A miticide containing an organotin compound and use thereof

Abstract

The application belongs to the technical field of pesticide mite-killing, and discloses a mite-killing agent containing organotin compounds and application thereof. The mite-killing agent comprises active ingredient A and active ingredient B. The active ingredient A is a compound of formula I. The active ingredient B is an organotin compound. The organotin compound is triazol tin or fentin hydroxide. The mass ratio of the active ingredient A to the active ingredient B is 1:50-45:1. The mite-killing agent has obvious synergistic effect on common agricultural mites, especially on Tetranychidae mites and Eriophyidae mites.

Description

Technical Field

[0001] This invention belongs to the field of pesticide acaricide technology, and discloses an acaricide containing organotin compounds and its application. Background Technology

[0002] Triazole tin, CAS Registry Number 41083-11-8, chemical name tricyclohexyl(1,2,4-triazol-1-yl)stanane, is widely used to control mites on fruit trees, flowers, and vegetables. Its structural formula is shown below:

[0003]

[0004] Phenylacetylene tin oxide, CAS Registry Number 13356-08-6, chemical name bis[tris(2-methyl-2-phenylpropyl)tin]oxide, can be used to control plant mites at various activity stages on fruit trees, tea trees, flowers, and other crops. Its structural formula is shown below:

[0005]

[0006] Compound I, chemical name: (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, has the following chemical structural formula:

[0007]

[0008] Triazole tin and fenbutatin belong to the organotin class of acaricides and are both oxidative phosphorylation inhibitors. Both primarily act as contact insecticides, with relatively weak oocyte-killing effects. However, compound I has a completely different chemical structure and mechanism of action from organotin acaricides. Studies have found that compound I, when combined with triazole tin or fenbutatin, exhibits a significant synergistic effect on harmful mites within a certain mass ratio range. Summary of the Invention

[0009] Based on the above, the purpose of this invention is to provide an acaricide containing organotin compounds and its application. This acaricide, through the rational compounding of different active ingredients, has a significant synergistic effect on the control of common agricultural mites, especially effective against spider mites and gall mites. Field application of this acaricide can effectively control the damage of mites to crops and control the spread of mites; furthermore, this acaricide reduces the dosage of pesticides and has a significant effect on delaying the development of mite resistance.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: an acaricide containing organotin compounds, wherein the acaricide comprises active ingredient A and active ingredient B, wherein active ingredient A is a compound of formula I: The active ingredient B is an organotin compound, specifically triazoletin or phenylbutanedinium, and the mass ratio of active ingredient A to active ingredient B is 1:50 to 45:1.

[0011] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:48 to 42:1;

[0012] Furthermore, the active ingredient B is triazole tin, and the mass ratio of active ingredient A to active ingredient B is 1:32 to 30:1;

[0013] Furthermore, the active ingredient B is triazole tin, and the mass ratio of active ingredient A to active ingredient B is 1:26 to 32:1.

[0014] Furthermore, the active ingredient B is phenylbutanol, and the mass ratio of active ingredient A to active ingredient B is 1:40 to 30:1;

[0015] Furthermore, the active ingredient B is phenylbutanol, and the mass ratio of active ingredient A to active ingredient B is 1:30 to 30:1.

[0016] Furthermore, the total weight of the acaricide is 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 2% to 70% of the total weight of the acaricide.

[0017] Furthermore, in addition to the active ingredient, the acaricide also includes auxiliary ingredients, which are selected from one or more of the following: wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoamers, solvents, preservatives, stabilizers, synergists, or carriers.

