A miticidal composition and use thereof

Abstract

The present application relates to pesticide mite killing technical field, disclose a kind of acaricidal composition, the acaricidal composition includes active ingredient A and active ingredient B, the active ingredient A is the compound shown in formula I: the active ingredient B is any one in diafenthiuron or fluazinam;The mass ratio of the active ingredient A and active ingredient B is 1:50~45:1.The acaricidal composition of the present application has excellent control effect on arachnida, Tetranychidae and other mite pests, can effectively control the damage of crop mite, reduce the dosage of pesticide, and is safe to non-target organisms and predatory mites, and is friendly to the environment.

Description

[0001] This invention application is a divisional application of application number CN202310043302.6, filed on January 29, 2023, entitled "An acaricide composition and its use". Technical Field

[0002] This invention belongs to the field of pesticide acaricide technology, specifically relating to an acaricide composition and its uses. Background Technology

[0003] Diethyl urea is a novel thiourea insecticide and acaricide with contact, stomach poison, systemic, and fumigation effects. It only becomes biologically active after being decomposed into carbodiimide derivatives under ultraviolet radiation or by the action of multifunctional oxidases within the insect. These carbodiimide derivatives selectively and covalently bind to Fo-ATPase on the inner mitochondrial membrane and porin on the outer membrane, inhibiting mitochondrial respiration. This hinders the function of mitochondria in the nerve cells of pests, affecting their respiration and energy conversion, thus causing insect death. Its structural formula is as follows:

[0004]

[0005] Fluazinam, a pyridine amine derivative belonging to the dinitroaniline class of compounds, is a bactericide and acaricide with protective, mild curative, and systemic effects. As an acaricide, fluazinam's mechanism of action involves altering the permeability of the mitochondrial inner membrane to protons and increasing SOD2 transcription levels, thus interfering with mitochondrial respiration and ultimately leading to mite death. Its structural formula is as follows:

[0006]

[0007] Compound I is a novel formamide acaricide discovered and developed by Nippon Nippon Kogyo Co., Ltd. The Insecticide Resistance Action Committee classifies it as Subgroup 25B (formamide class). It exhibits significant inhibitory activity against mitochondrial complex II of harmful mites. It demonstrates significant acaricidal activity against a variety of harmful mites. This acaricide is low in toxicity, highly effective, and selective, with extremely low toxicity to pollinating insects and beneficial arthropods such as natural enemies. Its structural formula is shown below:

[0008]

[0009] Tetranychus mites are a global pest that feeds on vegetables, fruit trees, and flowers through piercing and sucking their flesh. This causes chlorosis, scorching, and leaf drop, impairs photosynthesis, inhibits growth, and hinders fruit development, severely impacting yield and quality in various vegetable, flower, and fruit-producing regions of my country. These mites reproduce rapidly with significant generation overlap, and current control methods primarily rely on chemical methods. However, due to long-term, inappropriate use of pesticides, Tetranychus mites have developed varying degrees of resistance to acaricides with different mechanisms of action. Summary of the Invention

[0010] Based on the above, the present invention provides an acaricidal composition that is effective against a variety of plant-eating mites, effectively controls the damage caused by crop mites, reduces the dosage of pesticides, and is safe for non-target organisms and predatory mites, and is environmentally friendly.

[0011] To achieve the above objectives, the present invention adopts the following technical solution: an acaricidal composition, wherein the acaricidal composition comprises active ingredient A and active ingredient B, wherein active ingredient A is a compound represented by formula I:

[0012] The active ingredient B is either butylated urea or fluazinam; the mass ratio of active ingredient A to active ingredient B is 1:50 to 45:1.

[0013] Further, the mass ratio of active ingredient A to active ingredient B is 1:50, 1:45, 1:30, 1:15, 1:8, 1:5, 1:4, 1:3, 1:1, 3:1, 4:1, 5:1, 8:1, 15:1, 30:1, or 45:1.

[0014] Furthermore, the active ingredient B is butyl ether urea, and the mass ratio of active ingredient A to active ingredient B is 1:45 to 30:1;

[0015] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:45, 1:30, 1:15, 1:5, 1:3, 1:1, 3:1, 5:1, 15:1, or 30:1.

[0016] Furthermore, the active ingredient B is butyl ether urea, and the mass ratio of the active ingredient A to the active ingredient B is 1:45 to 5:1;

[0017] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:45, 1:30, 1:15, 1:5, 1:3, 1:1, 3:1, or 5:1.

