A miticidal composition and use thereof
By combining pyridaben or abamectin with compounds of formula (I), an acaricide composition is formed, which solves the problem of pesticide resistance in harmful mites and achieves the effects of synergistic effect, cost reduction and extended duration of effect.
Patent Information
- Application Number
- CN202310577829.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-05-22
- Publication Date
- 2025-10-21
- Estimated Expiration
- 2043-05-22
AI Technical Summary
Long-term use of pyridaben and abamectin alone can lead to the development of pesticide resistance in mites. Therefore, it is necessary to use a combination of these pesticides to delay the development of resistance and improve the control effect.
By combining pyridaben or abamectin with compounds of formula (I) in a certain proportion range to form an acaricidal composition, and adding agriculturally acceptable auxiliary ingredients, various formulations can be prepared.
It enhances the acaricidal effect, reduces the dosage, lowers costs, extends the duration of effectiveness, and is safe for crops and non-target organisms.
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Abstract
Description
Technical Field
[0001] The invention belongs to the field of pesticides, and particularly relates to an acaricidal composition and application thereof. Background Art
[0002] The chemical name of the compound of formula (I): (4'-chloro-6-fluoro-4-methyl-[1,1'-biphenyl]-3-yl)(2,2,2-trifluoroethyl) sulfide, and the chemical structure is as follows:
[0003]
[0004] Dabendazole is a mitochondrial electron transport inhibitor that mainly inhibits electron transfer at coenzyme Q0. This agent has a novel structure and a unique mechanism of action. It is highly effective and broad-spectrum in killing mites. It is currently widely used in fields, but long-term, large-scale, and single use can easily lead to the development of drug resistance in harmful mites.
[0005] Abamectin is a highly effective, broad-spectrum antibiotic insecticide and acaricide belonging to the macrolide class of compounds. It has stomach-toxic and contact-killing properties against mites and insects. When sprayed on leaf surfaces, it rapidly decomposes and dissipates. The active ingredients that penetrate into plant parenchyma remain there for extended periods of time and act as a transmissible agent, leaving a long-lasting residual effect against harmful mites and insects that feed within plant tissues.
[0006] Therefore, in order to slow down the resistance of pest mites to abamectin and pyridabenzine as much as possible and to improve the control effect of pest mites, it is necessary to use abamectin and pyridabenzine acaricides in combination to extend the service life of the agents. Summary of the Invention
[0007] In order to solve the above-mentioned problems existing in the prior art, the present invention provides a mite-killing composition, which can effectively prevent harmful mites, show a synergistic effect within a certain proportion range, reduce the cost of use, reduce the amount of medicine used, extend the lasting effect and delay the development of drug resistance.
[0008] In order to solve the above technical problems, the present invention provides the following technical solution: an acaricidal composition, comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is a compound of formula (I):
[0009] Active ingredient B is either pyridabenzyl or avermectin;
[0010] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:50 to 50:1;
[0011] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:40 to 30:1;
[0012] Furthermore, the mass ratio of the active ingredient A to the active ingredient B is 1:30 to 30:1;
[0013] Furthermore, the mass ratio of the compound of formula (I) to pyridaben is 1:40 to 25:1;
[0014] Furthermore, the mass ratio of the compound of formula (I) to pyridaben is 1:40, 1:25, 1:20, 1:14, 1:10, 1:8, 5:3, 1:1, 7:1, 3:1, 17:2, 10:1, 15:1, 25:1;
[0015] Furthermore, the mass ratio of the compound of formula (I) to pyridaben is 1:25 to 15:1;
[0016] Furthermore, the mass ratio of the compound of formula (I) to pyridaben is 1:25, 1:20, 1:14, 1:10, 1:8, 5:3, 1:1, 7:1, 3:1, 17:2, 10:1, 15:1;
[0017] Furthermore, the mass ratio of the compound of formula (I) to avermectin is 1:30 to 30:1;
[0018] Furthermore, the mass ratio of the compound of formula (I) to avermectin is 1:30, 1:25, 1:18, 1:12, 1:10, 1:7, 1:4, 5:1, 3:2, 3:1, 6:1, 15:2, 10:1, 15:1, 16:1, and 30:1;
[0019] Furthermore, the mass ratio of the compound of formula (I) to avermectin is 1:25 to 30:1;
[0020] Furthermore, the mass ratio of the compound of formula (I) to avermectin is 1:25, 1:18, 1:12, 1:10, 1:7, 1:4, 5:1, 3:2, 3:1, 6:1, 15:2, 10:1, 15:1, 16:1, and 30:1;
[0021] Furthermore, based on the total weight of the acaricidal composition being 100 wt%, the sum of the content of the active ingredient A and the active ingredient B in the acaricidal composition is 1 to 95 wt%;
[0022] Furthermore, the sum of the contents of the active ingredient A and the active ingredient B in the acaricidal composition is 2 to 80 wt %;
