from at least one of quicklime, magnesium lime, and diatomaceous earth; the plant materials are selected from at least one of citrus pomace, corn cob, rice husk powder, rice husk, soybean straw powder, tobacco powder, walnut shell, and sawdust; the synthetic fillers are selected from at least one of precipitated calcium carbonate hydrate, precipitated calcium carbonate, and silica; and the inorganic salts are selected from potassium chloride or sodium chloride.

[0093] The liquid carrier includes water and an organic solvent;

[0094] The water is preferably deionized water;

[0095] The organic solvent is selected from at least one of aromatic hydrocarbons, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones, special solvents, vegetable oils, and methylated vegetable oils;

[0096] The aromatic hydrocarbon is selected from at least one of benzene, xylene, trimethylbenzene, and toluene; the chlorinated aliphatic hydrocarbon is selected from at least one of chloroform, dichloromethane, chloroform, carbon tetrachloride, and polychlorinated ethanes; the aliphatic hydrocarbon is selected from at least one of petroleum fractions, cyclohexane, light mineral oil, and paraffin; the alcohol is selected from at least one of methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, and fatty alcohols; the ether is selected from at least one of propylene glycol ethyl ether, propylene glycol methyl ether, and petroleum ether; the ketone is selected from acetone, At least one of cyclohexanone, isoflurone, N-methylpyrrolidone, and N-octylpyrrolidone; the special solvent is selected from at least one of dimethylformamide, dimethyl sulfoxide, polyethylene glycol, and acetonitrile; the vegetable oil is selected from at least one of peanut oil, soybean oil, linseed oil, castor oil, and rapeseed oil; the methylated vegetable oil is selected from at least one of methyl oleate, methyl oleate, methyl laurate, methyl stearate, methyl myristate, methyl hexadecanoate, methyl octanoate, methyl caprylate, methyl cocoate, and mixed fatty acid methyl esters;

[0097] Furthermore, the pesticide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid and / or liquid formulations;

[0098] The solid dosage forms include powders, granules, balls, tablets, strips, wettable powders, oil-dispersible powders, emulsion powders, water-dispersible granules, emulsion granules, water-dispersible tablets, soluble powders, soluble tablets, or soluble granules.

[0099] The liquid formulations include soluble agents, colloids, oils, spreading oils, emulsions, latexes, dispersible liquids, ointments, water emulsions, oil emulsions, microemulsions, lipid suspensions, microcapsule suspensions, oil suspensions, dispersible oil suspensions, suspensions, microcapsule suspension-suspension agents, microcapsule suspension-water emulsions, or microcapsule suspension-suspension emulsions.

[0100] Furthermore, the solid dosage form is selected from wettable powders, water-dispersible granules, and soluble granules; the liquid dosage form is selected from emulsifiable concentrates, water-in-oil emulsions, and suspensions.

[0101] Application of a pesticide composition containing biphenyl sulfide compounds in the control of phytophagous mites;

[0102] According to the control method of the present invention, pests such as insects and mites can be controlled more safely with less dosage; the pest control composition of the present invention is applicable to pest control methods, especially the control method of the present invention. The pest control composition of the present invention is particularly suitable for insecticides and acaricides used in agriculture and horticulture.

[0103] Furthermore, the phytophagous mites mentioned are spider mites, galbidae, and / or eupodidae mites;

[0104] Furthermore, the phytophagous mites mentioned are spider mites;

[0105] Furthermore, the spider mites mentioned are: truncated spider mite, carmine spider mite, citrus spider mite, and two-spotted spider mite;

[0106] Furthermore, the acaricidal composition and / or its formulation are applied at an effective dose to the mites that need to be controlled or the medium in which they grow.

[0107] The beneficial effects of this invention are:

[0108] (1) The composition of the present invention exhibits a synergistic effect within the specified ratio range, and its acaricidal effect is significantly improved compared with that of a single agent, with good rapid effect and long-lasting effect;

[0109] (2) The active ingredients of the composition of the present invention do not have cross-resistance problems. By rationally mixing different modes of action and different mechanisms of action of mites, it can delay the development of mites' resistance and reduce the amount of pesticide used.