[0018] Furthermore, the active ingredient B is fluazinam, and the mass ratio of active ingredient A to active ingredient B is 1:50 to 8:1;

[0019] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:50, 1:30, 1:15, 1:8, 1:4, 1:1, 4:1, or 8:1.

[0020] Furthermore, the active ingredient B is fluazinam, and the mass ratio of active ingredient A to active ingredient B is 1:30 to 4:1;

[0021] Furthermore, the mass ratio of active ingredient A to active ingredient B is 1:30, 1:15, 1:8, 1:4, 1:1, or 4:1;

[0022] Furthermore, the total weight of the acaricide composition is 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 0.5% to 80% of the total weight of the acaricide composition.

[0023] Furthermore, the total weight of active ingredient A and active ingredient B accounts for 1% to 70% of the total weight of the acaricide composition.

[0024] Furthermore, in addition to the active ingredient, the acaricide composition also contains agriculturally permissible 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.

[0025] The wetting agent is selected from one or more of the following: alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, sodium dodecyl sulfate, sodium dioctyl succinate sulfonate, α-olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol ethoxylate, fatty alcohol ethoxylate, sodium fatty alcohol polyoxyethylene ether sulfate, silkworm excrement, soapberry powder, soapberry powder, SOPA, detergent, emulsifier 2000 series, and wetting and penetrating agent F; and / or

[0026] 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

[0027] The thickener is selected from one or more of xanthan gum, polyvinyl alcohol, organobentonite, magnesium aluminum silicate, and carboxymethyl cellulose; and / or

[0028] 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

[0029] 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

[0030] 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

[0031] 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

[0032] 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

[0033] The synergist is selected from synergistic phosphorus, synergistic ether; and / or

[0034] The carrier is selected from one or more of kaolin, bentonite, attapulgite, light calcium carbonate, diatomaceous earth, and precipitated silica; and / or

[0035] 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

[0036] All of the above auxiliary ingredients are commercially available.

[0037] Furthermore, the acaricide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid and / or liquid formulations;

[0038] Furthermore, the directly usable solid dosage form is a powder, granule, ball, tablet, or strip;

[0039] The dispersible solid dosage form is a wettable powder, an oil-dispersible powder, an emulsion powder, a water-dispersible granule, an emulsion granule, or a water-dispersible tablet;

[0040] The soluble solid dosage form is a soluble powder, soluble tablet, or soluble granule;

[0041] Furthermore, the liquid formulation is a solution formulation, a dispersed liquid formulation, an emulsion formulation, a suspension formulation, or a multiphase formulation;

[0042] Furthermore, the solution formulation is a soluble agent, a soluble gel, an oil, or a film-spreading oil;

[0043] The dispersed liquid formulation is an emulsifiable concentrate, latex, dispersible liquid, or ointment;

[0044] The emulsion formulation is an aqueous emulsion, an oil emulsion, a microemulsion, or a lipid formulation;

[0045] The suspension formulation is a suspension agent, microcapsule suspension agent, oil suspension agent, or dispersible oil suspension agent;

[0046] The multiphase formulation is a suspension emulsion, a microcapsule suspension-suspension, a microcapsule suspension-water emulsion, or a microcapsule suspension-suspension emulsion;

[0047] Furthermore, the liquid formulation is selected from emulsifiable concentrates and / or suspension concentrates, and the solid formulation is selected from water-dispersible granules and / or wettable powders.

[0048] The present invention also discloses the use of the acaricidal composition as described above for controlling crop pests;

[0049] Furthermore, the crops mentioned are cash crops and food crops; the mites mentioned are spider mites, gall mites and / or true mites.

[0050] Furthermore, the aforementioned spider mites include, but are not limited to: Carmine Spider Mite, Two-spotted Spider Mite, Hawthorn Leaf Mite, Citrus Pestilago, Apple Pestilago, Kanzawa Spider Mite, Wheat Mite, and Citrus Tetranychus.

[0051] The mites mentioned include, but are not limited to: citrus rust mite and wolfberry gall mite;

[0052] The aforementioned mites of the family Ephedra include, but are not limited to: the red spider mite (Ceratophora spp.).

[0053] Furthermore, the mites mentioned are spider mites;

[0054] Furthermore, the spider mites mentioned are *Tetranychus carmineus*, *Tetranychus two-spotted*, *Tetranychus hawthornus*, *Tetranychus truncatus*, *Tetranychus citrus*, and *Tetranychus maculata*.