[0023] Furthermore, the acaricidal composition further comprises, in addition to the active ingredient, agriculturally acceptable auxiliary ingredients, wherein the auxiliary ingredients are selected from one or more of a wetting agent, a dispersant, an emulsifier, a thickener, a disintegrant, an antifreeze agent, a defoaming agent, a solvent, a preservative, a stabilizer, a synergist or a carrier;
[0024] The wetting agent is selected from one or more of alkylbenzene sulfonate, alkylnaphthalene sulfonate, lignin sulfonate, sodium lauryl sulfate, sodium dioctyl sulfosuccinate, alpha olefin sulfonate, alkylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, ethylene glycol polyoxyethylene polyoxypropylene ether, fatty alcohol ethoxylate, isomeric alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether sodium sulfate, silkworm feces, soapberry powder, soapberry powder, SOPA, detergent, emulsifier 2000 series and wetting penetrant F; and / or
[0025] The dispersant is selected from one or more of lignin sulfonate, alkylnaphthalene sulfonate formaldehyde condensate, naphthalene sulfonate, tristyrylphenol ethoxylate phosphate, block polyether phosphate salt, arylphenol polyoxyethylene ether sulfate salt, 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
[0026] The emulsifier is selected from one or more of calcium dodecylbenzenesulfonate, dodecylbenzenesulfonamide, alkylphenol formaldehyde resin polyoxyethylene ether, phenylethylphenol polyoxyethylene polyoxypropylene ether, benzylphenol polyoxyethylene ether, fatty alcohol ethylene oxide-propylene oxide copolymer, styrylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether, alkylphenol ether phosphate and styrylphenol polyoxyethylene ether phosphate; and / or
[0027] The thickener is selected from one or more of xanthan gum, organobentonite, gum arabic, sodium alginate, magnesium aluminum silicate, carboxymethyl cellulose and white carbon black; and / or
[0028] Disintegrants: The disintegrants are 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 antifreeze agent is selected from one or more of alcohols, alcohol ethers, chlorinated hydrocarbons and inorganic salts; and / or
[0030] Defoaming agent selected from C 10 -C 20 Saturated fatty acid compounds, silicone oil, silicone compounds, C8-C 10 One or more of fatty alcohols; and / or
[0031] The solvent is selected from one or more of benzene, toluene, xylene, trimethylbenzene, durene, methanol, ethanol, isopropyl alcohol, n-butanol, isooctyl alcohol, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyldecylamide, N-methylpyrrolidone, cyclohexanone, propylene carbonate, alkylene carbonate, diesel, solvent oil, vegetable oil, vegetable oil derivatives and water; and / or
[0032] The preservative is selected from one or more of propionic acid, sodium propionic acid, sorbic acid, sodium sorbic acid, potassium sorbic acid, benzoic acid, sodium benzoic acid, sodium p-hydroxybenzoic acid, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, isothiazolinones, benzimidazoles, iodopropargyls, pyridinethiones, kasone and 1,2-benzisothiazolin-3-one; and / or
[0033] The stabilizer is selected from one or more of 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, white carbon black, talc, montmorillonite and starch; and / or
[0034] Synergists are selected from synergistic phosphorus, synergistic ether, synergistic amine; and / or
[0035] The carrier is selected from one or more of ammonium salts, ground natural minerals, ground artificial minerals, silicates, resins, waxes, solid fertilizers, water, organic solvents, mineral oils, vegetable oils and vegetable oil derivatives.
[0036] Furthermore, the acaricidal composition can be prepared into an agriculturally acceptable formulation, wherein the formulation is selected from a solid formulation and / or a liquid formulation;
[0037] The solid preparations include powders, granules, pellets, tablets, strips, wettable powders, oil-dispersible powders, emulsion powders, water-dispersible granules, emulsion granules, water-dispersible tablets, soluble powders, soluble tablets or soluble granules;
[0038] The liquid preparations include soluble solutions, soluble gels, oils, film-spreading oils, emulsifiable concentrates, latexes, dispersible solutions, ointments, aqueous emulsions, oil emulsions, microemulsions, lipid suspensions, microcapsule suspensions, oil suspensions, dispersible oil suspensions, suspoemulsions, microcapsule suspension-suspension concentrates, microcapsule suspension-water emulsions, or microcapsule suspension-suspoemulsions;
[0039] Furthermore, the solid preparation is selected from wettable powders, water-dispersible granules, and soluble granules; the liquid preparation is selected from emulsifiable concentrates, aqueous emulsions, suspensions, suspoemulsions, microemulsions, and dispersible oil suspensions;
[0040] Use of an acaricidal composition for controlling harmful mites;
[0041] Furthermore, the harmful mite is a root mite or a spider mite;
[0042] Furthermore, the root mite is the spiny-legged root mite, and the spider mite is the panonychus, cinnabarinus, two-spotted spider mite, and truncate spider mite.