[0018] 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

[0019] 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

[0020] The thickener is selected from one or more of xanthan gum, polyvinyl alcohol, organobentonite, magnesium aluminum silicate, and carboxymethyl cellulose; and / or

[0021] 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

[0022] The emulsifier is selected from one or more of the following: fatty alcohol polyoxyethylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, phenethylphenol polyoxyethylene polyoxypropylene ether, alkylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkylbenzene sulfonate, styrene-phenol polyoxyethylene ether, and fatty acid polyoxyethylene ester; and / or

[0023] The defoamer is selected from silicone oil, C 10 ~C 20 Saturated fatty acid compounds, C8-C 10 One or more of fatty alcohols or silicone compounds; and / or

[0024] The preservative is selected from one or more of sorbic acid, sodium sorbate, potassium sorbate, benzoic acid, sodium benzoate, sodium p-hydroxybenzoate, and methyl p-hydroxybenzoate; and / or

[0025] 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, and epoxidized vegetable oil; and / or

[0026] The synergist is selected from synergistic phosphorus, synergistic ether; and / or

[0027] The carrier is selected from one or more of kaolin, bentonite, attapulgite, light calcium carbonate, diatomaceous earth, and precipitated silica; and / or

[0028] The solvent is selected from one or more of benzene, toluene, xylene, methanol, ethanol, isopropanol, n-butanol, diesel oil, N,N-dimethylformamide, cyclohexanone, ethyl acetate, N-methylpyrrolidone, propanol, butanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether, butyl ether, solvent oil, vegetable oil, vegetable oil derivatives, and deionized water; and / or

[0029] All of the above auxiliary ingredients are commercially available.

[0030] Furthermore, the acaricide can be prepared into a formulation permitted by pesticides, wherein the formulation is a solid formulation and / or a liquid formulation;

[0031] Furthermore, the solid formulation is a water-dispersible granule, wettable powder, granule, soluble powder, or emulsion powder; the liquid formulation is a soluble concentrate, soluble gel, emulsifiable concentrate, water emulsion, oil emulsion, microemulsion, suspension concentrate, microcapsule suspension, oil suspension, dispersible oil suspension, or suspension emulsion.

[0032] The present invention also discloses the application of the acaricide described above for the prevention and control of harmful mites.

[0033] Furthermore, the pests are spider mites and / or gall mites, wherein the spider mites are *Tetranychus carmineus*, *Tetranychus two-spotted*, or *Tetranychus citrus*, and the gall mites are *Tetranychus citrus* or *Tetranychus lycopersicum*.

[0034] Furthermore, the harmful mites mentioned are carmine spider mites, citrus paris mite, or wolfberry gall mite.

[0035] The beneficial effects of this invention are as follows:

[0036] 1) The acaricide of the present invention rationally combines active ingredients with different mechanisms of action, which has a significant synergistic effect on common spider mites and gall mites, effectively controlling the damage and spread of mites;

[0037] 2) The acaricide of the present invention reduces the amount of pesticides used, thereby reducing agricultural production costs and ensuring environmental safety;

[0038] 3) The acaricide of the present invention effectively delays the development of drug resistance in harmful mites, does not cause phytotoxicity to crops, and is safe for non-target organisms. Detailed Implementation

[0039] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is further described in detail below with reference to embodiments. It should be understood that the specific embodiments and formulation preparation examples described herein are merely illustrative of the invention and are not intended to limit the invention.

[0040] Related formulation preparation examples:

[0041] Preparation Example 1: 24% Compound I Triazole Tin Water Dispersible Granules (1:1)

[0042] Formula composition: 12% Formula I compound, 12% triazole tin, 3% sodium dodecyl sulfate, 10% naphthalene sulfonate formaldehyde condensate, 5% sodium polycarboxylate, 5% white sugar, and kaolin to make up the balance.

[0043] Preparation method: According to the formulation ratio of the preparation example, add the active ingredient to the carrier, and add surfactants and other functional additives to it, mix, and after air jet pulverization, add 10-25% water, and then knead, granulate, dry and sieve to obtain water-dispersible granules; or spray water, granulate and dry the pulverized powder in a fluidized bed granulator, and then sieve to obtain the product.

[0044] Preparation Example 2: 25% Compound I Triazole Tin Emulsifiable Concentrate (3:2)

[0045] Formulation composition: 15% Formula I compound, 10% triazole tin, 18% EO / PO block copolymer, 12% acetophenone, 10% N-octylpyrrolidone, 1% calcium dodecylbenzenesulfonate, 15% dichloromethane, xylene to make up the balance.

[0046] Preparation method: According to the formulation ratio of the preparation example, the measured active ingredients, solvents and co-solvents are added to the mixing tank and stirred to dissolve them. Then, the emulsifier is added, and the remaining solvent is used to make up the balance. The mixture is stirred evenly in the mixing tank and filtered to obtain the emulsifiable oil required by the present invention.