[0055] Furthermore, the aforementioned spider mites are *Tetranychus carmineus*, *Tetranychus two-spotted*, and / or *Tetranychus citrus*.

[0056] Further, the acaricidal composition and / or its formulation are applied to the harmful mites or their growth medium at an effective dose.

[0057] The beneficial effects of this invention are:

[0058] 1) The acaricidal composition of the present invention has a good control effect on crop mites and a significant synergistic effect on multiple mites;

[0059] 2) The acaricide composition of the present invention can slow down the development of pesticide resistance in harmful mites, reduce the amount of pesticides used, and is safe for non-target organisms and predatory mites, and is environmentally friendly. Detailed Implementation

[0060] To make the technical solution clearer, the present invention will be clearly described in conjunction with the following specific embodiments. However, the present invention can be implemented in various forms and should not be limited to the embodiments described herein.

[0061] Formulation preparation example

[0062] Preparation Example 1: 12% Compound I·Butyl ether urea emulsifiable concentrate (1:3)

[0063] By weight percentage, 3% Formula I compound, 9% butyl ether urea, 15% N-methylpyrrolidone, 10% alkylphenol polyoxyethylene ether, 2% calcium dodecylbenzenesulfonate, 10% acetophenone, and xylene to make up the balance.

[0064] Preparation method: According to the formula ratio, the metered compound of formula I, butyl ether urea, solvent, and co-solvent are added to the mixing tank and stirred to dissolve. 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.

[0065] Preparation Example 2: 36% Formula I compound butyl ether urea water-dispersible granules (1:5)

[0066] By weight percentage, 6% Formula I compound, 30% butyl ether urea, 10% sodium lignosulfonate, 2% bleaching powder BX, 2% sodium polycarboxylate, 5% ammonium sulfate, and kaolin to make up the balance.

[0067] Preparation method: According to the formula ratio, add the active ingredient compound I and butyl ether urea to the carrier, and add surfactants and other functional additives. Mix, and after air jet milling, add 10-25% water. 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.

[0068] Preparation Example 3: 22% Formula I compound butyl ether urea wettable powder (1:10)

[0069] By weight percentage, 2% Formula I compound, 20% butyl ether urea, 8% naphthalene sulfonate formaldehyde condensate, 3% sodium dodecylbenzene sulfonate, 2% pull-out powder BX, and kaolin to make up the balance.

[0070] Preparation method: The active ingredient compound of formula I, butyl ether urea, dispersant, wetting agent and filler are mixed according to the formula ratio, stirred evenly in a stirring tank, and then pulverized and mixed evenly multiple times by an air jet mill to prepare the wettable powder of the composition of the present invention.

[0071] Preparation Example 4: 24% Compound I·Butyl ether urea suspension (1:3)

[0072] By weight percentage, 6% Formula I compound, 18% butyl ether urea, 3% alkylphenol polyoxyethylene ether phosphate, 4% alkylphenol polyoxyethylene ether, 1% sodium polycarboxylate, 1% succinate sulfonate, 1.5% magnesium aluminum silicate, 0.2% xanthan gum, 5% glycerol, 0.2% sodium benzoate, 0.5% silicone oil, and deionized water to make up the balance.

[0073] Preparation method: According to the formula ratio, the active ingredient compound I, butyl ether urea, surfactant 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.

[0074] Preparation Example 5: 18% Formula I compound·fludinamide suspension (1:8)

[0075] By weight percentage, 2% Formula I compound, 16% fluazinam, 2% sodium dodecylbenzenesulfonate, 1% fatty alcohol polyoxyethylene ether, 2% naphthalene sulfonate formic acid condensate, 2% styrene phenol polyoxyethylene ether sulfate, 1.5% magnesium aluminum silicate, 0.15% xanthan gum, 1% sodium sorbate, 5% ethylene glycol, 0.5% silicone oil, and deionized water to make up the balance.

[0076] Preparation method: According to the formula ratio, 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.

[0077] Preparation Example 6: 35% Formula I compound·fludinamide wettable powder (1:4)

[0078] By weight percentage, 7% Formula I compound, 28% fluazinam, 8% sodium lignosulfonate, 1% pull-out powder BX, 12% sodium dodecylbenzene cyclamate, 5% silica, and kaolin to make up the balance.