[0043] Furthermore, the acaricidal composition and / or its preparation is applied at an effective dose to the harmful mites to be controlled or the medium where they grow.
[0044] Beneficial effects of the present invention:
[0045] (1) The compound acaricide of the present invention has a significant synergistic effect compared to a single agent, thereby improving the control effect;
[0046] (2) The compound acaricide of the present invention improves the prevention effect while reducing the dosage, cost and residue;
[0047] (3) The compound acaricide of the present invention has a long lasting effect and can effectively control the damage of harmful mites to crops throughout the entire growth period. It is safe to crops, non-target organisms, beneficial organisms and natural enemies, and has the effect of increasing production and ensuring yield. DETAILED DESCRIPTION
[0048] In order to make the technical solutions, objectives and advantages of the present invention more clearly understood, 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.
[0049] Preparation example:
[0050] Preparation Example 1: 35% formula (I) compound·pyridabenzyl suspension (20:15)
[0051] Preparation formula: 20% compound of formula (I), 15% pyridaben, 2% sodium lignin sulfonate, 3% fatty amine polyoxyethylene ether, 2% polycarboxylate, 0.5% naphthalene sulfonate, 0.5% methyl parahydroxybenzoate, 0.2% xanthan gum, 1% magnesium aluminum silicate, 3.5% propylene glycol, 0.2% organosilicon defoamer, and deionized water to make up the balance;
[0052] Preparation method: According to the formula ratio of the embodiment, the active ingredients, surfactants and other functional additives are placed in a reactor in sequence, deionized water is added and mixed evenly, and the suspension product is obtained by high-speed shearing, wet sand grinding, and finally homogenization filtration.
[0053] Preparation Example 2: 22% Formula (I) Compound·Avermectin Suspension (18:4)
[0054] Preparation formula: 18% compound of formula (I), 4% avermectin, 4% castor oil polyoxyethylene ether phosphate, 1.5% block polyether, 0.5% sodium lignin sulfonate, 0.2% sodium sorbate, 0.1% kason, 0.2% xanthan gum, 1% magnesium aluminum silicate, 4.5% propylene glycol, 0.4% dimethyl silicone oil, 0.5% BHT, and deionized water to make up the balance;
[0055] Preparation method: Same as Preparation Example 1.
[0056] Preparation Example 3: 8% Formula (I) compound·pyridabenzyl emulsifiable concentrate (5:3)
[0057] Preparation formula: 5% compound of formula (I), 3% pyridabenz, 14% propylene carbonate, 15% DMDA, 15% cyclohexanone, 3% calcium dodecylbenzenesulfonate, 12% styrylphenol polyoxyethylene ether, and solvent oil to make up the balance;
[0058] Preparation method: Add the active ingredients into the cosolvent according to the formula ratio of the embodiment, and add surfactants and other functional additives thereto, stir and mix them evenly in a stirring mixing kettle to obtain the emulsifiable concentrate product.
[0059] Preparation Example 4: 8% Formula (I) compound·avermectin emulsifiable concentrate (5.5:2.5)
[0060] Preparation formula: 5.5% compound of formula (I), 2.5% avermectin, 1% BHT, 18% propylene carbonate, 15% DMF, 15% cyclohexanone, 4% calcium dodecylbenzenesulfonate, 12% fatty alcohol polyoxyethylene ether, and methyl oleate to make up the balance;
[0061] Preparation method: Same as Preparation Example 3.
[0062] Preparation Example 5: 45% formula (I) compound·pyridabenzyl wettable powder (30:15)
[0063] Preparation formula: 30% compound of formula (I), 15% pyridaben, 11% sodium lignin sulfonate, 2% sodium lauryl sulfate, 4.5% naphthalene sulfonate, 8% ammonium sulfate, 4.5% white carbon black, and kaolin to make up the balance;
[0064] Preparation method: According to the formula ratio of the embodiment, the active ingredients are added to the carrier, and the surfactant and other functional additives are added thereto, mixed, and then air flow pulverized and mixed again to obtain the wettable powder product.
[0065] Preparation Example 6: 5.5% compound of formula (I)·avermectin aqueous emulsion (5:0.5)
[0066] Preparation formula: 5% compound of formula (I), 0.5% avermectin, 5% xylene, 20% cyclohexanone, 1% BHT, 1% fatty alcohol polyoxyethylene ether phosphate, 7.5% ethylene oxide-propylene oxide copolymer, 5% ethylene glycol, 0.2% silicone defoamer, 0.1% xanthan gum, 0.2% benzoic acid, and deionized water to make up the balance;
[0067] Preparation method: According to the formula ratio of the embodiment, the active ingredient is dissolved in the solvent and an emulsifier is added to dissolve it into a uniform oil phase. Deionized water and antifreeze are mixed together to form a uniform water phase; under high-speed shear, the water phase is added to the oil phase, and finally a thickener, preservative and defoaming agent are added to form a well-dispersed water emulsion product.