[0110] (3) It is environmentally friendly, safe and efficient, and its promotion and application have huge economic and social benefits. Detailed Implementation

[0111] To make the technical solution, objectives and advantages of the present invention clearer, the present invention is described with reference to the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0112] Formulation preparation example:

[0113] Preparation Example 1:

[0114] 26% Formula (I) Compound·Azoxystrobin Suspension (22:4)

[0115] Preparation formula: 22% compound of formula (I), 4% azoxystrobin, 1% fatty alcohol polyoxyethylene ether, 3% phenethylphenol polyether phosphate salt, 1% sodium polycarboxylate salt, 3% alkyl aryl polyoxyethylene polyoxypropylene ether, 1% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% Kathon, 5% ethylene glycol, 0.4% silicone defoamer, deionized water to make up the balance;

[0116] Preparation method: According to the formulation ratio in the example, the active ingredients, surfactants and other functional additives are placed in the reaction vessel in sequence, water is added and mixed evenly, and then subjected to high-speed shearing, wet sand milling and finally homogenization filtration to obtain the suspension product.

[0117] Preparation Example 2:

[0118] 20% Formula (I) Compound·Ethoxyxazole Suspension (10:10)

[0119] Preparation formula: 10% compound (Ⅰ), 10% etoxazole, 1% sodium dioctyl succinate sulfonate, 3% fatty alcohol polyoxyethylene ether phosphate salt, 1% naphthalene sulfonate formaldehyde condensate, 3% alkyl aryl polyoxyethylene polyoxypropylene ether, 1% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% methylisothiazolinone, 5% glycerol, 0.4% organosilicon defoamer, deionized water to make up the balance;

[0120] Preparation method: Same as in preparation example 1.

[0121] Preparation Example 3:

[0122] 22% Formula (I) Compound Tetradamine Suspension (4:18)

[0123] Preparation formula: 4% compound (Ⅰ), 18% tetradifon, 1.5% fatty amine polyoxyethylene ether, 3% phenethylphenol polyether phosphate salt, 4% alkyl aryl polyoxyethylene polyoxypropylene ether, 1% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% Kathon, 5% propylene glycol, 0.4% silicone defoamer, deionized water to make up the balance;

[0124] Preparation method: Same as in preparation example 1.

[0125] Preparation Example 4:

[0126] 42% Formula (I) Compound·Butyl ether urea suspension (22:20)

[0127] Preparation formula: 22% compound of formula (I), 20% butyl ether urea, 2% phenethylphenol polyether phosphate salt, 1% fatty amine polyoxyethylene ether, 1% sodium polycarboxylate salt, 1% alkyl naphthalene sulfonate formaldehyde condensate, 0.1% xanthan gum, 0.01% carboxyethyl cellulose, 1% sodium sorbate, 5% glycerol, 0.4% silicone defoamer, deionized water to make up the balance;

[0128] Preparation method: Same as in preparation example 1.

[0129] Preparation Example 5:

[0130] 34% Formula (I) Compound·Fluoridamine Suspension (17:17)

[0131] Preparation formula: 17% compound of formula (I), 17% fluazinam, 2% alkyl naphthalene sulfonate formaldehyde condensate, 1% naphthalene sulfonate formaldehyde condensate, 3% styrene-phenol polyoxyethylene ether phosphate, 1% magnesium aluminum silicate, 0.16% xanthan gum, 5% propylene glycol, 0.02% potassium benzoate, 0.4% organosilicon defoamer, deionized water to make up the balance;

[0132] Preparation method: Same as in preparation example 1.