[0079] Preparation method: According to the formula ratio, the active ingredients, dispersant, wetting agent and filler are mixed and stirred evenly in a mixing tank. The mixture is then pulverized and mixed evenly multiple times by an air jet mill to prepare a wettable powder.

[0080] Preparation Example 7: 30% Formula I compound·fludinamide water-dispersible granules (1:1)

[0081] By weight percentage, 15% of Formula I compound, 15% of fluazinam, 8% sodium lignosulfonate, 2% sodium polycarboxylate, 5% ammonium sulfate, and kaolin to make up the balance.

[0082] Preparation method: According to the formula ratio, 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 spray drying and sieving to obtain water-dispersible granules.

[0083] Preparation Example 8: 20% Formula I compound·fludinamide suspension (4:1)

[0084] By weight percentage, 16% Formula I compound, 4% fluazinam, 1% fatty alcohol polyoxyethylene ether, 4% alkylphenol polyoxyethylene ether phosphate, 2% styrene-phenol polyoxyethylene ether sulfate, 2% isomeric alcohol polyoxyethylene ether, 0.25% xanthan gum, 5% ethylene glycol, 0.2% sodium benzoate, 0.5% silicone oil, and deionized water to make up the balance.

[0085] Preparation method: Same as in preparation example 5.

[0086] Preparation Example 9: 36% Formula I compound·fludinamide wettable powder (1:8)

[0087] By weight percentage, 4% Formula I compound, 32% fluazinam, 6% sodium lignosulfonate, 2% dispersant NNO, 2% sodium polycarboxylate, 4% sodium dodecylbenzenesulfonate, 5% silica, and kaolin to make up the balance.

[0088] Preparation method: Same as in preparation example 6.

[0089] Preparation Example 10: 32% Formula I compound·fluazinam aqueous dispersible granules (1:15)

[0090] By weight percentage, 2% Formula I compound, 30% fluazinam, 10% lignin sulfonate, 4% sodium dodecylbenzene sulfonate, 2.5% pull-out powder BX, 2% sodium polycarboxylate, and light calcium carbonate to make up the balance.

[0091] Preparation method: Same as in preparation example 7.

[0092] Indoor life test

[0093] Example 1: Indoor activity test of butyl urea combined with compound I against two-spotted spider mites

[0094] Test basis: The test was conducted in accordance with NY / T 1154.13-2008 "Guidelines for Indoor Bioassay of Pesticides - Insecticides - Part 13: Leaf Disc Spraying Method".

[0095] Experimental target: Two-spotted spider mite (Tetranychus urticae Koch), selected female adult mites cultured indoors and in the same physiological state.

[0096] Test reagents: 95% butyl urea technical grade and 92% compound I technical grade, both of which were provided by the Group's R&D Center.

[0097] Test material preparation: Select broad bean leaves with uniform growth, make leaf discs using a punch, place a wet sponge in the petri dish, place filter paper on it, and place leaf discs on the filter paper, with two leaf discs per dish. Inoculate the adult mites cultured indoors onto the leaf discs, 10 mites per leaf disc.

[0098] Drug preparation: Dissolve the above-mentioned raw drug in acetone, then dilute it with 0.1% Tween 80 aqueous solution to prepare a reasonable mass concentration gradient.

[0099] Chemical treatment: Adjust the spray pressure of the Potter spray tower to 1.47 × 10⁻⁶. 5 To ensure the stability of Pa, the cleaned spray head was first rinsed twice with acetone, and then twice with distilled water.

[0100] The petri dishes were placed in the bottom tray of the Potter spray tower and sprayed with 1 mL of solution. After the solution settled for 1 minute, the dishes were removed and transferred to the rearing conditions. Each treatment was repeated 4 times, and a treatment without the drug (containing all organic solvents and emulsifiers) was set up as a blank control.

[0101] Feeding and observation: The test insects were fed and observed at a temperature of (25±1)℃ and a photoperiod of L:D=(16:8)h.

[0102] Inspection: Check the mortality of the test insects 48 hours after treatment, and record the total number of insects and the number of dead insects.

[0103] Based on the survey data, the corrected mortality rates for each treatment were calculated. The calculations were performed using formulas (1) and (2):

[0104]

[0105] In the formula:

[0106] P – Mortality rate, expressed as a percentage (%);

[0107] K represents the number of dead insects, in heads;

[0108] N represents the total number of insects treated, in units of heads.

