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 selected from any one of diafenthiuron, etoxazole, diacloden, propargite, clofentezine, fluazaindolyl, and abamectin. The pesticide composition can effectively control various phytophagous mites, has obvious synergistic effect, delays the generation of mite resistance, reduces the pesticide use amount, and is friendly to the environment.

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] Biphenyl sulfide compounds are a new class of compounds with good acaricidal activity, exhibiting good control effects against various plant-eating mites. Their chemical structural formulas are as follows:

[0003]

[0004] Spider mites are a significant agricultural pest, damaging crops such as vegetables, fruit trees, and cotton, often causing devastating losses. Due to their short reproductive cycle, high reproductive rate, low mobility, and high degree of self-pollination, these important agricultural pests are particularly prone to developing pesticide resistance. Therefore, the development of highly effective, low-toxicity, low-residue compound formulations with different mechanisms of action and synergistic effects is urgently needed. Summary of the Invention

[0005] To address the aforementioned problems in the prior art, this invention provides a pesticide composition containing diphenyl sulfide compounds and its application. This pesticide composition can effectively control a variety of agronomic mites, exhibits a significant synergistic effect, improves the control effect against mites compared to single-agent use, delays the development of mites' resistance, reduces pesticide usage, and is environmentally friendly.

[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 insecticides and 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, B22 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] B16 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 27 Biologically 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 any one of abamectin, etoxazole, difenoconazole, propargite, tetradifon, fluazinam, and abamectin;

[0040] In the pesticide composition of the present invention, the mass ratio of active ingredient A to active ingredient B is not particularly limited, but the mass ratio of active ingredient A to active ingredient B is 1:200 to 200:1;

[0041] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:100 to 100:1;

[0042] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:80 to 80:1;

[0043] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:50 to 50:1;

[0044] Furthermore, the active ingredient A is...

[0045] Furthermore, the mass ratio of active ingredient A to azoxystrobin is 1:40 to 45:1.

[0046] The mass ratio of active ingredient A to etoxazole is 1:30 to 35:1.

[0047] The mass ratio of active ingredient A to butylated urea is 1:30 to 1:16.

[0048] The mass ratio of active ingredient A to propargite is 25:1 to 1:30.

[0049] The mass ratio of active ingredient A to tetradifon is 24:1 to 1:30.

[0050] The mass ratio of active ingredient A to fluazinam is 30:1 to 1:20.

[0051] The mass ratio of active ingredient A to abamectin is 35:1 to 1:25.

[0052] Furthermore, the mass ratio of active ingredient A to azoxystrobin is 1:30 to 35:1.

[0053] The mass ratio of active ingredient A to etoxazole is 1:30 to 17:1.

[0054] The mass ratio of active ingredient A to butylated urea is 1:30 to 1:32.

[0055] The mass ratio of active ingredient A to propargite is 20:1 to 1:10.

[0056] The mass ratio of active ingredient A to tetradifon is 24:1 to 1:28.

[0057] The mass ratio of active ingredient A to fluazinam is 17:1 to 1:20.

[0058] The mass ratio of active ingredient A to abamectin is 15:1 to 1:25;

[0059] Furthermore, the mass ratio of active ingredient A to azoxystrobin is 2:25 to 25:1.

[0060] The mass ratio of active ingredient A to etoxazole is 1:10 to 17:1.

[0061] The mass ratio of active ingredient A to butylated urea is 1:30 to 1:16.

[0062] The mass ratio of active ingredient A to propargite is 18:1 to 1:15.

[0063] The mass ratio of active ingredient A to tetradifon is 20:1 to 1:28.

[0064] The mass ratio of active ingredient A to fluazinam is 14:1 to 1:15.

[0065] The mass ratio of active ingredient A to abamectin is 15:1 to 1:20;

[0066] Furthermore, the mass ratio of active ingredient A to azoxystrobin is 1:40, 1:30, 2:25, 1:7, 5:1, 15:1, 25:1, 35:1, or 45:1.

[0067] Furthermore, the mass ratio of active ingredient A to etoxazole is 1:30, 1:25, 1:10, 1:5, 1:1, 5:1, 10:1, 17:1, or 35:1;

[0068] Furthermore, the mass ratio of active ingredient A to butyl urea is 1:30, 1:24, 1:15, 1:8, 5:1, 10:1, 16:1, or 32:1;

[0069] 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%.