[0133] Preparation Example 6:

[0134] 5.5% Formula (I) compound · abamectin emulsifiable concentrate (5:0.5)

[0135] Preparation formula: 5% compound of formula (I), 0.5% abamectin, 12% styrene-based phenol polyoxyethylene ether, 3% calcium dodecylbenzenesulfonate, 10% N-methylpyrrolidone, 20% cyclohexanone, xylene to make up the balance;

[0136] Preparation method: The active ingredients are added to the carrier according to the formulation ratio of the example, and surfactants and other functional additives are added thereto. The mixture is stirred and mixed evenly in a stirring mixing tank to obtain the emulsifiable oil product.

[0137] Preparation Example 7:

[0138] 15% Formula (I) Compound·Propylthiazox Microemulsion (1:14)

[0139] Preparation formula: 1% compound of formula (I), 14% propargite, 20% cyclohexanone, 15% styrene-phenol polyoxyethylene ether, 3% alkyl aryl polyoxyethylene polyoxypropylene ether, 1% fatty alcohol polyoxyethylene ether sulfate, 0.05% organosilicon defoamer, and deionized water to make up the balance.

[0140] Preparation method: According to the formulation ratio in the example, the active ingredients, solvent, emulsifier, etc. are mixed evenly to obtain the oil phase. The antifreeze and water are mixed evenly to obtain the aqueous phase. The oil phase is added to the aqueous phase under stirring and stirred evenly. Shearing is continued for 10 minutes. Then, the defoamer is added and stirred evenly to obtain small droplets with oil phase particles of 0.01-0.1 μm, which is the microemulsion product.

[0141] Preparation Example 8:

[0142] 12% Formula (I) Compound·Butyl ether urea microemulsion (10:2)

[0143] Preparation formula: 10% compound of formula (I), 2% butyl ether urea, 20% cyclohexanone, 15% styrene-phenol polyoxyethylene ether, 3% sorbitan oleate polyoxyethylene ether, 1% fatty alcohol polyoxyethylene ether sulfate, 0.05% silicone defoamer, deionized water to make up the balance;

[0144] Preparation method: Same as in preparation example 7.

[0145] Preparation Example 9:

[0146] 13% Formula (I) Compound·Azoxystrobin Water Emulsion (11:2)

[0147] Preparation formula: 11% compound of formula (I), 2% azoxystrobin, 20% cyclohexanone, 6% alkyl aryl polyoxyethylene polyoxypropylene ether, deionized water to make up the balance;

[0148] Preparation method: According to the formulation ratio in the example, the active ingredient is dissolved in the solvent and an emulsifier is added to form a homogeneous oil phase. Deionized water and antifreeze are mixed together to form a homogeneous aqueous phase. Under high-speed shearing, the aqueous phase is added to the oil phase to form a water emulsion product.

[0149] Preparation Example 10:

[0150] 10% Formula (I) Compound Tetradamine Wettable Powder (2:8)

[0151] Preparation formula: 2% compound of formula (I), 8% tetradifon, 2% fatty alcohol polyoxyethylene ether, 5% silica, 8% formaldehyde condensate of sodium methylnaphthalene sulfonate, 10% tea saponin, 2% sodium dodecyl sulfate, and kaolin to make up the balance;

[0152] Preparation method: According to the formulation ratio in the example, the active ingredients are added to the carrier, and surfactants and other functional additives are added thereto. After mixing, the mixture is pulverized by air jet and then mixed again to obtain a wettable powder product.

[0153] Indoor toxicity

[0154] The examples refer to Part 13 of the Guidelines for Indoor Bioassay Testing of Pesticides: Leaf Disc Spray Method NY / T 1154.13-2008; and Part 7: Determination of the Combined Effects of Mixtures NY / T 1154.7-2006.

[0155] Test reagents: The technical grade compounds of formula (Ⅰ), azithromycin, etoxazole, abamectin, methyl abamectin benzoate, tetradifon, propargite, difenoconazole, bismuth subtilis, trifluralin, fluazinam, spirotetramat, etoxazole, cyprodinil, bifenazate, thiamethoxam, and lufenuron were all provided by the Group's R&D Center;

[0156]

[0157]

[0158] Experimental target: citrus psoriatic mites (panonychus citri McGregor);

[0159] Select female adult mites that are kept indoors and are in the same physiological state. Temperature: (25±1)℃. Relative humidity: 65%±5%, light cycle: 16 / 8h (L / D).