[0109]

[0110] In the formula:

[0111] P1 – Corrected mortality rate, in percentage (%);

[0112] P t —The mortality rate is expressed as a percentage (%).

[0113] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0114] If the control mortality rate is <5%, no correction is needed; if the control mortality rate is between 5% and 20%, correction should be made according to formula (2); if the control mortality rate is >20%, the experiment needs to be repeated.

[0115] The DPS statistical analysis system was used to analyze and derive the toxicity regression equation and LC. 50 The values ​​and correlation coefficients are used to evaluate the activity of the test reagent on the biological sample.

[0116] The co-toxicity coefficient (CTC value) of the mixture is calculated according to formulas (3), (4), and (5):

[0117]

[0118] In the formula:

[0119] ATI – Actual Measured Toxicity Index of Mixtures;

[0120] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0121] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0122] TTI = TI A ×P A +TI B ×P B ……(4)

[0123] In the formula:

[0124] TTI – Theoretical Toxicity Index of Mixtures;

[0125] TI A —A. Toxicity index of drug A;

[0126] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0127] TI B —Toxicity index of drug B;

[0128] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0129]

[0130] In the formula:

[0131] CTC – Cotoxicity Coefficient;

[0132] ATI – Actual Measured Toxicity Index of Mixtures;

[0133] TTI – Theoretical Toxicity Index of Mixtures.

[0134] The co-toxicity coefficients (CTC) of the compound formulations were ≥120, indicating a synergistic effect; CTC ≤80, indicating an antagonistic effect; and 80 < CTC < 120, indicating an additive effect. The results of the indoor toxicity tests are shown in the table below:

[0135] Table 1: Results of indoor activity tests of butyl urea combined with compound I on Tetranychus bicolor.

[0136] Formula I compound y = 4.3224 + 1.7365x 0.9998 2.4561 / Butyl ether urea y = 3.2382 + 1.6539x 0.9997 11.6204 / Compound of Formula I: Butyl ether urea = 1:50 y = 3.3317 + 1.7558x 0.9941 8.9152 121.458 Compound of Formula I: Butyl ether urea = 1:45 y = 3.7256 + 1.4635x 0.9919 7.4264 144.734 Compound of Formula I: Butyl ether urea = 1:30 y = 3.7762 + 1.4955x 0.9908 6.5815 157.593 Compound of Formula I: Butyl ether urea = 1:15 y = 4.0732 + 1.2146x 0.9960 5.7952 162.599 Compound of Formula I: Butyl ether urea = 1:5 y = 4.1991 + 1.4752x 0.9970 3.4905 205.266 Compound of Formula I: Butyl ether urea = 1:3 y = 4.2603 + 1.4240x 0.9976 3.3072 181.791 Compound of Formula I: Butyl ether urea = 1:1 y = 4.4470 + 1.3684x 0.9930 2.5357 159.921 Formula I compound: Butyl ether urea = 3:1 y = 4.6047 + 1.2301x 0.9900 2.0957 145.978 Compound of Formula I: Butyl ether urea = 5:1 y = 4.6531 + 1.1787x 0.9989 1.9691 143.608 Compound of Formula I: Butyl ether urea = 15:1 y = 4.6002 + 1.3107x 0.9985 2.0184 127.994 Compound of Formula I: Butyl ether urea = 30:1 y = 4.5698 + 1.4159x 0.9989 2.0129 125.203 Compound of Formula I: Butyl ether urea = 45:1 y = 4.5811 + 1.3274x 0.9992 2.0682 120.827

[0137] Indoor test results showed that the combination of buprofen and compound I exhibited good acaricidal effects. When the mass ratio of compound I to buprofen was 1:50–45:1, the co-toxicity coefficient was greater than 120, indicating a synergistic effect. When the mass ratio of compound I to buprofen was 1:45–5:1, the co-toxicity coefficient was greater than 140, demonstrating a significant synergistic effect.

[0138] Example 2: Indoor activity test of compound I and fluazinam in combination with citrus psyllids

[0139] Test basis: The test was conducted in accordance with NY / T 1154.13-2008 "Guidelines for Indoor Bioassay of Pesticides - Insecticides - Part 13: Leaf Disc Spraying Method".

[0140] Experimental target: Citrus psoriatic mites (Panonychus cirtri Wcgregov), female adult mites with consistent physiological states were selected.

[0141] Test reagents: 92% Formula I compound technical grade and 98% fluazinam technical grade, both provided by the Group's R&D Center.