[0070] Furthermore, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 1-90 wt%; in a preferred embodiment,

[0071] Furthermore, the sum of the contents of the compound of formula (I) and abamectin, etoxazole, difenoconazole, propargite, tetradifon, fluazinam, and abamectin in the pesticide composition is,

[0072] pesticide compositions Sum of contents The sum of preferred contents Formula (I) compound + azoxystrobin 1wt%~80wt% 2wt%~50wt% Formula (I) compound + etoxazole 5wt%~80wt% 5wt%~80wt% Formula (I) compound + butyl ether urea 5wt%~80wt% 5wt%~80wt% Formula (I) compound + propargite 1wt%~85wt% 5wt%~60wt% Formula (I) compound + tetradifon 1wt%~80wt% 5wt%~50wt% Formula (I) compound + fluazinam 1wt%~80wt% 5wt%~50wt% Formula (I) compound + avermectin 1wt%~85wt% 5wt%~45wt%

[0073] 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.

[0074] Further, the wetting agent is selected from one or more of 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

[0075] Further, the dispersant is selected from one or more of the following: lignin sulfonate, alkyl naphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, fatty alcohol ethoxylate, alkylphenol polyoxyethylene ether, alkylphenol polyoxyethylene ether methyl ether condensate sulfate, fatty amine polyoxyethylene ether, glycerol fatty acid ester polyoxyethylene ether, polycarboxylates, polyacrylic acids, phosphates, EO-PO block copolymers, and EO-PO graft copolymers; and / or

[0076] Further, 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

[0077] Furthermore, 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

[0078] Further, 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

[0079] Furthermore, the antifreeze is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons, and inorganic salts; and / or

[0080] Furthermore, the defoamer is selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of the fatty alcohols; and / or

[0081] Further, 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

[0082] Further, 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

[0083] Furthermore, 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

[0084] Furthermore, the synergist is selected from synergistic phosphorus, synergistic ether; and / or

[0085] Furthermore, 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.

[0086] The carrier can be a solid carrier or a liquid carrier;

[0087] The solid carrier includes: minerals, plant materials, synthetic fillers, and inorganic salts;

[0088] The minerals mentioned include silicates, carbonates, sulfates, and oxides.

[0089] 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.

[0090] The liquid carrier includes water and an organic solvent;

[0091] The water is preferably deionized water;

[0092] 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;

[0093] The aromatic hydrocarbon is selected from at least one of benzene, xylene, trimethylbenzene, and toluene;

[0094] The chlorinated aliphatic hydrocarbon is selected from at least one of chloroform, dichloromethane, chloroform, carbon tetrachloride, and polychlorinated ethanes;

[0095] The aliphatic hydrocarbon is selected from at least one of petroleum fractions, cyclohexane, light mineral oil, and paraffin.

[0096] The alcohols are selected from at least one of methanol, ethanol, isopropanol, butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, and fatty alcohols.

[0097] The ether is selected from at least one of propylene glycol ethyl ether, propylene glycol methyl ether, and petroleum ether;

[0098] The ketones are selected from at least one of acetone, cyclohexanone, isoflurone, N-methylpyrrolidone, and N-octylpyrrolidone;

[0099] The special solvent is selected from at least one of dimethylformamide, dimethyl sulfoxide, polyethylene glycol, and acetonitrile;

[0100] The vegetable oil is selected from at least one of peanut oil, soybean oil, flaxseed oil, castor oil, and rapeseed oil;

[0101] The methylated vegetable oil is selected from at least one of the following: methyl oleate, methyl oleate, methyl laurate, methyl stearate, methyl tetradecanoate, methyl hexadecanoate, methyl octanoate, methyl caprylate, methyl cocoate, and mixed fatty acid methyl esters.

[0102] Furthermore, the pesticide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid and / or liquid formulations;

[0103] 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.

[0104] 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.

[0105] Furthermore, the solid dosage form is selected from wettable powders, water-dispersible granules, and soluble granules;

[0106] Furthermore, the liquid formulation is selected from emulsifiable concentrates, water-in-oil emulsions, and suspensions;

[0107] Application of a pesticide composition containing biphenyl sulfide compounds in the control of phytophagous mites;

[0108] According to the control method of the present invention, pests such as insects and mites can be controlled more safely with less pesticide.