[0047] Preparation Example 3: 16% Formula I compound·triazole tin dispersible oil suspension (7:1)

[0048] Formula composition: 14% Formula I compound, 2% triazole tin, 2% lignosulfonate, 12% phenethylphenol polyoxyethylene polyoxypropylene ether, 3% Gelbert alcohol polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, 0.5% silica, 0.5% organobentonite, 15% 200# solvent oil, methyl oleate to make up the balance;

[0049] Preparation method: According to the formula ratio, the active ingredients, surfactants and other functional additives are placed in the reaction vessel in sequence, oil is added and mixed evenly, and then subjected to high-speed shearing, wet sand milling and finally homogenization filtration to obtain the dispersible oil suspension product.

[0050] Preparation Example 4: 18% Formula I compound·triazole tin suspension (1:5)

[0051] Formula composition: 3% Formula I compound, 15% triazole tin, 1% sodium lignosulfonate, 1% naphthalene sulfonate formaldehyde condensate, 3% fatty alcohol polyoxyethylene ether, 3% alkyl phosphate salt, 0.3% xanthan gum, 1% magnesium aluminum silicate, 4% propylene glycol, 0.01% potassium benzisothiazolinone, 0.5% silicone oil, deionized water to make up the balance;

[0052] Preparation method: According to the formulation ratio in the preparation 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.

[0053] Preparation Example 5: 21% Compound I Triazole Tin Suspension Emulsion (5:2)

[0054] Formula composition: 15% Formula I compound, 6% triazole tin, 1% calcium dodecylbenzenesulfonate, 1% alkylphenol polyoxyethylene ether, 1% sodium polycarboxylate, 4% alkylphenol polyoxyethylene ether phosphate, 2% styrene-phenol polyoxyethylene polyoxypropylene ether, 0.1% hydroxyethyl cellulose, 1% magnesium aluminum silicate, 0.1% Kathon, 0.5% silicone defoamer, 5% ethylene glycol, 8% dichloromethane, 6% cyclohexanone, deionized water to make up the balance;

[0055] Preparation method: According to the formulation ratio in the example, the active ingredient B is completely solventized to form an oil phase; the compound of formula I is wet-milled with wetting and dispersing agent, antifreeze agent, defoamer, deionized water, etc. until D90 is less than 5μm to form a suspension mother liquor; the oil phase is added to the suspension mother liquor and stirred evenly, and then a thickener is added and stirred and sheared evenly to prepare the suspension emulsion formulation of the composition of the present invention.

[0056] Preparation Example 6: 40% Compound I·Styrene-Butylene Water Dispersible Granules (1:7)

[0057] Formula composition: 5% Formula I compound, 35% phenylbutanol, 5% sodium polycarboxylate, 10% sodium lignosulfonate, 3% sodium dodecyl sulfate, 10% ammonium sulfate, starch to make up the balance;

[0058] Preparation method: Same as in preparation example 1.

[0059] Preparation Example 7: 20% Compound I·Styrene-Butylene Emulsifiable Concentrate (3:1)

[0060] Formulation composition: 15% Formula I compound, 5% phenylbutanol, 12% DMF, 5% octylphenol polyoxyethylene ether phosphate, 0.5% glacial acetic acid, 10% tristyrene-phenylphenol polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, 15% propylene carbonate, xylene to make up the balance;

[0061] Preparation method: Same as in preparation example 2.

[0062] Preparation Example 8: 18% Compound I · Styrene-Butylene Tin Dispersible Oil Suspension (1:8)

[0063] Formula composition: 2% Formula I compound, 16% phenylbutanol, 4% alkylphenol polyoxyethylene ether, 8% glycerol fatty acid ester polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, 1% sodium polycarboxylate, 1% sodium alkyl polyoxyethylene ether sulfonate, 0.5% organic bentonite, soybean oil to make up the balance;

[0064] Preparation method: Same as in preparation example 3.