[0142] Test material preparation: Select citrus leaves with uniform growth, make suitable leaf discs using a punch, place a wet sponge in the petri dish, place filter paper on it, and place leaf discs on the filter paper, with 2 leaf discs per dish. Inoculate the target mites raised indoors onto the leaf discs, 10 mites per leaf disc.

[0143] Drug preparation: Dissolve the above raw materials in a suitable solvent, and design 5 groups of ratios according to the purpose of mixing and drug activity. Each single agent and each group of mixed agents are prepared into a series of mass concentration gradients.

[0144] Experimental method: Adjust the pressure of the Potter spray tower to 1.47 × 10⁻⁶. 5 To ensure the stability of Pa, the cleaned spray head was first rinsed twice with acetone, and then twice with distilled water.

[0145] The petri dishes were placed on the bottom of the Potter spray tower and sprayed with 1 mL of liquid. After the liquid settled for 1 minute, the dishes were removed. Each treatment was repeated 4 times, and a treatment without the drug was set as a blank control.

[0146] Feeding and observation: The treated test insects were placed under suitable conditions for feeding and observation. After 48 hours, the mortality of the test insects was checked, and the total number of insects and the number of dead insects were recorded.

[0147] Calculation method:

[0148] Calculate the mortality rate for each treatment based on the survey data. Use the following formula:

[0149]

[0150] In the formula:

[0151] P – Mortality rate, expressed as a percentage (%);

[0152] K represents the number of dead insects, in heads;

[0153] N represents the total number of insects treated, in units of heads.

[0154]

[0155] In the formula:

[0156] P1 – Corrected mortality rate, in percentage (%);

[0157] P t —The mortality rate is expressed as a percentage (%).

[0158] P0 – Mortality rate in the blank control group, expressed as a percentage (%).

[0159] 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.

[0160] The DPS statistical analysis system was used to analyze the data and derive the toxicity regression equation and LC. 50 The values ​​and correlation coefficients are used to evaluate the activity of the test reagent on the biological sample.

[0161] The co-toxicity coefficient (CTC value) of the mixture is calculated using the following formula:

[0162]

[0163] In the formula:

[0164] ATI – Actual Measured Toxicity Index of Mixtures;

[0165] S – LC50 of standard acaricides 50 The unit is milligrams per liter (mg / L);

[0166] M – LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0167] TTI = TI A ×P A +TI B ×P B

[0168] In the formula:

[0169] TTI – Theoretical Toxicity Index of Mixtures;

[0170] TI A —A. Toxicity index of drug A;

[0171] P A —Percentage content of drug A in the mixture, expressed as percentage (%);

[0172] TI B —Toxicity index of drug B;

[0173] P B —Percentage content of agent B in the mixture, expressed as percentage (%).

[0174]

[0175] In the formula:

[0176] CTC – Cotoxicity Coefficient;

[0177] ATI – Actual Measured Toxicity Index of Mixtures;

[0178] TTI – Theoretical Toxicity Index of Mixtures.

[0179] 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.

[0180] The results of the indoor tests are shown in the table below:

[0181] Table 2. Results of indoor activity tests of compound I and fluazinam on *Pseudomonas citrus*.

[0182]

[0183]

[0184] The experimental results in the table above show that the combination of compound I and fluazinam in a reasonable ratio exhibits good acaricidal effects. Compound I shows high toxicity against *Pachycarpus citrinum*, with a LC50 value of [missing information]. 50 The concentration was 1.6858 mg / L. When the mass ratio of compound I to fluazinam was 1:50–50:1, the co-toxicity coefficient was greater than 80, indicating a synergistic or additive effect. When the mass ratio of compound I to fluazinam was 1:50–8:1, the co-toxicity coefficient was greater than 120, indicating a synergistic effect. When the mass ratio of compound I to fluazinam was 1:30–4:1, the co-toxicity coefficient was greater than 140, indicating a significant synergistic effect.

[0185] Field efficacy trials

[0186] Example 3: Field efficacy test of buprofen combined with compound I on spider mites

[0187] Experimental basis: The experiment was conducted in accordance with GB / T 17980.17-2000 "Guidelines for Field Efficacy Tests of Pesticides (I) Acaricides for the Control of Spider Mites on Legumes and Vegetables".

[0188] Experimental target: a mixed population of Tetranychus cinnabarinnum Boisduval and Tetranychus urticae Koch.

