A synergistic acaricidal composition

Abstract

The present application belongs to the technical field of pesticides, and particularly relates to a synergistic acaricidal composition. The effective component of the acaricidal composition comprises active ingredient A and active ingredient B. The active ingredient A is preferably a compound of the following formula Ia, and the active ingredient B is preferably at least one of abamectin, etoxazole, fenbutatin-oxide, ethoxy pyrimidine, spirodien, and bifenthrin. The pesticide composition of the present application can effectively improve the control effect on harmful mites, has a significant synergistic effect compared with a single agent, can effectively reduce the use amount, reduce the use cost, and reduce the influence on the environment. Formula Ia.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of pesticides, and particularly relates to a synergistic acaricidal composition. BACKGROUND

[0002] A trifluoroethyl sulfide (sulfoxide) substituted benzene compound and its acaricidal use are disclosed in Chinese patent application CN110028431A, which has outstanding control effect on harmful mites. The compound has the general formula:

[0003]

[0004] In the above formula 1, R1, R2 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl;

[0005] n is selected from 0 or 1;

[0006] R3, R4, R5, R6 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0007] In specific agricultural production practice, if a single active ingredient-containing acaricide is used continuously for many years, the harmful mites are likely to develop resistance to different degrees. To solve this problem, the person skilled in the art usually compounding two active ingredients, and through specific tests, a composition with synergistic effect and a weight ratio can be screened out, which can effectively improve the control effect, reduce the amount of pesticide used, reduce the use cost, and delay the development of resistance of harmful mites. However, after compounding two active ingredients, there may be three different results, namely antagonism, addition or synergism. Whether the synergistic effect can be produced is unpredictable and needs to be known through specific tests.

[0008] The applicant found through specific test that when R1 is F, R2 is Me, R3 is H, R4 is H, R5 is H, R6 is H, and n is 1 in the above formula I, i.e. the compound No. 2 disclosed in patent document CN110028431A (hereinafter referred to as SA2002), the acaricidal activity is excellent, and the compound and other existing acaricidal compounds have significant synergistic effect after compounding in a specific ratio. The specific compound has the structural formula shown in formula Ia as follows:

[0009]

[0010] The compound with the structural formula of formula Ia and other compounds have not been reported in the prior art. SUMMARY

[0011] The present application aims to provide a synergistically active ingredient acaricidal composition to meet the demand for improving the control effect and delaying the development of resistance in the field of controlling pests and mites in agriculture. And under the policy of pesticide reduction and synergistic effect advocated by the state, it can replace high-toxic or environmentally unfriendly pesticides.

[0012] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is:

[0013] A synergistic acaricidal composition, comprising: (A) at least one compound of formula I:

[0014]

[0015] In the above formula 1, R1, R2 are each independently selected from hydrogen, halogen, cyano, C1-C4 alkyl or C1-C4 haloalkyl;

[0016] n is selected from 0 or 1;

[0017] R3, R4, R5, R6 are each independently selected from hydrogen, halogen, cyano, nitro, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy or C1-C4 haloalkoxy.

[0018] and at least one other active compound (B), said other active compound B is selected from:

[0019] (1) glutamate-gated chloride channel modulators: abamectin, emamectin benzoate and milbemectin;

[0020] (2) mite growth inhibitors: clofentezine, flubendiamide, hexythiazox, etoxazole;

[0021] (3) mitochondrial ATP synthase inhibitors: azocyclotin, cyhexatin, fenbutatin oxide, propargite, diafenthiuron;

[0022] (4) complex II electron transport inhibitors: cymiazole, ethyl, fluensulfone;

[0023] (5) complex III electron transport inhibitors: bifenazate, dinocap, pyridaben;

[0024] (6) acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat;

[0025] (7) complex I electron transport inhibitors: pyridaben, fenazaquin, pyrimidifen, pyridifen, pyrimidifen, pyridifen, rotenone;

[0026] (8) sodium channel modulators: bifenthrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, ethofenprox, fenpropathrin;

[0027] (9) Octopamine receptor agonists: amitraz;

[0028] (10) Other mode of action: azadirachtin, mineral oil, vegetable oil, bromopropylate, fluazinam;

[0029] (11) γ-aminobutyric acid-gated chloride channel modulator: spirodiclofen

[0030] Further,

[0031] The compound (A) in the synergistic acaricidal composition of the present application is preferably a compound of the following formula Ia:

[0032]

[0033] The weight ratio of the compound (A) to the compound (B) is 50:1 to 1:50, preferably 20:1 to 1:20, more preferably 10:1 to 1:10.