[0109] The pest control composition of the present invention is applicable to pest control methods, particularly the pest control methods of the present invention. The pest control composition of the present invention is particularly suitable for insecticides and acaricides used in agriculture and horticulture.

[0110] Furthermore, the phytophagous mites mentioned are spider mites, galbidae, and / or eupodidae mites;

[0111] Furthermore, the phytophagous mites mentioned are spider mites;

[0112] Furthermore, the spider mites mentioned are *Tetranychus truncatus*, *Tetranychus carmineus*, *Tetranychus citrus*, and *Tetranychus two-spotted*.

[0113] Furthermore, the spider mite mentioned is a truncated spider mite;

[0114] 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.

[0115] The beneficial effects of this invention are:

[0116] (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;

[0117] (2) The composition of the present invention can be rationally mixed to target different modes of action and different mechanisms of action of mites, which can delay the development of pesticide resistance in mites and reduce the amount of pesticide used.

[0118] (3) It is environmentally friendly, safe and efficient, and its promotion and application have huge economic and social benefits. Detailed Implementation

[0119] 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.

[0120] Formulation preparation example:

[0121] Preparation Example 1:

[0122] 32% Formula (I) Compound·Azoxystrobin Suspension (4:28)

[0123] Preparation formula: 4% compound of formula (I), 28% abamectin, 1.5% fatty alcohol polyoxyethylene ether, 2% phenethylphenol polyether phosphate salt, 1.5% sodium polycarboxylate salt, 3% EO-PO block copolymer, 1.0% magnesium aluminum silicate, 0.25% xanthan gum, 0.1% Kathon, 5% ethylene glycol, 0.4% silicone defoamer, deionized water to make up the balance;

[0124] 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.

[0125] Preparation Example 2:

[0126] 25% Formula (I) Compound·Ethoxydazole Suspension (12:13)

[0127] Preparation formula: 12% compound (Ⅰ), 13% etoxazole, 1.5% naphthalene sulfonate formaldehyde condensate, 1% sodium dioctyl succinate sulfonate, 3% fatty alcohol polyoxyethylene ether phosphate, 3% sodium alkyl lignin sulfonate, 1% magnesium aluminum silicate, 0.2% xanthan gum, 0.1% methylisothiazolinone, 5% glycerol, 0.35% organosilicon defoamer, deionized water to make up the balance;

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

[0129] Preparation Example 3:

[0130] 26% Formula (I) Compound·Butyl ether urea suspension (3:23)

[0131] Preparation formula: 3% compound of formula (I), 23% butyl ether urea, 3.5% phenethylphenol polyether phosphate salt, 1% sodium polycarboxylate salt, 4% naphthalene sulfonate, 0.5% fatty amine polyoxyethylene 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;

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

[0133] Preparation Example 4:

[0134] 25% Formula (I) Compound·Fluoridamine Suspension (10:15)

[0135] Preparation formula: 10% compound (Ⅰ), 15% fluazinam, 2% sodium dioctyl succinate sulfonate, 3.5% phenethylphenol polyether phosphate, 1% sodium polycarboxylate, 4% sodium lignosulfonate, 1% magnesium aluminum silicate, 0.2% xanthan gum, 0.1% Kathon, 5% ethylene glycol, 0.5% silicone oil, deionized water to make up the balance;

[0136] Preparation method: Same as in preparation example 1.

[0137] Preparation Example 5:

[0138] 14% Formula (I) Compound·Azoxystrobin Water Emulsion (2:12)

[0139] Preparation formula: 2% compound of formula (I), 12% abamectin, 18% cyclohexanone, 6.5% alkyl aryl polyoxyethylene polyoxypropylene ether, 0.2% sodium sorbate, 0.1% silicone oil, and deionized water to make up the balance;

[0140] 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 well-dispersed water emulsion product.

[0141] Preparation Example 6:

[0142] 12% Formula (I) compound·butyl ether urea water emulsion (1.5:10.5)

[0143] Preparation formula: 1.5% compound of formula (Ⅰ), 10.5% butyl ether urea, 20% cyclohexanone, 3.5% dehydrated sorbitan oleate polyoxyethylene ether, 1% fatty alcohol polyoxyethylene ether sulfate, 0.2% sodium sorbate, 0.1% silicone oil, deionized water to make up the balance;

[0144] Preparation method: Same as in preparation example 5.