[0189] Experimental crop: common bean.

[0190] Experimental location: The experiment was conducted in Jimo City, Qingdao, Shandong Province. The soil fertility of the experimental site was moderate to high, and the irrigation conditions were good, which was in line with the agricultural production practices at that time.

[0191] Experimental cell arrangement: Experimental cells are arranged in random blocks, with a cell area of ​​20m². 2 Each treatment was repeated 4 times.

[0192] Experimental method: The experiment was conducted once during the flowering period of green beans. The Gongnong-16 backpack sprayer was used to spray the entire green bean plant, making sure that both the upper and lower surfaces of the leaves were sprayed.

[0193] Investigation methods: A baseline survey was conducted before pesticide application, and surveys were conducted 3 days and 14 days after pesticide application. Twenty leaves were taken from each plot to count the number of live mites.

[0194] Methods for calculating drug efficacy:

[0195]

[0196]

[0197] Pesticide damage observation: During the trial, field observations were conducted irregularly. No effects of the tested pesticides on the growth of common beans or on other non-target organisms and predatory mites were found.

[0198] The test drug, control drug, and dosage are shown in the table below.

[0199] Table 3: Field efficacy test results of buprofen combined with compound I on spider mites

[0200]

[0201] Field efficacy trials showed that the combination of buprofen and compound I exhibited good control effects against spider mites. Three days after application, the combined formulation showed an overall control efficacy of over 80% against spider mites, demonstrating better rapid action compared to the control single agent. Fourteen days after application, the control efficacies of 22% compound I·buprofen wettable powder (1:10), 12% compound I·buprofen emulsifiable concentrate (1:3), and 36% compound I·buprofen water-dispersible granules (1:5) were 87.19%, 90.15%, and 92.29%, respectively.

[0202] Example 4: Field efficacy test of buprofen combined with compound I against citrus psyllid.

[0203] Experimental basis: The experiment was conducted in accordance with GB / T 17980.11-2000 "Guidelines for Field Efficacy Tests of Pesticides (I) Acaricides for the Control of Citrus Paronychia".

[0204] Experimental target: Citrus psoriatic mites (Panonychus citri). The occurrence of mite infestation was relatively uniform in the experimental area.

[0205] Experimental crop: Citrus.

[0206] Experimental location: The experiment was conducted in a citrus orchard in Dayu County, Ganzhou City, Jiangxi Province. The soil fertility at the experimental site was moderate, and the soil was clay.

[0207] Experimental plots: 2 trees per plot, with protective rows set up around them, and each treatment was repeated 4 times.

[0208] Application time: The experiment was carried out once in mid-October, which was the initial stage of the citrus paronychia mite outbreak. The Tengfei brand 3WBS-16 backpack sprayer was used to apply the pesticide to ensure that both sides of the leaves were evenly covered with the pesticide.

[0209] Experimental survey: Surveys were conducted 3, 10, and 15 days after pesticide application, and the number of live mites was recorded. During the survey, tender shoots were marked in five directions (east, west, south, north, and center) on each tree in each plot. 25 leaves were surveyed on each tree, and a total of 50 leaves were surveyed in each plot to count the number of live mites. The leaf surface was directly observed using a handheld magnifying glass, and the number of mites was counted.

[0210] Methods for calculating drug efficacy:

[0211]

[0212]

[0213] Direct impact on crops: During the trial, field observations were conducted periodically, and no effects of the tested pesticides on citrus growth or on other non-target organisms and predatory mites were found.

[0214] The results of the field efficacy trials are shown in the table below:

[0215] Table 4: Field efficacy test results of buprofen combined with compound I for *Pachycarpus citrinum*

[0216]

[0217] As can be seen from the field efficacy test in the table above, the combination of buprofen and compound I showed good control effect against citrus psyllid. 15 days after application, the 36% compound I·buprofen water-dispersible granules (1:5) achieved a control efficacy of 96.54% against citrus psyllid.

[0218] Example 5: Field efficacy test of compound I and fluazinam combined with citrus psyllids.

[0219] Test basis: GB / T 17980.11-2000 "Guidelines for Field Efficacy Tests of Pesticides (I) Acaricides for the Control of Citrus Paronychia".

[0220] Experimental target: Citrus psoriatic mites (Panonychus cirtri).

[0221] The experiment was conducted in a citrus orchard in Taiping Town, Nanning City, Guangxi Zhuang Autonomous Region, where the citrus trees were planted at a uniform density and water and fertilizer management was consistent with local scientific agricultural practices.