[0068] Indoor toxicity
[0069] Indoor Example 1
[0070] For example, reference is made to: Guidelines for Indoor Bioassay Tests of Pesticides - Part 7: Determination of Combined Actions of Mixtures (NY / T 1154.7-2006) and Guidelines for Indoor Bioassay Tests of Pesticides - Part 13: Leaf Disk Spray Method (NY / T 1154.13-2008).
[0071] Test insect source: Tetranychus cinnabarinus (raised at the R&D center). Select female adult mites raised indoors and in a consistent physiological state. Temperature: (25±1)°C. Relative humidity: 65%±5%. Photoperiod: 16 / 8h (L / D).
[0072] Preparation of test materials: Select broad bean leaves of uniform growth, use a hole punch to make leaf discs, place a wet sponge in a culture dish, put filter paper on it, and put leaf discs on the filter paper, with 2 leaf discs per dish, and inoculate the leaf discs with adult mites raised indoors, 15 heads per dish.
[0073] Preparation: Dissolve the original drug in acetone and dilute with a 0.1% Tween-80 solution. Prepare the stock solutions for each single dose, and design the proportions based on the mixing purpose and the drug's activity. Prepare five series of mass concentrations for each single dose and each mixture using the same ratio.
[0074] Test method: Place the culture dish on the bottom plate of the Potter spray tower for spraying, the spray volume is 1mL, the liquid is taken out after settling for 1min, and transferred to the breeding conditions for breeding.
[0075] Experimental repetition: Each treatment was repeated at least 4 times, and a treatment without drug (including all organic solvents and emulsifiers) was set as a blank control.
[0076] Data statistics and analysis: 48 h after treatment, the mortality of the test insects was checked and the total number of mites and the number of dead mites were recorded respectively (death standard: use a needle tip to poke the mite appendages, those that do not move are dead, and those that move are alive).
[0077] Based on the survey data, the adjusted mortality rate of each treatment was calculated.
[0078] Calculate using the following formula, with the results rounded to two decimal places:
[0079]
[0080] Where:
[0081] P——mortality rate, in percentage (%);
[0082] K——indicates the number of dead insects, the unit is head;
[0083] N——represents the total number of insects processed, in heads.
[0084]
[0085] Where:
[0086] P1——adjusted mortality rate, in percentage (%);
[0087] P t ——Treatment mortality rate, expressed in percentage (%);
[0088] P0 - blank control mortality rate, in percentage (%).
[0089] If the control mortality rate is less than 5%, no correction is required; if the control mortality rate is between 5% and 20%, correction should be made; if the control mortality rate is greater than 20%, the test needs to be repeated.
[0090] The data were processed using the probability value analysis method. The DPS statistical analysis system can be used to analyze and calculate the LC of the toxicity regression line. 50 The activity of the test agent on the biological test material was evaluated by using the b value and its 95% confidence limit.
[0091] The co-toxicity coefficient (CTC value) of the mixture is calculated as follows:
[0092]
[0093] Where:
[0094] ATI - measured toxicity index of mixture;
[0095] S——LC of standard acaricide 50 , the unit is milligrams per liter (mg / L);
[0096] M——LC of the mixture 50 , the unit is milligrams per liter (mg / L).
[0097] TTI=TI A *P A +TI B *P B
[0098] Where:
[0099] TTI – Theoretical Toxicity Index of Mixtures;
[0100] TI A ——Agent toxicity index;
[0101] P A ——The percentage of agent A in the mixture, in percentage (%);
[0102] TI B ——Toxicity index of agent B;
[0103] P B ——The percentage of agent B in the mixture, in percentage (%).
[0104]
[0105] Where:
[0106] CTC – Co-toxicity coefficient;
[0107] ATI - measured toxicity index of mixture;
[0108] TTI - Theoretical Toxicity Index of Mixture.
[0109] A co-toxicity coefficient (CTC) of 120 or higher indicates a synergistic effect; a co-toxicity coefficient (CTC) of 80 or lower indicates an antagonistic effect; and a co-toxicity coefficient (CTC) of 80 or lower indicates an additive effect.
[0110] Test results:
[0111] The test results in Table 1 and Table 2 show that pyridabenzyl and avermectin have high toxicity to Tetranychus cinnabarinus. 50 The concentrations of the compound of formula (I) and idarubicin were 0.219 mg / L and 0.204 mg / L, respectively. The compound of formula (I) showed a synergistic effect with pyridabenz in the range of 1:20 to 15:1; the compound of formula (I) showed a synergistic effect with avermectin in the range of 1:10 to 15:1.