[0145] Preparation Example 7:

[0146] 15% Formula (I) Compound·Propylthiazox microemulsion (9:6)

[0147] Preparation formula: 9% compound (Ⅰ), 6% propargite, 22% cyclohexanone, 12.5% ​​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;

[0148] Preparation method: According to the formulation ratio in the example, the active ingredients, solvent, emulsifier, etc. are mixed evenly to obtain the oil phase, and the antifreeze is mixed evenly with water 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, and 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.

[0149] Preparation Example 8:

[0150] 30% Formula (I) Compound·Ethoxydazole Wettable Powder (15:15)

[0151] Preparation formula: 15% compound of formula (I), 15% etoxazole, 2% fatty alcohol polyoxyethylene ether, 1% styrene phenol ethoxylate phosphate, 5% silica, 2% bentonite, 7.5% formaldehyde condensate of sodium methylnaphthalene sulfonate, 8% tea saponin, 10% starch, 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] Preparation Example 9:

[0154] 25% Formula (I) Compound Tetradamine Wettable Powder (5:20)

[0155] Preparation formula: 5% compound of formula (I), 20% tetradifon, 2% glycerol fatty acid ester polyoxyethylene ether, 2% silica, 2% bentonite, 8% formaldehyde condensate of sodium methylnaphthalene sulfonate, 4% tea saponin, 2% sodium dodecyl sulfate, and kaolin to make up the balance;

[0156] Preparation method: Same as in preparation example 8.

[0157] Preparation Example 10:

[0158] 24% Formula (I) Compound Avermectin Wettable Powder (4:20)

[0159] Preparation formula: 4% compound of formula (I), 20% abamectin, 3% glycerol fatty acid ester polyoxyethylene ether, 5% attapulgite, 3% bentonite, 8% formaldehyde condensate of sodium methylnaphthalene sulfonate, 5% sodium dodecyl sulfate, and kaolin to make up the balance;

[0160] Preparation method: Same as in preparation example 8.

[0161] Indoor toxicity

[0162] 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.

[0163] Test reagents: 96% of compound (I) technical grade, 96% of azoxystrobin technical grade, 96% of etoxazole technical grade, 97% of buprofen technical grade; 90% of propargite technical grade, 96% of tetradifon technical grade, 98% of fluazinam technical grade, 92% of abamectin technical grade;

[0164] Experimental target: Tetranychus truncates Ehara;

[0165] Select nymphs that are kept indoors and have the same physiological condition. Temperature: (25±1)℃. Relative humidity: 65%±5%, light cycle: 16 / 8h (L / D).

[0166] Select uniformly grown citrus leaves and make leaf discs with a diameter of 2cm using a punch. Place agar in the petri dish to keep it moist, then place filter paper on top, and finally place the leaf discs on the filter paper. Place 3 leaf discs per dish. Inoculate the leaf discs with 10-15 nymphs raised indoors.

[0167] Drug preparation: Dissolve the drug in acetone and 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 by equal proportion.

[0168] 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).

[0169] Data statistics and analysis: The mortality of test insects was checked 36 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.

[0170] Calculate using the following formula, and round the results to two decimal places:

[0171]

[0172] In the formula:

[0173] P – Mortality rate, expressed as a percentage (%);

[0174] K represents the number of dead insects, in heads;

[0175] N represents the total number of insects treated, in units of heads.

[0176]

[0177] In the formula:

[0178] P1 – Corrected mortality rate, in percentage (%);

[0179] P t —The mortality rate is expressed as a percentage (%).

[0180] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0181] 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.

[0182] 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.

[0183] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0184]

[0185] In the formula:

[0186] ATI – Actual Measured Toxicity Index of Mixtures;

[0187] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0188] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0189] TTI = TI A *P A +TI B *P B

[0190] In the formula:

[0191] TTI – Theoretical Toxicity Index of Mixtures;

[0192] TI A —A. Toxicity index of drug A;

[0193] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0194] TI B —Toxicity index of drug B;

[0195] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0196]

[0197] In the formula:

[0198] CTC – Cotoxicity Coefficient;

[0199] ATI – Actual Measured Toxicity Index of Mixtures;

[0200] TTI – Theoretical Toxicity Index of Mixtures.