[0034] In particular, when the compound (A) in the synergistic acaricidal composition of the present application is the compound of the above formula Ia and the compound (B) is abamectin, the weight ratio of the two is most preferably 10:1 to 2:1;

[0035] When the compound (A) in the synergistic acaricidal composition of the present application is the compound of the above formula Ia and the compound (B) is bifenazate, spirodiclofen or fenbutatin oxide, the weight ratio of the two is most preferably 1:1 to 1:5;

[0036] When the compound (A) in the synergistic acaricidal composition of the present application is the compound of the above formula Ia and the compound (B) is etoxazole or etoxam, the weight ratio of the two is most preferably 2:1 to 1:2;

[0037] The acaricide for controlling harmful mites of the present application is characterized in that the acaricide comprises the active ingredient in a high purity form (solid active substance of a specific purity) and at least one of the conventional adjuvants in the field of pesticide processing, including surfactants, antifreezing agents, antifoaming agents, thickening agents, preservatives, acid-base adjusting agents, deionized water.

[0038] The surfactant depends on the type of the formulation of the active ingredient to be prepared. Suitable surfactants are anionic, cationic, nonionic surfactants or surfactant mixtures, which have good emulsifying, dispersing, wetting, spreading, penetrating and synergistic properties, are the ingredients commonly used or allowed to be used in the field of pesticide formulation processing, and are not particularly limited. The specific ingredients and amounts are determined by tests according to the requirements of the formula.

[0039] Examples of the anionic surfactants are water-soluble synthetic anionic and water-soluble soap anionic surfactants. The synthetic anionic surfactants are particularly specified as fatty sulfonates, fatty sulfates, alkyl aryl sulfonates. The fatty sulfonates and the fatty sulfates are usually in the form of alkali metal salts, alkaline earth metal salts, (substituted or unsubstituted) triethanolamine salts, and they usually contain an alkyl group having about 8 to 22 carbon atoms, and the alkyl group here should also be understood to include the alkyl part of acyl groups, such as sodium / calcium salts of lignosulfonates, dodecyl sulfate or sodium dodecyl sulfate, and also the sulfates or sulfonates of fatty alcohol / ethylene oxide adducts. Examples of the alkyl aryl sulfonates are sodium, calcium, (substituted or unsubstituted) triethanolamine salts of dibutylnaphthalene sulfonic acid or naphthalene sulfonic acid / formaldehyde condensates, and also possible phosphates, such as alkyl aryl (4-14) ethylene oxide adduct phosphates or sulfates; the water-soluble soap anionic surfactants are usually alkali metal, alkaline earth metal or ammonium salts of fatty acids having about 10 to 22 carbon atoms, such as sodium or potassium salts of oleic acid or stearic acid, and also sodium or potassium salts of natural fatty acid mixtures obtained from natural fats and oils, and here particular emphasis is given to fatty acid methyl taurides.

[0040] The cationic surfactants include amine salt cations, quaternary ammonium salt cations. The amine salt cations are usually ammonium salts formed by neutralization of higher primary, secondary, tertiary amines with acids, and the hydrophobic moiety usually contains between 10 and 18 carbon atoms, and the acids used for neutralizing the fatty amines are hydrochloric acid, formic acid, acetic acid, sulfuric acid. The quaternary ammonium salt cations are generally quaternary ammonium salts having at least one alkyl group having 8 to 22 carbon atoms as a substituent and a lower alkyl group or a hydroxyalkyl group or a benzyl group as a substituent.

[0041] The nonionic surfactants are particularly specified as polyethylene glycol ether derivatives of fatty or cycloaliphatic alcohols, saturated or unsaturated fatty acids or alkyl phenols, which fatty or cycloaliphatic alcohol moieties contain 8 to 16 carbon atoms or the alkyl moieties of the alkyl phenols contain 6 to 18 carbon atoms, and the polyethylene glycol ether derivatives contain 3 to 30 ethylene glycol ether groups. Another group is represented by the adducts of polyethylene oxide with polypropylene glycol or alkyl polypropylene glycol, ethylenediamine polypropylene glycol, and generally speaking, these adducts contain an alkyl moiety having about 1 to 10 carbon atoms, 10 to 250 ethylene glycol ether units and 10 to 100 propylene glycol ether units, and examples that can be mentioned are castor oil polyethylene glycol ether, polyethylene oxide / polypropylene oxide, tributyl phenoxypolyethylene glycol, polyoxyethylene sorbitan trioleate.