[0160] Select citrus leaves that grow uniformly, and use a punch to make leaf discs with a diameter of 2cm. Place agar in the petri dish to keep it moist, place filter paper on top, and place leaf discs on the filter paper. Place 3 leaf discs in each dish. Inoculate the adult mites raised indoors onto the leaf discs, with 10-15 mites on each leaf disc.

[0161] Drug preparation: Dissolve the drug in acetone, then dilute with 0.1% Tween-80 aqueous solution. Prepare single-dose stock solutions separately, and design 5 formulations according to the purpose of mixing and drug activity. Prepare 5 series of mass concentrations for each single agent and each formulation mixture according to the ratio method.

[0162] Chemical treatment: Place the petri dishes on the bottom of the Potter spray tower and spray with 1 ml of solution. After the solution settles for 1 minute, remove the dishes and transfer them to the rearing conditions. Each treatment should be replicated at least 4 times, and each dose should be used to treat at least 120 insects. A blank control should be set up with no chemical treatment (containing all organic solvents and emulsifiers).

[0163] Data Statistics and Analysis: The mortality of test insects was checked 48 hours after treatment, and the total number of insects and the number of dead insects were recorded. Based on the survey data, the corrected mortality rate for each treatment was calculated.

[0164] Calculate using the following formula, and round the results to two decimal places:

[0165]

[0166] In the formula:

[0167] P – Mortality rate, expressed as a percentage (%);

[0168] K represents the number of dead insects, in heads;

[0169] N represents the total number of insects treated, in units of heads.

[0170]

[0171] In the formula:

[0172] P1 – Corrected mortality rate, in percentage (%);

[0173] P t —The mortality rate is expressed as a percentage (%).

[0174] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0175] If the control mortality rate is <5%, no correction is needed; if the control mortality rate is between 5% and 20%, correction should be performed; if the control mortality rate is >20%, the trial needs to be repeated.

[0176] The data was processed using probability value analysis. The LC-value of the toxicity regression line can be calculated using the IBM SPSS Statistics 20 statistical analysis system. 50 The b-value, its 95% confidence limit, and the b-value are used to evaluate the activity of the test reagent on the biological material.

[0177] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0178]

[0179] In the formula:

[0180] ATI – Actual Measured Toxicity Index of Mixtures;

[0181] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0182] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0183] TTI = TI A *P A +TI B *P B

[0184] In the formula:

[0185] TTI – Theoretical Toxicity Index of Mixtures;

[0186] TI A —A. Toxicity index of drug A;

[0187] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0188] TI B —Toxicity index of drug B;

[0189] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0190]

[0191] In the formula:

[0192] CTC – Cotoxicity Coefficient;

[0193] ATI – Actual Measured Toxicity Index of Mixtures;

[0194] TTI – Theoretical Toxicity Index of Mixtures.

[0195] The co-toxicity coefficient of the compound is ≥120, which shows a synergistic effect; CTC≤80 shows an antagonistic effect; and 80<CTC<120 shows an additive effect.

[0196] Experimental results:

[0197] As shown in Table 1, compound (I) exhibits high toxicity against *Pachycercus citrinum* as a single agent, with an LC50 value of [missing information]. 50 The value was 11.279 mg / L. The indoor toxicity results of each single agent showed that the toxicity of various acaricides against adult female citrus paris mite was as follows: azoxystrobin > avermectin > propargite > difenoconazole > fluazinam > etoxazole > tetradifon.