[0201] 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.

[0202] Experimental results:

[0203] As can be seen from Tables 1, 2, and 3, compound (I) exhibits high toxicity against Tetranychus truncatula by a single agent, with an LC50 value of [missing information]. 50 The value was 25.786 mg / L. The indoor toxicity results for each single dose showed that azoxystrobin > etoxazole > buprofen.

[0204] Compound (I) exhibits a synergistic effect with azoxystrobin in the range of 35:1 to 1:30; compound (I) exhibits a synergistic effect with etoxazole in the range of 17:1 to 1:30; compound (I) exhibits a synergistic effect with buprofen in the range of 16:1 to 1:30.

[0205] Table 1. Determination of the combined toxicity of compound (I) with azoxystrobin in different ratios to Tetranychus truncatula (nymphs).

[0206] Test reagents <![CDATA[LC 50 (95% confidence interval) mg·L -1 ]]> <![CDATA[r 2 ]]> Regression equation CTC interaction Formula (I) 25.786(21.434～31.474) 0.982 y = 2.206x - 3.113 / / Azoxystrobin 4.972(4.144～6.036) 0.995 y = 2.246x - 1.564 / / 45:1 21.908(18.278～26.385) 0.999 y = 2.275x - 3.049 107.883 Additive effect 35:1 17.044(14.370～20.273) 0.989 y = 2.453x - 3.021 135.531 Enhancement effect 25:1 13.061(10.836～15.819) 0.994 y = 2.195x - 2.450 170.048 Enhancement effect 15:1 11.144(9.447～13.204) 0.993 y = 2.543x - 2.663 183.403 Enhancement effect 5:1 8.065(6.764～9.618) 0.997 y = 2.384x - 2.161 188.329 Enhancement effect 1:7 2.643(2.270～3.107) 0.980 y = 2.818x - 1.189 209.230 Enhancement effect 2:25 2.787(2.366～3.327) 0.982 y = 2.576x - 1.147 189.745 Enhancement effect 1:30 4.099(3.429～4.906) 0.994 y = 2.335x - 1.431 124.541 Enhancement effect 1:40 4.833(4.044～5.832) 0.999 y = 2.305x - 1.577 104.942 Additive effect

[0207] Table 2. Determination of the combined toxicity of compound (I) with etoxazole against Tetranychus truncatula (nymphs) at different ratios.

[0208] Test reagents <![CDATA[LC 50 (95% confidence interval) mg·L -1 ]]> <![CDATA[r 2 ]]> Regression equation CTC interaction Formula (I) 25.786(21.434～31.474) 0.982 y = 2.206x - 3.113 / / etoxazole 6.348(5.130～7.889) 0.993 y = 1.895x - 1.521 / / 35:1 20.737(16.911～25.493) 0.965 y = 1.996x - 2.628 114.600 Additive effect 17:1 14.269(11.393～17.701) 0.979 y = 1.854x - 2.141 154.441 Enhancement effect 10:1 13.158(10.528～16.200) 0.986 y = 1.920x - 2.148 153.298 Enhancement effect 5:1 8.733(7.040～10.610) 0.990 y = 2.078x - 1.956 195.499 Enhancement effect 1:1 4.753(3.837～5.795) 0.985 y = 2.029x - 1.374 214.347 Enhancement effect 1:5 4.610(3.698～5.639) 0.994 y = 1.989x - 1.320 157.487 Enhancement effect 1:10 4.897(3.977～5.951) 0.973 y = 2.070x - 1.428 139.167 Enhancement effect 1:25 5.197(4.214～6.346) 0.968 y = 2.017x - 1.444 125.795 Enhancement effect 1:30 5.420(4.472～6.530) 0.988 y = 2.197x - 1.612 120.040 Enhancement effect

[0209] Table 3. Determination of the combined toxicity of compound (I) with buprofen against Tetranychus truncatula (mite) at different ratios.