[0112] Table 1 Combined toxicity test of different ratios of compound of formula (I) and pyridabenzyl against Tetranychus cinnabarinus
[0113]
[0114] Table 2 Combined toxicity test of different ratios of compound of formula (I) and avermectin against Tetranychus cinnabarinus
[0115]
[0116] Indoor Example 2
[0117] For example, reference is made to: Guidelines for Indoor Bioassay Tests of Pesticides - Part 7: Determination of Combined Actions of Mixtures (NY / T 1154.7-2006) and Guidelines for Indoor Bioassay Tests of Pesticides - Part 13: Leaf Disk Spray Method (NY / T 1154.13-2008).
[0118] Test insect source: Panonychus citri (R&D center), selected female adult mites raised indoors with consistent physiological status. Temperature: (25±1)°C, relative humidity: 65%±5%, photoperiod: 16 / 8h (L / D).
[0119] Preparation of test materials: Select broad bean leaves of uniform growth, use a hole punch to make leaf discs, place a wet sponge in a culture dish, put filter paper on it, and put leaf discs on the filter paper, with 2 leaf discs per dish, and inoculate the leaf discs with adult mites raised indoors, 15 heads per dish.
[0120] Preparation: Dissolve the original drug in acetone and dilute with a 0.1% Tween-80 solution. Prepare the stock solutions for each single dose, and design the proportions based on the mixing purpose and the drug's activity. Prepare five series of mass concentrations for each single dose and each mixture using the same ratio.
[0121] Test method: Place the culture dish on the bottom plate of the Potter spray tower for spraying, the spray volume is 1mL, the liquid is taken out after settling for 1min, and transferred to the breeding conditions for breeding.
[0122] Experimental repetition: Each treatment was repeated at least 4 times, and a treatment without drug (including all organic solvents and emulsifiers) was set as a blank control.
[0123] Data statistics and analysis: 48 h after treatment, the mortality of the test insects was checked and the total number of mites and the number of dead mites were recorded respectively (death standard: use a needle tip to poke the mite appendages, those that do not move are dead, and those that move are alive).
[0124] Based on the survey data, the adjusted mortality rate of each treatment was calculated.
[0125] Calculate using the following formula, with the results rounded to two decimal places:
[0126]
[0127] Where:
[0128] P——mortality rate, in percentage (%);
[0129] K——indicates the number of dead insects, the unit is head;
[0130] N——represents the total number of insects processed, in heads.
[0131]
[0132] Where:
[0133] P1——adjusted mortality rate, in percentage (%);
[0134] P t ——Treatment mortality rate, expressed in percentage (%);
[0135] P0 - blank control mortality rate, in percentage (%).
[0136] If the control mortality rate is less than 5%, no correction is required; if the control mortality rate is between 5% and 20%, correction should be made; if the control mortality rate is greater than 20%, the test needs to be repeated.
[0137] The data were processed using the probability value analysis method. The DPS statistical analysis system can be used to analyze and calculate the LC of the toxicity regression line. 50 The activity of the test agent on the biological test material was evaluated by using the b value and its 95% confidence limit.
[0138] The co-toxicity coefficient (CTC value) of the mixture is calculated as follows:
[0139]
[0140] Where:
[0141] ATI - measured toxicity index of mixture;
[0142] S——LC of standard acaricide 50 , the unit is milligrams per liter (mg / L);
[0143] M——LC of the mixture 50 , the unit is milligrams per liter (mg / L).
[0144] TTI=TI A *P A +TI B *P B
[0145] Where:
[0146] TTI – Theoretical Toxicity Index of Mixtures;
[0147] TI A ——Agent toxicity index;
[0148] P A ——The percentage of agent A in the mixture, in percentage (%);
[0149] TI B ——Toxicity index of agent B;
[0150] P B ——The percentage of agent B in the mixture, in percentage (%).
[0151]
[0152] Where:
[0153] CTC – Co-toxicity coefficient;
[0154] ATI - measured toxicity index of mixture;
[0155] TTI - Theoretical Toxicity Index of Mixture.
[0156] A co-toxicity coefficient (CTC) of 120 or higher indicates a synergistic effect; a co-toxicity coefficient (CTC) of 80 or lower indicates an antagonistic effect; and a co-toxicity coefficient (CTC) of 80 or lower indicates an additive effect.
[0157] Test results:
[0158] Table 3 The test results show that avermectin has a high toxicity to Panonychus mites, LC 50 The concentration of the compound of formula (I) and abamectin is 0.558 mg / L, and the compound of formula (I) and abamectin show a synergistic effect in a mass ratio within the range of 1:18 to 16:1. Among them, when the mass ratio of the compound of formula (I) to abamectin is within the range of 1:18 to 10:1, the co-toxicity coefficient CTC is greater than 140, and the synergistic effect is obvious.