[0042] The antifreezing agents are various antifreezing agents known in the field of pesticide formulations, and the antifreezing agent can be one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, urea, inorganic salts.

[0043] The defoaming agent is various defoaming agents known in the field of pesticide formulations, which can be one or more of silicone compounds, epoxy soybean oil, emulsified silicone oil, fatty alcohols.

[0044] The thickening agent is various thickening agents known in the field of pesticide formulations, which can be one or more of xanthan gum, polyvinyl alcohol, sodium alginate, gum arabic, magnesium aluminum silicate, white carbon black.

[0045] The preservative is various preservatives known in the field of pesticide formulations, which can be one or more of carboxin, sodium benzoate, benzoic acid, potassium sorbate, formaldehyde.

[0046] The acid-base regulator is various acid, base and buffer solutions known in the field of pesticide formulations. Specific examples of acids are hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, citric acid, tartaric acid, maleic acid, acidic amino acids, malic acid, potassium bisulfate, ammonium sulfate; specific examples of bases are sodium hydroxide, potassium hydroxide, aqueous ammonia solution, ethylenediamine, ethanolamine, dipotassium hydrogen phosphate, basic amino acids; examples of buffer solutions are phosphate buffer solution, borate buffer solution, boric acid buffer solution.

[0047] The deionized water is industrialized deionized water.

[0048] Generally, these compositions contain 0.1% to 95% of the active ingredient, 5% to 99.9% of at least one solid or liquid dosage form adjuvant.

[0049] Further, the present application provides the use of the above-mentioned synergistic acaricidal composition or acaricide for controlling harmful mites. Preferably, the harmful mites are spider mites.

[0050] The technical effects achieved by the present application are as follows:

[0051] 1. The synergistic acaricidal composition of the present application has a synergistic coefficient much higher than 120 relative to single agents at a ratio of 50:1 to 1:50, and has a significant synergistic effect;

[0052] 2. Reduces the amount of pesticides used and reduces the cost of pesticide use;

[0053] 3. Improves the control effect of the pesticide on harmful mites;

[0054] 4. Delays the development of pesticide resistance in harmful mites and prolongs the service life of the pesticide. DETAILED DESCRIPTION

[0055] The following indoor toxicity test is used to illustrate the indoor toxicity of SA2002 and abamectin / bifenazate / etoxazole / spirodiclofen / etoxazole / phenbutatin complex on T. cinnabarinus, respectively. The indoor toxicity test method refers to "NY / T 1154.13-2008 Pesticide Indoor Biological Test Guidelines Insecticide Part 13: Leaf Disc Spray Method".

[0056] First, the test solution is prepared into a mother liquor with acetone, and then 5 equidifferent mass concentrations are prepared with Tween-80 aqueous solution. Select the consistent growth of bean leaves, punch into leaf discs, place a piece of wet sponge in the petri dish, place the filter paper on it, place the leaf discs on the filter paper, 3 leaf discs per petri dish, then inoculate the well-fed female adult mites on the leaf discs, 20 female adult mites of relatively consistent size per leaf disc. Place the petri dish in the potter spray tower bottom tray for spraying, the amount of liquid is 1 ml, take out after 1 min of liquid settlement, finally transfer to the feeding condition for feeding, 3 times of treatment per repetition, and set up water treatment as blank control. Check the mortality of T. cinnabarinus 48 hours after treatment, and calculate the mortality. The indoor toxicity test of mite eggs also refers to the leaf disc spray method, 5 female adult mites per leaf disc, remove the female adult mites after egg laying, and calculate the mite egg base under the microscope. Each treatment is repeated 3 times, and a blank control is set up. Investigate when the mite eggs in the blank control are completely hatched, calculate the number of hatched eggs and unhatched eggs, and calculate the egg hatching rate.

[0057] The test data is statistically processed by DPS software to obtain the correlation coefficient, toxicity regression equation, and median lethal concentration. The co-toxicity coefficient is calculated by Sun Yunpei method. The co-toxicity coefficient of Sun Yunpei is used to evaluate the joint action of the complex pesticide on T. cinnabarinus. The co-toxicity coefficient > 120 indicates synergistic effect, the co-toxicity coefficient between 80 and 120 indicates additive effect, and the co-toxicity coefficient < 80 indicates antagonistic effect. The results are shown in the table below.