[0198] Compound (I) exhibits a synergistic effect with azoxystrobin in the range of 25:1 to 1:24; Compound (I) exhibits a synergistic effect with etoxazole in the range of 15:1 to 1:32; Compound (I) exhibits a synergistic effect with tetradifon in the range of 15:1 to 1:20; Compound (I) exhibits a synergistic effect with abamectin in the range of 15:1 to 1:15; Compound (I) exhibits a synergistic effect with propargite in the range of 20:1 to 1:20; Compound (I) exhibits a synergistic effect with buprofen in the range of 18:1 to 1:18; Compound (I) exhibits a synergistic effect with fluazinam in the range of 15:1 to 1:15.

[0199] Table 1. Determination of the combined toxicity of compound (I) with various acaricides in different ratios against adult female *Pachydermus citrinum*.

[0200]

[0201]

[0202] The above experiments also determined the indoor toxicity of compound (I) mixed with emamectin benzoate, bis(triflufenoxam) and trifluralin against the citrus pterocaryon. The results showed that:

[0203] When active ingredient B is emamectin benzoate, its LC 50 The concentration was 7.532 mg / L. When the mass ratio of compound (I) to emamectin benzoate was between 100:1 and 5:1, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to emamectin benzoate was 16:1, the co-toxicity coefficient was the largest, at 175.241, and the synergistic effect was the most obvious.

[0204] When active ingredient B is bis(triflufenican), its LC 50 The concentration was 11.273 mg / L. When the mass ratio of compound (I) to bis(triflufenicol) was 20:1 to 1:20, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to bis(triflufenicol) was 3:4, the co-toxicity coefficient was the largest, at 183.055, and the synergistic effect was the most obvious.

[0205] When active ingredient B is trifluoromethyl methyl ether, its LC 50 The concentration was 15.251 mg / L. When the mass ratio of compound (I) to trifluoromethylpyrazine was 15:1 to 1:20, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to trifluoromethylpyrazine was 2:1, the co-toxicity coefficient was the largest, at 217.108, and the synergistic effect was the most obvious.

[0206] When active ingredient B is spirotetramat, its LC50 50 The concentration was 272.433 mg / L. When the mass ratio of compound (I) to spirotetramat was 18:1 to 1:24, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to spirotetramat was 5:1, the co-toxicity coefficient was the largest, at 207.529, and the synergistic effect was the most obvious.

[0207] When active ingredient B is etoxazole, its LC... 50 The concentration was 1.192 mg / L. When the mass ratio of compound (I) to etoxazole was 35:1 to 1:25, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to etoxazole was 5:1, the co-toxicity coefficient was the largest, at 207.529, and the synergistic effect was the most obvious.

[0208] When active ingredient B is cypermethrin, its LC 50 The concentration was 2.062 mg / L. When the mass ratio of compound (I) to cyproterone was 35:1 to 1:25, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to cyproterone was 2:3, the co-toxicity coefficient was the largest, at 185.283, and the synergistic effect was the most obvious.

[0209] When active ingredient B is biphenylhydrazine ester, its LC 50 The concentration was 3.1148 mg / L. When the mass ratio of compound (I) to biphenylhydrazine was 35:1 to 1:30, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to biphenylhydrazine was 2:7, the co-toxicity coefficient was the largest, at 221.427, and the synergistic effect was the most obvious.

[0210] When active ingredient B is thiamethoxam, its LC 50 The concentration was 12.072 mg / L. When the mass ratio of compound (I) to thiamethoxam was 30:1 to 1:25, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to thiamethoxam was 1:3, the co-toxicity coefficient was the largest, at 193.057, and the synergistic effect was the most obvious.

[0211] When active ingredient B is chlorfenapyr, its LC50 50 The concentration was 16.225 mg / L. When the mass ratio of compound (I) to lufenuron was 35:1 to 1:25, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to lufenuron was 5:2, the co-toxicity coefficient was the largest, at 184.664, and the synergistic effect was the most obvious.