[0065] Preparation Example 9: 20% Compound I · Styrene-Butylene Suspension (1:3)

[0066] Formula composition: 5% Formula I compound, 15% phenylbutanol, 2% castor oil polyoxyethylene ether, 1% alkyl aryl polyoxyethylene ether polyoxypropylene ether, 2% castor oil polyoxyethylene ether phosphate, 2% sodium polycarboxylate, 1.5% magnesium aluminum silicate, 0.1% carboxyethyl cellulose, 1% sodium benzoate, 5% ethylene glycol, 0.5% silicone oil, deionized water to make up the balance;

[0067] Preparation method: Same as in preparation example 4.

[0068] Preparation Example 10: 24% Compound I · Styrene-Butylene Suspension Emulsion (5:1)

[0069] Formula composition: 20% Formula I compound, 4% phenylbutanol, 5% dichloromethane, 5% cyclohexanone, 0.2% glacial acetic acid, 2% castor oil polyoxyethylene ether, 3% fatty alcohol polyoxyethylene ether phosphate, 1% sodium polycarboxylate, 2% styrene-phenol polyoxyethylene polyoxypropylene ether, 1% fatty alcohol polyoxyethylene ether sulfate, 4% glycerol, 0.1% hydroxyethyl cellulose, 1% magnesium aluminum silicate, 0.5% sodium diacetate, 0.5% silicone defoamer, deionized water to make up the balance;

[0070] Preparation method: Same as in preparation example 5.

[0071] All the preparations prepared in the above examples have been tested and found to meet the quality and technical indicators required for the corresponding preparations. The preparations obtained are qualified preparations recognized in this field.

[0072] Example 1: Indoor Bioactivity Test of Compound Acaricides Against Tetranychids

[0073] Test basis: The test was conducted in accordance with NY / T 1154.12-2008 "Guidelines for the determination of biological activity of pesticides in the laboratory - Insecticides - Part 12: Tetranychus slide immersion method".

[0074] Experimental targets: adult female Panonychus citri and adult female Tetranychus cinnabarinus.

[0075] Experimental Method: Select female adult mites in the same physiological state. Cut 2cm lengths of double-sided tape and attach them to one end of a glass slide. Select healthy female adult mites and attach them to the double-sided tape, 30 mites per slide. After treatment, place the mites in a container lined with a damp sponge, cover, and place at (25±1)℃. After 2 hours, examine under a microscope, remove dead, injured, and inactive individuals, and replenish to 30 mites per slide.

[0076] Pharmaceutical preparation: The technical grade of compound I, phenylbutazone technical grade, and triazole tin technical grade are dissolved in a solvent and the dissolved technical grade is prepared into a stock solution. Then, five series of mass concentration gradients are prepared by using 0.1% Tween-80 aqueous solution in equal proportions.

[0077] Experimental method: Immerse the glass slide in the above reagent and gently shake for 5 seconds. Remove the slide, absorb the excess reagent with absorbent paper, place it in a white porcelain dish with a damp sponge, and cover it with a transparent plastic film. Repeat each treatment 4 times, and set up a blank control with no reagent (containing all organic solvents and emulsifiers).

[0078] Feeding and observation: The treated mites were fed and observed at (25±1)℃ with a photoperiod L:D = (16:8)h. After 48 hours of treatment, the mites were checked for mortality, and the total number of mites and the number of dead mites were recorded.

[0079] Data statistics and analysis:

[0080] Based on the survey data, the corrected mortality rates for each treatment were calculated using the following formula, and the results were rounded to two decimal places.

[0081]

[0082] In the formula:

[0083] P – Mortality rate, expressed as a percentage (%);

[0084] K represents the number of dead insects, in heads;

[0085] N represents the total number of insects treated, in units of heads.

[0086]

[0087] In the formula:

[0088] P1 – Corrected mortality rate, in percentage (%);

[0089] P t —The mortality rate is expressed as a percentage (%).

[0090] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0091] 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 according to the corrected mortality rate formula; if the control mortality rate is >20%, the trial needs to be repeated.

[0092] The LC was determined using the DPS statistical analysis system. 50The value is used to evaluate the activity of the test reagent on the biological sample.