[0058] The joint toxicity of the mixed preparation is determined by Sun Yunpei's co-toxicity coefficient method:

[0059]

[0060] Theoretical toxicity index TTI = Σ (certain drug ATI × percentage of effective ingredient in the mixture)

[0061]

[0062] Table 1 Toxicity test results of SA2002 and abamectin / bifenazate / etoxazole / spirodiclofen / etoxazole / phenbutatin complex on T. cinnabarinus adult mites

[0063]

[0064]

[0065] From Table 1, it can be seen that SA2002 and abamectin / bifenazate / etoxazole / phenbutatin oxide show certain synergistic effects on T. urticae adult mites in the weight ratio range of 50:1-1:50, and the synergistic effects are most significant when the weight ratio is 20:1-1:20, especially 10:1-1:10.

[0066] Table 2 Toxicity test results of SA2002 and etoxazole / spirodiclofen mixed preparation on T. urticae eggs

[0067]

[0068]

[0069] From Table 2, it can be seen that SA2002 and etoxazole / spirodiclofen show certain synergistic effects on T. urticae eggs in the weight ratio range of 50:1-1:50, and the synergistic effects are most significant when the weight ratio is 20:1-1:20, especially 10:1-1:10.

[0070] From the above, it can be seen that SA2002 and abamectin / bifenazate / etoxazole / spirodiclofen / etoxazole / phenbutatin oxide show certain synergistic effects on T. urticae in the weight ratio range of 50:1-1:50.

[0071] Preparation Example 1

[0072] SA2002 20%, abamectin 4%, naphthalene sulfonic acid / formaldehyde condensate sodium salt 3%, triphenyl ethenyl polyoxyethylene ether phosphate 3%, magnesium aluminum silicate 1.2%, fumed white carbon 1.0%, ethylene glycol 5%, benzoic acid 0.1%, polysiloxane 0.2%, xanthan gum 0.24%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersed for 30 min, and then ground by a sand mill to a particle size D90 of less than 5.0 μm. Then, the formulation amount is adjusted to obtain 24% SA2002·abamectin suspension.

[0073] Preparation Example 2

[0074] SA2002 20%, bifenazate 30%, calcium dodecylbenzenesulfonate 1.5%, polyethylene oxide polypropylene oxide polymer 2.5%, alkylphenol polyoxyethylene ether sulfate 2.5%, magnesium aluminum silicate 1.5%, ethylene glycol 5%, benzoic acid 0.1%, polysiloxane 0.22%, xanthan gum 0.2%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersed for 30 min, and then ground by a sand mill to a particle size D90 of less than 5.0 μm. Then, the formulation amount is adjusted to obtain 40% SA2002·bifenazate suspension.

[0075] Preparation Example 3

[0076] SA2002 20%, abamectin 15%, sodium alkyl polyoxyethylene ether sulfonate 4%, alkylphenol formaldehyde resin polyoxyethylene ether 4%, magnesium aluminum silicate 1.8%, ethylene glycol 5%, benzoic acid 0.1%, polysiloxane 0.2%, xanthan gum 0.25%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersion for 30 min, and sand milling to a particle size D90 of less than 5.0 μm. Then, the formulation is prepared according to the amount of the formula by adjusting the amount of the formula to obtain 30% SA2002·abamectin suspension concentrate.

[0077] Preparation Example 4

[0078] SA2002 20%, spirodiclofen 20%, sodium dodecyl sulfate 0.5%, calcium lignosulfonate 2.5%, polyethylene oxide polypropylene oxide polymer 4%, magnesium aluminum silicate 2.0%, ethylene glycol 5%, benzoic acid 0.1%, polysiloxane 0.2%, xanthan gum 0.22%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersion for 30 min, and sand milling to a particle size D90 of less than 5.0 μm. Then, the formulation is prepared according to the amount of the formula by adjusting the amount of the formula to obtain 40% SA2002·spirodiclofen suspension concentrate.

[0079] Preparation Example 5

[0080] SA2002 20%, ethyl 3-(2-chloro-5-thiazolyl)-2,2-dimethylcyclopropanecarboxylate 20%, fatty alcohol polyoxyethylene ether 3%, calcium lignosulfonate 2%, polyvinyl alcohol / polypropylene glycol ether 3%, magnesium aluminum silicate 1.5%, white carbon black 1.5%, propylene glycol 5%, casson 0.02%, polysiloxane 0.2%, xanthan gum 0.24%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersion for 30 min, and sand milling to a particle size D90 of less than 5.0 μm. Then, the formulation is prepared according to the amount of the formula by adjusting the amount of the formula to obtain 40% SA2002·ethyl 3-(2-chloro-5-thiazolyl)-2,2-dimethylcyclopropanecarboxylate suspension concentrate.