[0212] Example 2

[0213] citrus parchomitid field trial

[0214] Test crop: Citrus tree (variety: Wenzhou mandarin orange);

[0215] Test subject: Citrus red spider mite (panonychus citri McGregor);

[0216] Experimental location: Chuangxin Village, Huanxi Town, Jin'an District, Fuzhou City. The orchard is flat, with loam soil, pH 6.0, and moderate soil fertility (organic content 1g / kg). Trees are uniformly growing, and fertilizer and water management is consistent. The trees are 8 years old, with trifoliate orange rootstock. The planting spacing is 5×4m, with 33 trees per mu (approximately 0.067 hectares). The average tree height is 2.0m, and the average crown width is 2.0m×2.5m. No fertilizer or irrigation was applied during the experiment.

[0217] Experimental treatment: Each plot was randomly assigned to a block design, with 2 trees per plot and 4 replicates. The spraying equipment was a Singapore Linong 16L HD-400 backpack sprayer, with an average spray volume of 5.0 liters (4500 L / hm²) per tree. 2 The spraying should be even and thorough, ensuring that the fruit, leaves (both front and back), and branches are all moistened.

[0218] Trial date: April 28, 2021. The drug was applied only once during the entire trial.

[0219] The weather was good on and during the day of the experiment. On the day of the test, the average daily temperature was 18°C, the highest temperature was 23°C, the lowest temperature was 13°C, and the relative humidity was 70%.

[0220] Survey method: Two trees were surveyed in each plot. Each time, 25 leaves of the current year's spring shoots were randomly surveyed from different positions around the tree crown. The number of live mites on the front and back of each leaf was observed directly in the field without removing the leaves using a 10x insect magnifying glass. The base population of mites was surveyed before the pesticide was applied, and the number of live mites was surveyed 3 days and 14 days after the pesticide was applied.

[0221] Method for calculating drug efficacy: Drug efficacy is calculated using the following formula:

[0222]

[0223] During the experiment, the citrus trees in each treatment plot grew well, and no pesticide damage was observed in any treatment.

[0224] Experimental results:

[0225] Table 2 Results of inter-spray tests on citrus red spider mite using different test agents

[0226]

[0227]

[0228] Note: The efficacy (%) in the table above is the average of each replicate.

[0229] According to field surveys, no adverse reactions to the pesticide were observed in leaves or young branches under any of the treatments, indicating that the treatments were safe for citrus growth at the concentrations used in the experiments.

[0230] Table 2 shows the results of field trials of different tested pesticides against citrus red spider mites. It can be seen that compound (I) mixed with abamectin, avermectin, propargite, difenoconazole, fluazinam, etoxazole, and tetradifon showed better control effects against citrus red spider mites, with significantly higher efficacy than the single-agent control. Three days after application, the efficacy of each compound was above 90%, demonstrating good rapid-acting properties. Fourteen days after application, the efficacy of each compound increased, exceeding 90%, showing good sustained efficacy.

[0231] Example 3

[0232] Orange-red spider field experiment

[0233] Test crop: Citrus (Mandarin orange);

[0234] Test subject: Citrus red spider mite (panonychus citri McGregor);

[0235] Experimental location: Shuangqiao Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region. The orchard is flat, with loam soil, pH 6.0, and moderate soil fertility. The trees are growing uniformly, and fertilizer and water management levels are consistent. The trees are 6 years old, and the age and canopy size of all trees in the field are basically the same.

[0236] Experimental treatment: Each plot was randomly assigned to a block design, with 4 trees per plot and 4 replicates. The spraying equipment was a Singapore Linong 16L HD-400 backpack sprayer. Based on actual field conditions and farmers' water usage habits, the water volume per citrus tree was determined to be 1.5L. Spraying was carried out evenly and thoroughly, ensuring the fruit, the front and back of the leaves, and the branches were all moistened.

[0237] Trial date: October 18, 2022. The pesticide was applied only once during the entire trial. The weather was good on the day of the trial and during the trial period.