[0222] Plant arrangement: 2 citrus trees per plantation, 4 replicates per treatment.

[0223] Experimental Design: The experiment consisted of 5 pesticide treatments and 1 blank control, for a total of 6 treatment groups. The pesticide was applied once on August 5, 2019, with 4 kg of pesticide applied to each citrus tree. A Gongnong 16 backpack sprayer was used to spray the entire tree, ensuring even spraying, covering both sides of the leaves and branches.

[0224] Survey Method: In each plot, tender shoots were marked at five points (east, west, south, north, and center) on the tree, and the number of active mites on a total of 25 leaves was investigated. The leaf surface was observed using a handheld magnifying glass, and the number of mites was counted.

[0225] Investigation time: The initial mite population was investigated before the experiment, and the population was investigated again at 1 day, 3 days, 10 days and 15 days after treatment, and the number of active mite stages was recorded.

[0226] Methods for calculating drug efficacy:

[0227]

[0228]

[0229] Results of field efficacy trials:

[0230] Table 5: Results of field efficacy trials of compound I and fluazinam combined with citrus pseudococcus in 2019

[0231]

[0232] On July 25, 2020, and August 3, 2021, pesticides were applied to the same plot of citrus orchard in Taiping Town, Nanning City, Guangxi Zhuang Autonomous Region. The experimental design and methods are as described above. The field efficacy of the pesticide after application in 2021 was statistically investigated.

[0233] Table 6: Results of field efficacy trials of compound I and fluazinam combined with citrus pseudococcus in 2021

[0234]

[0235] The results of the 2019 field efficacy trials (Table 5) show that the combination of Formula I compound and fluazinam has a good control effect on citrus pseudococcus. At 1 and 3 days post-application, the 30% Formula I compound·fluazinam water-dispersible granules (1:1), 35% Formula I compound·fluazinam wettable powder (1:4), and 18% Formula I compound·fluazinam suspension (1:8) showed good rapid-acting effects, with an overall control efficacy of over 75%. At 15 days post-application, the 18% Formula I compound·fluazinam suspension (1:8) achieved a control efficacy of 97.40%, and all treatments showed good residual efficacy.

[0236] The results of the 2021 field survey (Table 6) show that the combination of Formula I compound and fluazinam can effectively slow down the development of pesticide resistance in mites. After three years of continuous application in the same plot, the single-agent 25% Formula I compound suspension and 40% fluazinam suspension significantly reduced the control efficacy against citrus parchomitid.

[0237] In summary, both indoor bioassays and field efficacy trials demonstrate that the pesticide composition of this invention exhibits good control effects against mites, effectively controlling the damage caused by mites in crops, delaying the development of pesticide resistance in target mites, reducing the dosage of pesticides used, and is safe for natural enemies and environmentally friendly.

Claims

1. A mite-killing composition, characterized in that, The acaricide composition comprises active ingredient A and active ingredient B, wherein active ingredient A is a compound represented by formula I: The active ingredient B is fluoroquinolone; the mass ratio of active ingredient A to active ingredient B is 1:50 to 8:

1.

2. The acaricide composition according to claim 1, characterized in that, The mass ratio of active ingredient A to active ingredient B is 1:30 to 4:

1.

3. The acaricide composition according to claim 1, characterized in that, The total weight of the acaricide composition is 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 0.5% to 80% of the total weight of the acaricide composition.

4. The acaricide composition according to claim 3, characterized in that, The total weight of the acaricide composition is 100 wt%, and the total weight of active ingredient A and active ingredient B accounts for 1% to 70% of the total weight of the acaricide composition.

5. The acaricide composition according to claim 1, characterized in that, In addition to the active ingredient, the acaricide composition contains agriculturally permissible 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.

6. The acaricide composition according to claim 1, characterized in that, The acaricide composition can be prepared into an agriculturally permissible formulation, wherein the formulation is selected from solid or liquid formulations; The liquid formulation is selected from emulsifiable concentrates, suspensions, or microemulsions, and the solid formulation is selected from water-dispersible granules.

7. The use of the acaricidal composition according to any one of claims 1-6 for controlling crop mites, characterized in that, The pest mentioned is the citrus parrot mite.

8. The use according to claim 7, characterized in that, The acaricidal composition or its formulation is applied to the harmful mites or their growth medium at an effective dose.

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