[0210] Test reagents <![CDATA[LC 50 (95% confidence interval) mg·L -1 ]]> <![CDATA[r 2 ]]> Regression equation CTC interaction Formula (I) 25.786(21.434～31.474) 0.982 y = 2.206x - 3.113 / / Butyl ether urea 7.785(6.326～9.561) 0.999 y = 1.981x - 1.765 / / 32:1 20.373(16.514～25.169) 0.974 y = 1.8937x - 2.536 118.282 Additive effect 16:1 14.071(11.112～17.610) 0.961 y = 1.8771x - 2.033 161.315 Enhancement effect 10:1 12.244(9.970～14.795) 0.970 y = 2.145x - 2.333 174.021 Enhancement effect 5:1 7.464(5.905～9.215) 0.974 y = 1.890x - 1.650 249.370 Enhancement effect 1:8 3.105(2.496～3.794) 0.981 y = 2.003x - 0.985 271.808 Enhancement effect 1:15 4.597(3.675～5.638) 0.999 y = 1.960x - 1.298 177.076 Enhancement effect 1:24 4.802(3.929～5.793) 0.985 y = 2.167x - 1.477 166.777 Enhancement effect 1:30 5.223(4.277～6.324) 0.963 y = 2.123x - 1.524 152.486 Enhancement effect

[0211] The above experiments also determined the indoor toxicity of compound (I) mixed with propargite, tetradifon, fluazinam, and avermectin on Tetranychus truncatula (nymphs). The results showed that:

[0212] When active ingredient B is propargite, its LC 50 The concentration was 245.845 mg / L. When the mass ratio of compound (I) to propargite was 20:1 to 1:10, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to propargite was 3:2, the co-toxicity coefficient was the largest and the synergistic effect was the most obvious.

[0213] When active ingredient B is tetradifon, its LC 50The concentration was 8.566 mg / L. When the mass ratio of compound (I) to tetradifon was 24:1 to 1:28, the co-toxicity coefficient was greater than 120, showing a synergistic effect. Among them, when the mass ratio of compound (I) to tetradifon was 1:5, the co-toxicity coefficient was the largest and the synergistic effect was the most obvious.

[0214] When active ingredient B is fluazinam, its LC 50 The concentration was 116.215 mg / L. When the mass ratio of compound (I) to fluazinam was 17:1 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 fluazinam was 3:4, the co-toxicity coefficient was the largest and the synergistic effect was the most obvious.

[0215] When active ingredient B is avermectin, its LC 50 The concentration was 1.262 mg / L. When the mass ratio of compound (I) to abamectin was 15:1 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 abamectin was 1:5, the co-toxicity coefficient was the largest and the synergistic effect was the most obvious.

[0216] Example 2: Field trial for the control of Tetranychus truncatus

[0217] Test crop: Citrus tree (variety: mandarin orange);

[0218] Test subject: Tetranychus truncatula;

[0219] 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 30 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.

[0220] Experimental treatment: Each plot was arranged in a randomized block design, with 2 trees per plot and 4 replicates. The spraying equipment was a Singapore Linong 16L HD-400 backpack sprayer. The average amount of spray solution per tree was 5.0 liters. The spraying was carried out evenly and thoroughly, and the fruits, the front and back of the leaves and the branches were all sprayed with water.

[0221] Trial date: April 22, 2021. The drug was applied only once during the entire trial.

[0222] The weather was good on and during the day of the experiment. On the day of the test, the highest temperature was 26°C, the lowest temperature was 15°C, and the relative humidity was 65%.

[0223] 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.

[0224] Investigate the initial mite population before application and the number of live mites 3 and 14 days after application.

[0225] Drug efficacy calculation method: Drug efficacy is calculated according to the following formula:

[0226]

[0227] During the experiment, the citrus trees in each treatment plot grew well, and no pesticide damage was observed in any treatment.

[0228] Experimental results:

[0229] Table 4. Results of field trials on Tetranychus truncatula using different tested pesticides.

[0230]

[0231]

[0232] Note: The efficacy (%) in the table above is the average of each replicate.

[0233] 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.

[0234] Table 4 shows the results of field trials. Compound (I) mixed with abamectin, etoxazole, propargite, tetradifon, difenoconazole, fluazinam, and abamectin exhibited good control efficacy against Tetranychus truncatula, with significantly higher efficacy than the control single agent. Three days after application, the efficacy of each compound was above 80%, demonstrating good rapid-acting properties. Fourteen days after application, the efficacy of each compound group increased, exceeding 90%, showing good sustained efficacy.

[0235] 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, propargite, tetradifon, difenoconazole, fluazinam, or abamectin, 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.