[0238] Survey Method: Randomly select one point from each citrus tree along the east, west, south, north, and center directions. Mark one branch at each point and record the total number of live citrus red spider mites on the leaves of the marked branch (starting from the top leaves, with a minimum of 5 leaves). The survey primarily focuses on adult and nymphal mites (which can be observed with a magnifying glass). The initial mite population is assessed before pesticide application, and the number of live mites is assessed 3 and 14 days after application.

[0239] Method for calculating drug efficacy: Drug efficacy is calculated using the following formula:

[0240]

[0241] During the experiment, the citrus trees in each treatment plot grew well, and no pesticide damage was observed in any treatment.

[0242] Experimental results:

[0243] Table 3. Results of inter-mite tests using different test agents on citrus red spider mite.

[0244]

[0245] Note: The efficacy (%) in the table above is the average of each replicate.

[0246] Table 3 shows the results of field trials on citrus red spider mites using different tested pesticides. It can be seen that compound (I) mixed with abamectin, etoxazole, tetradifon, abamectin, propargite, difenoconazole, and fluazinam exhibited better control effects against citrus red spider mites, with significantly higher efficacy than the single-agent control. Three days after application, the efficacy of each compound pesticide was above 90%, demonstrating good rapid-acting properties. Fourteen days after application, the efficacy of each compound group increased, exceeding 90%, showing good sustained efficacy.

[0247] Through indoor toxicity testing and field trials on citrus fruits, the acaricidal composition of formula (I) described in this invention, combined with any one of abamectin, etoxazole, tetradifon, avermectin, propargite, difenoconazole, or fluazinam, showed good control efficacy against phytophagous mites. The acaricidal composition or its formulation obtained by this invention exhibits significant efficacy, superior to single agents in delaying the development of resistance and prolonging pesticide retention. Furthermore, no phytotoxicity was observed in the experiments with the combined agents, indicating that the improved synergistic effect of the acaricidal composition or formulation reduces production and usage costs while ensuring crop safety.

[0248] Although the present invention has been described in detail above with general description and specific embodiments, some modifications or improvements can be made to it based on the present invention, which will be obvious to those skilled in the art. Therefore, all such modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. A pesticide composition containing a diphenyl sulfide compound, characterized in that, The pesticide composition includes active ingredient A and active ingredient B, wherein active ingredient A is a biphenyl sulfide compound as shown in formula (I): (I), The active ingredient B is azoxystrobin, and the mass ratio of the compound of formula (I) to azoxystrobin is 25:1 to 1:

24.

2. The pesticide composition according to claim 1, characterized in that, The mass ratio of the compound of formula (I) to azoxystrobin is 25:1 to 1:

14.

3. The pesticide composition according to claim 1, characterized in that, The mass ratio of the compound of formula (I) to azoxystrobin is 25:1, 20:1, 35:2, 6:1, 1:5, 1:14, and 1:

24.

4. The pesticide composition according to claim 1, characterized in that, Based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 1 to 95 wt%.

5. The pesticide composition according to claim 1, characterized in that, Based on a total weight of 100 wt% of the pesticide composition, the sum of the contents of active ingredient A and active ingredient B in the pesticide composition is 5-80 wt%.

6. The pesticide composition according to claim 1, characterized in that, In addition to the active ingredient, the pesticide composition also includes agriculturally acceptable auxiliary ingredients, which are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists or carriers.

7. The pesticide composition according to claim 6, characterized in that, The pesticide composition is prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid formulations and / or liquid formulations; the solid formulation is selected from wettable powders, water-dispersible granules, and soluble granules; and the liquid formulation is selected from emulsifiable concentrates, water-in-oil emulsions, and suspension concentrates.

8. The application of the pesticide composition according to any one of claims 1-7 in the control of phytophagous mites, wherein the phytophagous mites are spider mites.

9. The application according to claim 8, characterized in that, The spider mite mentioned is the citrus parrot mite.

10. The application according to claim 8, characterized in that, The pesticide composition is applied at an effective dose to the mites that need to be controlled or to the medium in which they grow.

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