[0159] Table 3 Combined toxicity test of different ratios of compound of formula (I) and avermectin against Panonychus mites
[0160]
[0161]
[0162] Indoor Example 3
[0163] Test insect source: spiny-legged root mites (raised at the R&D center). Select female adult mites raised indoors and in a consistent physiological state. Temperature: (25±1)°C. Relative humidity: 65%±5%. Photoperiod: 16 / 8h (L / D).
[0164] Preparation: Dissolve the original drug in acetone and dilute with a 0.1% Tween-80 solution. Prepare separate single-dose stock solutions. Design five groups of mixes based on the mixing objectives and drug activity. Prepare five series of mass concentrations for each single dose and each mix using the same ratio.
[0165] Test method: Take a glass tube with a diameter of 1 cm and roll it evenly with 250ul of drug solution. After the drug solution is naturally dried, 15 female adult mites are sucked into the glass tube and sealed with a 200-mesh gauze.
[0166] Test repetition: Each treatment shall be repeated at least 4 times, and the number of test insects in each dose treatment shall be at least 60. A treatment without pesticide (including all organic solvents and emulsifiers) shall be set as blank control.
[0167] Data statistics and analysis: 48 h after treatment, the mortality of the test insects was checked and the total number of mites and the number of dead mites were recorded respectively (death standard: use a needle tip to poke the mite appendages, those that do not move are dead, and those that move are alive).
[0168] Based on the survey data, the adjusted mortality rate of each treatment was calculated.
[0169] Calculate using the following formula, with the results rounded to two decimal places:
[0170]
[0171] Where:
[0172] P——mortality rate, in percentage (%);
[0173] K——indicates the number of dead insects, the unit is head;
[0174] N——represents the total number of insects processed, in heads.
[0175]
[0176] Where:
[0177] P1——adjusted mortality rate, in percentage (%);
[0178] P t ——Treatment mortality rate, expressed in percentage (%);
[0179] P0 - blank control mortality rate, in percentage (%).
[0180] If the control mortality rate is less than 5%, no correction is required; if the control mortality rate is between 5% and 20%, correction should be made; if the control mortality rate is greater than 20%, the test needs to be repeated.
[0181] The data were processed using the probability value analysis method. The DPS statistical analysis system can be used to analyze and calculate the LC of the toxicity regression line. 50 The activity of the test agent on the biological test material was evaluated by using the b value and its 95% confidence limit.
[0182] The co-toxicity coefficient (CTC value) of the mixture is calculated as follows:
[0183]
[0184] Where:
[0185] ATI - measured toxicity index of mixture;
[0186] S——LC of standard acaricide 50 , the unit is milligrams per liter (mg / L);
[0187] M——LC of the mixture 50 , the unit is milligrams per liter (mg / L).
[0188] TTI=TI A *P A +TI B *P B
[0189] Where:
[0190] TTI – Theoretical Toxicity Index of Mixtures;
[0191] TI A ——Agent toxicity index;
[0192] P A ——The percentage of agent A in the mixture, in percentage (%);
[0193] TI B ——Toxicity index of agent B;
[0194] P B ——The percentage of agent B in the mixture, in percentage (%).
[0195]
[0196] Where:
[0197] CTC – Co-toxicity coefficient;
[0198] ATI - measured toxicity index of mixture;
[0199] TTI - Theoretical Toxicity Index of Mixture.
[0200] A co-toxicity coefficient (CTC) of 120 or higher indicates a synergistic effect; a co-toxicity coefficient (CTC) of 80 or lower indicates an antagonistic effect; and a co-toxicity coefficient (CTC) of 80 or lower indicates an additive effect.
[0201] Test results:
[0202] The test results in Table 4 and Table 5 show that pyridabenz and avermectin have high toxicity to the root mite. 50The concentrations of the compound of formula (I) and idarubicin were 9.7744 mg / L and 1.0479 mg / L, respectively. The compound of formula (I) showed a synergistic effect with pyridabenz in the range of 1:25 to 15:1; the compound of formula (I) showed a synergistic effect with avermectin in the range of 1:25 to 30:1.
[0203] Table 4 Combined toxicity test of different ratios of the compound of formula (I) and pyridabenzyl against Rhizoctonia spinulosa
[0204]
[0205] Table 5 Combined toxicity test of different ratios of compound of formula (I) and avermectin against Rhizoctonia spinulosa
[0206]
[0207] Field Example 1
[0208] Field trials on the efficacy of pesticides against citrus red spider mites
[0209] Test crops: Citrus (Wogan);
[0210] Test subjects: Citrus spider mite;
[0211] Experimental Design: 8% Formula (I) compound + pyridabenzyl EC (5:3) and 8% Formula (I) compound + abamectin EC (5.5:2.5) were used as control treatments, with 20% Formula (I) compound suspension concentrate, 15% pyridabenzyl EC, and 1.8% abamectin EC used as controls. A water control was also used. Six treatments were used, with three replicates and 18 plots. Each plot contained two trees, and the plots were randomly arranged, with a row of fruit trees between each plot.