[0093] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0094]

[0095] In the formula:

[0096] ATI – Actual Measured Toxicity Index of Mixtures;

[0097] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0098] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0099] TTI = TI A ×P A +TI B ×P B

[0100] In the formula:

[0101] TTI – Theoretical Toxicity Index of Mixtures;

[0102] TI A —A. Toxicity index of drug A;

[0103] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0104] TI B —Toxicity index of drug B;

[0105] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0106]

[0107] In the formula:

[0108] CTC – Cotoxicity Coefficient;

[0109] ATI – Actual Measured Toxicity Index of Mixtures;

[0110] TTI – Theoretical Toxicity Index of Mixtures.

[0111] 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.

[0112] The indoor activity test results are shown in the table below:

[0113] Table 1. Results of indoor bioactivity tests of compound I and triazole tin in combination with *Paecilomyces citrus*.

[0114] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Compound (A) of Formula I 3.1977 100.000 / / Triazole Tin (B) 15.4767 20.661 / / A:B(1:32) 10.2566 31.177 23.066 135.167 A:B(1:23) 9.1429 34.975 23.967 145.928 A:B(1:15) 8.0327 39.809 25.620 155.380 A:B(1:10) 6.8922 46.396 27.874 166.449 A:B(1:5) 4.9791 64.222 33.884 189.534 A:B (1:1) 2.8993 110.292 60.331 182.813 A:B(5:1) 2.1298 150.141 86.777 173.019 A:B(12:1) 2.2070 144.889 93.897 154.306 A:B(25:1) 2.3024 138.886 96.949 143.257 A:B(30:1) 2.5663 124.604 97.441 127.876 A:B(40:1) 3.2023 99.856 98.065 101.827

[0115] The results of the indoor tests in Table 1 show that compound I and triazole tin have good activity against *Pseudomonas citrinum*. The mass ratio of the two compounds is 1:32 to 30:1. The co-toxicity coefficient against *Pseudomonas citrinum* is greater than 120, indicating a significant synergistic effect.

[0116] Table 2 shows the results of indoor bioactivity tests of compound I and phenylbutazone in combination with *Pseudomonas citrus*.

[0117] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Compound (A) of Formula I 3.1977 100.000 / / Phenylated tin(B) 29.9939 10.661 / / A:B(1:48) 19.4115 16.473 12.484 131.950 A:B(1:32) 16.7223 19.122 13.368 143.042 A:B(1:21) 13.8448 23.097 14.722 156.886 A:B(1:12) 11.3893 28.076 17.533 160.131 A:B(1:7) 7.6238 41.944 21.829 192.151 A:B(3:1) 2.2749 140.564 77.665 180.987 A:B(7:1) 2.1095 151.586 88.833 170.642 A:B(14:1) 2.3217 137.731 94.044 146.454 A:B(21:1) 2.4228 131.984 95.939 137.570 A:B(33:1) 2.6182 122.134 97.372 125.429 A:B(42:1) 2.6755 119.518 97.922 122.054

[0118] The results of the indoor tests in Table 2 show that compound I and phenylbutazone have good activity against *Pseudomonas citrinum* when combined. The mass ratio of the two compounds is 1:48 to 42:1. The co-toxicity coefficient against *Pseudomonas citrinum* is greater than 120, indicating a significant synergistic effect.

[0119] Table 3. Results of indoor bioactivity tests of compound I and triazole tin in combination with Tetranychus cinnabarinus.

[0120] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Compound (A) of Formula I 0.3087 100.000 / / Triazole Tin (B) 35.3544 0.873 / / A:B(1:46) 11.242 2.746 2.982 92.077 A:B(1:32) 6.3315 4.876 3.877 125.758 A:B(1:28) 4.9664 6.216 4.291 144.845 A:B(1:14) 2.5428 12.140 7.482 162.267 A:B(1:7) 1.1997 25.731 13.264 193.994 A:B(3:2) 0.2762 111.767 60.349 185.200 A:B(7:1) 0.2252 137.078 87.609 156.466 A:B(10:1) 0.2359 130.861 90.988 143.821 A:B(20:1) 0.2367 130.418 95.280 136.879 A:B(30:1) 0.2520 122.500 96.802 126.547 A:B(45:1) 0.2697 114.461 97.845 116.981

[0121] The results of the indoor tests in Table 3 show that compound I and triazole tin have good activity against Tetranychus cinnabarinus. The mass ratio of the two compounds is 1:32 to 20:1. The co-toxicity coefficient against Tetranychus cinnabarinus is greater than 120, and the synergistic effect is significant.