[0081] Preparation Example 6

[0082] SA2002 20%, fenbutatin oxide 20%, polyethylene oxide polypropylene oxide polymer 1%, arylphenol polyoxyethylene ether phosphate 4%, potassium dihydrogen phosphate 0.2%, magnesium aluminum silicate 0.6%, white carbon black 2.2%, propylene glycol 5%, casson 0.02%, polysiloxane 0.2%, xanthan gum 0.22%, and deionized water to 100% by weight. The above raw materials are mixed, high-speed shearing dispersion for 30 min, and sand milling to a particle size D90 of less than 5.0 μm. Then, the formulation is prepared according to the amount of the formula by adjusting the amount of the formula to obtain 30% SA2002·fenbutatin oxide suspension concentrate.

[0083] Biological Example 1: Field trial for controlling Panonychus citri.

[0084] The applicant carried out field efficacy tests of Formulation Example 1, Formulation Example 2, Formulation Example 3, Formulation Example 4, Formulation Example 5, Formulation Example 6 for preventing and treating Panonychus citri in Shuangqiao Town, Wuming District, Nanning, Guangxi in 2021.

[0085] Test method: 2 citrus trees per plot, 4 times of repetition per treatment, plot group was randomly arranged, and water treatment was blank control. The spraying method was conventional spraying method, and the pesticide was uniformly sprayed on the front and back of citrus branches and leaves, so as to make the leaves wet but not dripping. The mite population was investigated before spraying, and the fixed-point investigation method was used after spraying, 2 citrus trees per plot were investigated, each tree was marked east, south, west, north and center, 1 branch per point, 5 leaves per branch were investigated, 50 leaves per plot were investigated in total, the number of live mites was recorded, and the number of active mites on leaves was checked and recorded at 3, 7, 15 and 25 days after spraying, the mite population reduction rate and control effect of each treatment were calculated, and the test results are shown in Table 3 below.

[0086]

[0087] PT is the mite population reduction rate of the pesticide treatment area; CK is the mite population reduction rate of the blank control area.

[0088] Table 3 Field control effect of SA2002 compound preparation on Panonychus citri

[0089]

[0090]

[0091] As shown in Table 3, the control effect of the SA2002 and abamectin / biphenylhydrazine / ethomecarb / spirodiclofen / ethacubrid / phenbutyltin compound preparation on Panonychus citri is greatly improved compared with single agent, and the effect is significantly better than that of single agent.

[0092] In summary, the synergistic acaricidal composition has obvious synergistic effect, can effectively reduce the amount of pesticide used, reduce the use cost, protect the environment, and delay the generation of pest mites. It should be noted that the examples described in the application are exemplary and not exhaustive, the protection scope of the application is not limited to the disclosed examples, and the modifications made without deviating from the scope and subjective consciousness of the described examples belong to the protection scope of the application.

Claims

1. A synergistic acaricidal composition, characterized by, Comprise: (A) a compound of formula Ia and at least one other active compound (B) selected from the group consisting of abamectin, etoxazole, phenthoate, etoxamium, bifenazate, spirodiclofen; the weight ratio of the compound (A) and the compound (B) is 50:1-1:

50.

2. The synergistic acaricidal composition according to claim 1, characterized in that, the weight ratio of the compound (A) and the compound (B) is 20:1-1:

20.

3. An acaricide, characterized by comprising a compound represented by the general formula (I) or a salt thereof. The preparation comprises a miticidal active ingredient and an auxiliary agent, wherein the miticidal active ingredient is the synergistic miticidal composition according to any one of claims 1-2.

4. The acaricide according to claim 3, characterized in that, The miticidal agent is in the form of a suspension concentrate, a microemulsion, a water dispersible granule, a soluble liquid, a dispersible oil suspension, an ultra-low volume liquid, a dispersible liquid, a soluble gel, an emulsion oil, an aqueous emulsion, a microcapsule suspension, a microcapsule suspension-aqueous emulsion, a microcapsule suspension-suspension, a microcapsule suspension-suspension emulsion, a suspension emulsion, an oil, a powder, a soluble powder, a soluble granule, a wettable powder.

5. The acaricide according to claim 3, characterized in that, The total mass of the miticidal active ingredient accounts for 1-60% of the total mass of the preparation.

6. Use of the synergistic miticidal composition according to any one of claims 1-2 for controlling agricultural mites.

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