[0236] 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): Active ingredient B is selected from one or more of the following insecticides and acaricides; 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.

2. The pesticide composition containing biphenyl sulfide compounds according to claim 1, characterized in that, The active ingredient B is selected from: B1 heterocyclic compounds: pyridaben, azoxystrobin; B2 Quaternary keto acids: Spirodiclofen, Spirodiclofen, Spirodiclofen diester, Quaternary ketoclofen, Quaternary ketoclofen; B3 benzoyl acetonitrile derivatives: buflufenicol; B4 oxazoles: etoxazole, fluxametamide, isocycloseram; B5 pyrazole amides: pyridaben, pyflubumide, etoxazole, cyprodinil; B6 biphenylhydrazine derivatives: biphenylhydrazine esters; B7 antibiotics: avermectin, methylavermectin benzoate, liuyangmycin, huaguangmycin, mibamectin; B8 Organotin compounds: Triazole tin, Benzobutyltin; B9 Tetraazine: Tetramethrin, Fluoxetine; B 10 Thiazolidinediones: Thiamethoxam; B 11 Sulfites: Propylene; B 12 Thioureas: difenoconazole, dicofol; B 13 Sulfoxides: flupentiofenox; B 14 Bridged cyclic amines: acynonapyr; B 15 Quinoline derivatives: floctoquin; B 16 Quinazoline derivatives: Quinidazole; B 17 Pyridazinone derivatives: pyridaben; B 18 Benzoylurea derivatives: Lufenuron, Flufenoxuron, Flufenoxuron, Diflubenzuron; B 19 Methoxyacrylates: pyrimethanil, fluopyram, pyrimethanil; B 20 Benzoic acid esters: amidoflumet; B 21 Pyrazole derivatives: Acetaminophen, vaniliprole, fipronil; B 22 Pyrroles: Chlorfenapyr, Brofenoxam; B 23 Pyrimidine derivatives: pyrimethanil; B 24 Naphthoquinones: Acaricides; B 25 Pyridazine derivatives: pyridaben; B 26 Pyrethroids: high-efficiency cypermethrin, deltamethrin, cypermethrin, bifenthrin, flufenoxuron, bromofenoxuron; B 27 Biologically derived substances: matrine, veratrine, azadirachtin, pyrethroids, rotenone, pine mites, olive shark; B 28 Non-systemic organic nitrogen compounds: bis(formamidin), monoformamidin; B 29 Other classes: at least one of the following insecticides and acaricides: mivorilaner, modoflaner, tigolaner, umifoxolaner, trifluralin, fluazinam, spinosad, and mineral oil.

3. The pesticide composition containing biphenyl sulfide compounds according to claim 2, characterized in that, The active ingredient B is selected from any one of abamectin, etoxazole, difenoconazole, propargite, tetradifon, fluazinam, and abamectin.

4. The pesticide composition containing biphenyl sulfide compounds according to claim 1, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:100 to 100:1; preferably 1:80 to 80:1; more preferably 1:50 to 50:1; further preferably 1:45 to 45:1; and even more preferably 1:25 to 25:

1.

5. The pesticide composition containing biphenyl sulfide compounds 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 the active ingredient A and the active ingredient B in the pesticide composition is 1 to 95 wt%. Preferably, the sum of the contents of the active ingredient A and the active ingredient B in the pesticide composition is 5 to 80 wt%.

6. The pesticide composition containing biphenyl sulfide compounds 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 containing biphenyl sulfide compounds according to claim 5, characterized in that, The pesticide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid and / or liquid formulations; 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. 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. Preferably, the solid formulation is selected from wettable powder, water-dispersible granules, and soluble granules; the liquid formulation is selected from emulsifiable concentrate, water emulsion, and suspension concentrate.

8. The application of the pesticide composition containing a diphenyl sulfide compound according to any one of claims 1-7 in the control of phytophagous mites.

9. The application according to claim 8, characterized in that, The phytophagous mites mentioned are spider mites, malariae, and / or eupodid mites; Preferably, the phytophagous mites are spider mites; More preferably, the spider mite is *Tetranychus truncatus*, *Tetranychus carmineus*, *Tetranychus citrinum*, or *Tetranychus two-spotted*.

10. The application according to claim 8, characterized in that, The acaricide composition and / or its formulation are 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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