[0122] Table 4 shows the results of indoor bioactivity tests of compound I and phenylbutazone on Tetranychus cinnabarinus.

[0123]

[0124]

[0125] The results of the indoor tests in Table 4 show that the compound of Formula I combined with phenylbutazone exhibits good activity against Tetranychus cinnabarinus. The mass ratio of the two compounds is [value missing], and the co-toxicity coefficient against Tetranychus cinnabarinus is greater than 120, indicating a significant synergistic effect.

[0126] Example 2: Indoor Bioactivity Test of Compound Acaricide Against Lycium barbarum Gall Mite

[0127] Experimental basis: The experiment was conducted in accordance with the "Guidelines for Indoor Bioassay of Pesticides - Insecticides - Part 13: Leaf Disc Spraying Method".

[0128] Experimental target: Lycium barbarum gall mite (Aceri macrodonis Keifer).

[0129] Test material preparation: Select adult mites with the same physiological state and wolfberry leaves with the same growth.

[0130] Pharmaceutical preparation: The technical grade of compound I, phenylbutazone technical grade, and triazole tin technical grade are dissolved in a solvent and the dissolved technical grade is prepared into a stock solution. Then, five series of mass concentration gradients are prepared by using 0.1% Tween-80 aqueous solution in equal proportions.

[0131] Experimental Method: Healthy, newly emerged adult mites were picked up with a pointed brush and placed on the upper surface of fresh wolfberry leaves wrapped with moistened absorbent cotton. Fifteen mites were picked from each leaf. After the mites stabilized, their survival was observed. Dead mites were removed, and new adult mites were added. Each treatment was repeated four times, with two leaves per treatment, for a total of 30 mites. Different concentrations of pesticide solution were evenly sprayed onto the upper surface of the wolfberry leaves using a Potter spray tower. The initial spray volume was 1 mL, and the spraying time was 1 min, used as the standard parameters. The treated wolfberry leaves were wrapped with a layer of absorbent cotton and placed in an incubator at a temperature of 25±1℃, a relative humidity of 70%–80%, and a photoperiod L:D = 14:10 h.

[0132] Check the mite mortality 48 hours after treatment and record the total number of mites and the number of dead mites.

[0133] Data statistics and analysis:

[0134] Based on the survey data, the corrected mortality rates for each treatment were calculated using the following formula, and the results were rounded to two decimal places.

[0135]

[0136] In the formula:

[0137] P – Mortality rate, expressed as a percentage (%);

[0138] K represents the number of dead insects, in heads;

[0139] N represents the total number of insects treated, in units of heads.

[0140]

[0141] In the formula:

[0142] P1 – Corrected mortality rate, in percentage (%);

[0143] P t —The mortality rate is expressed as a percentage (%).

[0144] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0145] 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 according to the corrected mortality rate formula; if the control mortality rate is >20%, the trial needs to be repeated.

[0146] The LC was determined using the DPS statistical analysis system. 50 The value is used to evaluate the activity of the test reagent on the biological sample.

[0147] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0148]

[0149] In the formula:

[0150] ATI – Actual Measured Toxicity Index of Mixtures;

[0151] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0152] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0153] TTI = TI A ×P A +TI B ×P B

[0154] In the formula:

[0155] TTI – Theoretical Toxicity Index of Mixtures;

[0156] TI A —A. Toxicity index of drug A;

[0157] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0158] TI B —Toxicity index of drug B;

[0159] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0160]

[0161] In the formula:

[0162] CTC – Cotoxicity Coefficient;

[0163] ATI – Actual Measured Toxicity Index of Mixtures;

[0164] TTI – Theoretical Toxicity Index of Mixtures.

[0165] 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.