[0212] Table 6 Test agents and dosage
[0213]
[0214] The test site was a citrus orchard in Shuangqiao Town, Wuming District, Nanning City, Guangxi Zhuang Autonomous Region. Citrus trees in the test area grew uniformly, but citrus spider mite infestations have been severe in recent years. The soil fertility of the test site was high, and cultivation and management conditions were favorable, with year-round planting.
[0215] The pesticide was applied on October 28, 2022. It was sunny on the day of application, with a maximum temperature of 30°C, a minimum temperature of 19°C, and a northeast wind of level 1. It was cloudy during the test.
[0216] Application method, timing, and frequency: Use a motorized sprayer (WL-ABSC) and manually apply spray evenly throughout the tree. Based on field conditions and farmer water usage habits, use 1.8 L of water per citrus tree. Apply enough to ensure even coverage of the leaves with slight dripping. Apply once.
[0217] Survey Method: Randomly select a point on each citrus plant in the east, west, south, north, and center directions. Mark a branch at each point and record the total number of live citrus red spider mites on leaves on the marked branches (starting with the top leaf, with at least five leaves). Focus on adult and nymph mites (observe with a magnifying glass). Surveys should be conducted before, 3 days after, and 10 days after treatment.
[0218] Calculation method of drug efficacy: The drug efficacy is calculated according to the following formula:
[0219]
[0220] During the experiment, the citrus trees in each experimental plot grew well and no phytotoxicity was observed in any treatment.
[0221] As can be seen from Table 7, the mixture of the compound of formula (I) with pyridaben and abamectin has a good control effect on citrus red spider mites, showing good fast-acting property. 3 days after application, the control efficacy of 8% compound of formula (I)·pyridaben emulsifiable concentrate (5:3) and 8% compound of formula (I)·avermectin emulsifiable concentrate (5.5:2.5) were 95.23% and 94.44%, respectively. At the 0.05 level, through difference analysis, the mixed preparation of the compound of formula (I) with pyridaben and abamectin was significantly higher than the control single-dose 20% suspension concentrate of the compound of formula (I), 15% pyridaben emulsifiable concentrate and 1.8% abamectin emulsifiable concentrate.
[0222] Table 7 Control effect of each treatment on citrus red spider mites 3 days after application
[0223]
[0224] Note: The protective effect (%) in the table is the average value of each replicate, with the difference at the 0.05% level. The same applies to the following tables.
[0225] As can be seen from Table 8, as time goes by, the control effect of the compound of formula (I) with pyridaben and abamectin on citrus red spider mites increases and the duration of effect is long. Ten days after application, the control effects of 8% compound of formula (I)·pyridaben emulsifiable concentrate (5:3) and 8% compound of formula (I)·avermectin emulsifiable concentrate (5.5:2.5) were 97.85% and 98.49%, respectively. At the 0.05 level, through difference analysis, the mixed preparation of compound of formula (I) with pyridaben and abamectin was significantly higher than the control single dose of 20% suspension concentrate of compound of formula (I), 15% pyridaben emulsifiable concentrate and 1.8% abamectin emulsifiable concentrate.
[0226] Table 8 Control effect of each treatment on citrus red spider mites 10 days after application
[0227]
[0228] Note: Same as above.
[0229] Indoor toxicity assays and field tests on citrus fruits have shown that the acaricidal composition of the present invention, formulated with either the compound of formula (I) and either pyridabenzyl or abamectin, exhibits excellent control efficacy against phytophagous mites. The resulting acaricidal composition or formulation exhibits significant control efficacy, outperforming single agents in delaying the development of resistance and prolonging drug retention. Furthermore, no crop damage was observed with the combined formulation, demonstrating that the enhanced synergistic acaricidal efficacy of the resulting acaricidal composition or formulation can reduce production and usage costs and is safe for crops.
[0230] Field Example 2
[0231] Test crops: garlic, variety: Jinxiang white garlic;
[0232] Test subjects: Rhizopus radicifolius;
[0233] The experimental site is Jinxiang, Jining City, Shandong Province. The experimental field is flat, the previous crop is soybean, and the soil is sandy loam with medium fertility.