[0166] The indoor activity test results are shown in the table below:

[0167] Table 5. Results of indoor bioactivity tests of compound I and triazole tin in *Gallus lychnophora*.

[0168]

[0169]

[0170] The results of the indoor tests in Table 5 show that compound I and triazole tin have good activity against Lycium barbarum gall mite. The mass ratio of the two is 1:26 to 32:1, and the co-toxicity coefficient against Lycium barbarum gall mite is greater than 120, indicating a significant synergistic effect.

[0171] Table 6 shows the results of indoor bioactivity tests of compound I and phenylbutazone combined with Lycium barbarum gall mite.

[0172] Test reagents <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Compound (A) of Formula I 6.6087 100.000 / / Phenylated tin(B) 24.3524 27.138 / / A:B(1:30) 17.6691 37.403 29.488 126.839 A:B(1:20) 16.1809 40.843 30.607 133.440 A:B(1:10) 12.3670 53.438 33.762 158.281 A:B(1:5) 10.0148 65.989 39.281 167.991 A:B(1:3) 7.9577 83.048 45.353 183.113 A:B(2:1) 4.9816 132.662 75.713 175.218 A:B(5:1) 4.514 146.405 87.856 166.641 A:B (10:1) 4.9737 132.873 93.376 142.299 A:B(15:1) 5.0658 130.457 95.446 136.682 A:B(20:1) 5.2943 124.827 96.530 129.313 A:B(30:1) 5.4116 122.121 97.650 125.060

[0173] The results of the indoor tests in Table 6 show that compound I and phenylbutazone have good activity against Lycium barbarum gall mite when combined. The mass ratio of the two is 1:30 to 30:1, and the co-toxicity coefficient against Lycium barbarum gall mite is greater than 120, indicating a significant synergistic effect.

[0174] Field efficacy trials:

[0175] Example 3: Field trial for the control of citrus spider mites

[0176] The test crop was a citrus tree, specifically a sugar mandarin orange.

[0177] Test target: Citrus phanonychus citri.

[0178] Experimental Site: The experiment was conducted in a citrus orchard in Gugan Village, Dahua Town, Dahua County, Hechi City, Guangxi Zhuang Autonomous Region. The trees in the experimental site were two years old, and the fertilizer and water management was consistent, resulting in uniform citrus growth. The fertility conditions were moderate, consistent with local scientific agricultural practices.

[0179] Test reagents: See Table 7 for test and control reagents and dosages.

[0180] Experimental setup: 2 fruit trees per plot, 4 replicates per treatment, and all experimental plots were randomly arranged in a block design.

[0181] Experimental method: This experiment only applied the pesticide once, on July 22, 2023. The diluted pesticide was sprayed evenly on the citrus leaves, while the blank control was sprayed with an equal amount of water.

[0182] Survey time and frequency: Mite population density surveys were conducted before application and on the 3rd and 15th day after application. For each plot, tender shoots were marked in five directions (east, west, south, north, and center) of the tree. The number of active mites on a total of 25 leaves was surveyed, and the number of live mites was counted.

[0183] Methods for calculating drug efficacy:

[0184]

[0185]

[0186] Results and Analysis:

[0187] Table 7 Results of field trials for controlling citrus spider mites

[0188]

[0189] Field efficacy trials of citrus spider mite control showed that combining compound I with either triazole tin or benzo[a]tin resulted in good control of citrus spider mites in the field.

[0190] Example 4: Field trial for the control of wolfberry gall mite

[0191] The test crop was wolfberry (Ningqi No. 1), with a tree age of about 5 years.

[0192] Test subject: Lycium barbarum gall mite (Aceri macrodonis Keifer).

[0193] Test and control drugs: See Table 8 for test, control drugs and dosages.

[0194] Experimental Site: The experiment was conducted at a wolfberry plantation in Jingyuan County, Baiyin City, Gansu Province. The wolfberry trees in the experimental site were approximately 5 years old and of uniform age. The soil fertility was moderate, the ground was flat, and irrigation conditions were good.

[0195] Experimental setup: Each experimental plot has an area of ​​30m². 2 Each treatment was repeated four times in a randomized block design, with protective rows or isolation zones between plots. At the initial stage of the wolfberry gall mite infestation, the entire wolfberry tree was sprayed using a Gongnong-16 backpack electric sprayer. The leaves of each tree were sprayed evenly on both sides until they were moist but no droplets fell. The experiment was conducted twice, with a 7-day interval between applications.

[0196] Investigation Method: Gall mite infestation was investigated in each plot 7 days and 14 days after the second application of pesticide. Two wolfberry plants were investigated in each plot. For each plant, one current-year branch was investigated from each of the five directions (east, south, west, north, and center) and tagged. 25 leaves at the tip of each branch were investigated, and the total number of leaves and the number of leaves at each level of infestation were recorded. The mite infestation index was investigated, and the control efficacy was calculated.

[0197] Grading standards:

[0198] Grade 0: Leaves are not damaged;

[0199] Grade 1: Only 1-2 insect galls smaller than 1 mm are present on the leaves;

[0200] Grade 3: There are 2 to 3 insect galls on the leaves that are larger than 1 mm but smaller than 2 mm;

[0201] Grade 5: There are more than 3 insect galls smaller than 2mm on the leaves;

[0202] Grade 7: There are insect galls larger than 2mm on the leaves;

[0203] Level 9: Leaves or young branches that are deformed due to severe damage from gall mites.

[0204] Methods for calculating drug efficacy:

[0205]

[0206]

[0207] Results and Analysis:

[0208] Table 8 Results of field trials for controlling Lycium barbarum gall mite

[0209]

[0210] Field efficacy experiments showed that the acaricide of the present invention is significantly effective against Lycium barbarum gall mite. The experiment was conducted with two applications. The control effect was investigated 7 days after the second application. The overall control efficacy of the compound formulation against Lycium barbarum gall mite was over 84%. 14 days after the second application, the control effect of 18% Formula I compound·triazole tin suspension (1:5) reached 94.17%.

[0211] 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, 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. An acaricide containing an organotin compound, characterized in that, The acaricide comprises active ingredient A and active ingredient B, wherein the active ingredient A is a compound of formula I: (Formula I), and the active ingredient B is an organotin compound, which is triazol tin or fentin hydroxide; when the active ingredient B is triazol tin, the mass ratio of the active ingredient A to the active ingredient B is 1:32-30:1; when the active ingredient B is fentin hydroxide, the mass ratio of the active ingredient A to the active ingredient B is 1:40-30:

1.

2. The acaricide according to claim 1, characterized in that, The active ingredient B is triazamate, and the mass ratio of the active ingredient A to the active ingredient B is 1:26-32:

1.

3. The acaricide according to claim 1, characterized in that, The active ingredient B is fenbutatin-oxide, and the mass ratio of the active ingredient A to the active ingredient B is 1:30-30:

1.

4. The acaricide according to claim 1, characterized in that, The total weight of the acaricide is 100 wt%, and the total weight of the active ingredient A and the active ingredient B accounts for 2%-70% of the total weight of the acaricide.

5. The acaricide according to claim 1, characterized in that, The acaricide comprises, in addition to the active ingredients, an auxiliary ingredient selected from one or more of wetting agents, dispersants, emulsifiers, thickening agents, disintegrating agents, antifreezing agents, antifoaming agents, solvents, preservatives, stabilizers, synergists or carriers.

6. The acaricide according to claim 1, characterized in that, The acaricide is prepared into a formulation dosage form allowed in pesticides, which is a solid formulation and / or a liquid formulation.

7. The acaricide according to claim 6, characterized in that, The solid formulation is water dispersible granules, wettable powder, granules, soluble powder or milk powder; and the liquid formulation is soluble liquid, soluble gel, emulsion, water emulsion, oil emulsion, microemulsion, suspension, microcapsule suspension, oil suspension, dispersible oil suspension or suspending emulsion.

8. Use of a miticide according to any one of claims 1 to 7 for controlling a harmful mite, characterized in that, The harmful mites are Tetranychidae mites and / or Eriophyidae mites, the Tetranychidae mites are Tetranychus cinnabarinus, Tetranychus urticae or Panonychus citri, and the Eriophyidae mites are Panonychus citri or Aculops goeze.

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