[0234] Test agent:
[0235] Table 9 Experimental treatment and dosage
[0236] Experimental treatment Experimental drugs Dosage mL / kg seeds 1 8% formula (Ⅰ) compound·pyridabenzyl emulsifiable concentrate (5:3) 0.2 2 8% formula (Ⅰ) compound·avermectin emulsifiable concentrate (5.5:2.5) 0.2 3 15% pyridabenzan EC 0.3 4 1.8% Abamectin EC 0.5 5 6% Imidacloprid Suspension Seed Coating Agent 8 6 Clean Water Treatment (CK) /
[0237] Experimental design: The experiment set up 5 pesticide seed treatments and 1 water treatment (CK), with random arrangement and 3 replicates for each treatment. The plot area was 20m 2 Before seed mixing, dilute the agent with 100mL of water. On October 4, 2021, seed mixing was carried out. Garlic cloves harvested that year were selected, with a single clove weight of about 5g, firm and plump, white in color, without disease spots or wounds, and of uniform size. After mixing, they were dried and sown the next day. The planting density was 600,000 plants / hm2. 2 .
[0238] Investigation method: The damage situation of spiny-footed root mites was investigated on November 22, 2021, the peak period of infestation. 15 plants were randomly sampled from each treatment to investigate the spiny-footed root mites in the diseased plants (spiny-footed root mite investigation method: investigate the total number of mites on the pseudostem and bulb, combining above-ground observation with indoor microscopic examination after pulling out the seedlings).
[0239] During the harvest period, the incidence of diseased plants in each plot was investigated. Fifty plants were randomly surveyed in each treatment, and the number of diseased plants was recorded, and the incidence rate and control effect were calculated.
[0240] Calculation method of drug efficacy: The drug efficacy is calculated according to the following formula:
[0241]
[0242] During the experiment, garlic in each treatment plot grew well and no phytotoxicity was observed in any treatment.
[0243] Test results:
[0244] The control effects of each treatment on garlic root mite are shown in Table 10. The number of root mites, diseased plant rate and diseased index of diseased plants in each treatment were lower than those in the control. The control effects of 8% formula (I) compound·pyridabenz-methyl emulsifiable concentrate (5:3) and 8% formula (I) compound·avermectin emulsifiable concentrate (5.5:2.5) were 88.38% and 89.34%, respectively.
[0245] Table 10 Control effects of different treatments on garlic root mites
[0246]
[0247] Note: The control efficacy (%) in the above table is the average of each replicate. Lowercase letters indicate significant differences at the 5% level.
[0248] According to the field investigation, no adverse reaction of leaves to the pesticide was found in any treatment, indicating that all treatments were safe for garlic growth at the concentrations used in the experiment.
[0249] Furthermore, no phytotoxicity to crops was found in the test, indicating that the obtained acaricidal composition or preparation can reduce production and use costs and is safe for crops when the acaricidal synergistic effect is improved.
[0250] Although the present invention has been described in detail above using general descriptions and specific implementation plans, it is obvious to those skilled in the art that some modifications or improvements can be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention shall fall within the scope of protection claimed by the present invention.
Claims
1. A mite-killing composition, characterized in that: The acaricidal composition comprises active ingredient A and active ingredient B, wherein active ingredient A is a compound of formula (I): (I), active ingredient B is pyridaben, and the mass ratio of the compound of formula (I) to pyridaben is 1:25~15:
1.
2. The acaricidal composition according to claim 1, characterized in that The mass ratio of the compound of formula (I) to pyridaben is 1:25, 1:20, 1:14, 1:10, 1:8, 5:3, 1:1, 7:1, 3:1, 17:2, 10:1, and 15:
1.
3. The acaricidal composition according to claim 1, characterized in that Based on the total weight of the acaricidal composition being 100 wt %, the sum of the contents of the active ingredient A and the active ingredient B in the acaricidal composition is 2 to 80 wt %.
4. The acaricidal composition according to claim 1, characterized in that In addition to the active ingredients, the acaricidal composition also includes auxiliary ingredients acceptable to agricultural biology, and the auxiliary ingredients are selected from one or more of wetting agents, dispersants, emulsifiers, thickeners, disintegrants, antifreeze agents, defoaming agents, solvents, preservatives, stabilizers, synergists or carriers.
5. The acaricidal composition according to claim 4, characterized in that The acaricidal composition can be prepared into an agriculturally acceptable formulation, which is selected from a solid formulation and / or a liquid formulation.
6. The acaricidal composition according to claim 5, characterized in that The solid preparation is selected from wettable powder, water-dispersible granules, and soluble granules; the liquid preparation is selected from soluble solution, emulsifiable concentrate, aqueous emulsion, suspension, suspoemulsion, microemulsion, and dispersible oil suspension.
7. Use of the acaricidal composition according to any one of claims 1 to 6 for controlling harmful mites, characterized in that: The harmful mites are root mites or spider mites; the root mite is the spiny-legged root mite, and the spider mites are the panonychus, cinnabarinus, two-spotted spider mites, and truncate spider mites.
8. The use according to claim 7, characterized in that The acaricidal composition and / or its preparation is applied at an effective dose to the harmful mites to be controlled and / or the medium where they grow.
Citation Information
Patent Citations
Para-substituted diphenyl sulfide compound, composition and application thereof
CN114957062A