A synergistic pesticidal composition comprising bromopropylate and abamectin

Abstract

The present application aims at the harm of Tetranychus urticae Koch to cotton being more serious, long-term medication leading to the obvious increase of the drug resistance of Tetranychus urticae Koch, and a miticidal composition containing bromopyrrol nitrile and abamectin which can effectively control Tetranychus urticae Koch is screened out, wherein the weight ratio of bromopyrrol nitrile to abamectin is 1-8:8-1, the composition further comprises an agriculturally acceptable carrier and / or an auxiliary agent, and is prepared into an agriculturally usable dosage form, such as an emulsifiable concentrate, a dispersible oil suspension, a wettable powder or an aqueous emulsion, etc. Another aspect of the present application relates to the use of the miticidal composition for controlling agricultural mites. It is proved by indoor and field tests that the reasonable combination of the two miticides in the present application has a significant synergistic effect.

Description

Technical Field

[0001] This invention belongs to the field of pesticide compound technology, specifically relating to a pesticide synergistic composition containing brominated pyrrolidone and abamectin and its application in controlling crop mites. Background Technology

[0002] Bromopyrrolidone (tralopyril), CAS No.: 122454-29-9, Molecular Formula: C 12 H5BrClF3N2, chemically named 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrrolo-3-carboxylonitrile, is an optimized derivative of dioxopyrrolidone. It is considered an uncoupling agent with excellent insecticidal and acaricidal activity. Its mechanism of action primarily involves blocking oxidative phosphorylation in the mitochondria of mites, preventing the mitochondria from converting adenosine diphosphate (ADP) to adenosine triphosphate (ATP). This prevents the mites from producing energy normally, ultimately leading to their death. Bromopyrrolonitrile is widely used as a marine antifouling agent to eliminate hard-shelled and soft-bodied invertebrates on ship hulls and other marine structures. Current research indicates that bromopyrrolonitrile possesses insecticidal and acaricidal activity.

[0003] Abamectin (CAS No. 71751-41-2) is a sixteen-membered ring lactone insecticide and acaricide developed by Merck. Developed in 1979, it is an antibiotic insecticide, acaricide, and nematicide produced by fermentation of *Streptomyces avermectin*. It has contact, stomach poison, and weak fumigation effects on mites, but no ovicidal effect. Abamectin primarily affects the nervous system of mites, interfering with their neurophysiological activities. When the agent enters the mite's body, the massive release of γ-aminobutyric acid (GABA) forces the prolonged opening of GABA-gated chloride ion channels. The large amount of chloride ions causes hyperpolarization of neuronal potentials, blocking nerve impulses, leading to paralysis, loss of appetite, and death of the pests. Abamectin has been registered in my country for the control of various mites, including citrus spider mites, apple spider mites, and hawthorn spider mites, on cotton, citrus, wheat, and apple trees.

[0004] Long-term, high-dose use of single pesticides can lead to mites developing resistance, resulting in poor pesticide efficacy. Increasing pesticide dosage also raises costs and causes further environmental pollution. The combined application of acaricides with different mechanisms of action is a crucial method for controlling and delaying mite resistance. Because mixed or compounded pesticides exhibit synergistic and enhanced effects, they significantly reduce the amount of pesticide used, improve efficacy, and effectively delay the development and spread of mite resistance. This effectively overcomes the drawbacks of single-agent use, making pesticide mixing an important means of integrated mite control.

[0005] In recent years, the two-spotted spider mite has caused serious damage to cotton. Long-term and excessive use of pesticides has led to a significant increase in the two-spotted spider mite's resistance to pesticides. Currently, there is a lack of effective pesticides on the market to control it. Summary of the Invention

[0006] To address the difficulty in controlling the two-spotted spider mite, the inventors, through extensive screening experiments, proposed a pesticide compound composition of bromoxynil and abamectin. This compound composition can effectively control the two-spotted spider mite, solving the agricultural problem.

[0007] The objective of this invention is achieved through the following technical solution:

[0008] An acaricide composition containing bromoxypyrrolidone and abamectin, wherein the active ingredients are bromoxypyrrolidone and abamectin. Preferably, the active ingredients of the pesticide composition consist solely of bromoxypyrrolidone and abamectin.

[0009] In a preferred embodiment of the present invention, the weight ratio of the bromoxypyrrolidone to avermectin is 1-8:8-1, preferably 1-4:1, and more preferably 1:1.

[0010] In a preferred embodiment of the invention, the composition further comprises an agriculturally acceptable carrier and / or adjuvants, prepared into an agriculturally usable dosage form. The carriers and / or adjuvants used include, but are not limited to, solvents, cosolvents, emulsifiers, dispersants, wetting agents, binders, disintegrants, thickeners, antifreeze agents, capsule wall materials, defoamers, preservatives, stabilizers, pH adjusters, dispersion media, and / or carriers.

[0011] Preferably, the dosage form is an emulsifiable concentrate, a suspension concentrate, a wettable powder, or an emulsion, wherein the weight percentage of the active ingredient is 5%-50%, preferably 10-40%.

[0012] In one embodiment of the present invention, the pesticide composition of the present invention is prepared into an emulsifiable concentrate, the formulation of which is (by weight percentage): 0.5-50% bromopyrrolidone, 0.1-5% abamectin, 1-20% emulsifier, 1-20% wetting agent, and solvent to make up to 100%.

[0013] The preparation method is as follows: the active ingredients and various additives are added to the solvent and stirred to fully dissolve the ingredients to obtain an emulsifiable concentrate.

[0014] In one embodiment of the present invention, the pesticide composition of the present invention is prepared into a suspension, the formulation of which is (by weight percentage): 0.5-50% bromopyrrolidone, 0.1-5% abamectin, 1-10% dispersant, 1-10% wetting agent, 0.1-10% thickener, 1-5% antifreeze, 0.1-1% preservative, 0.1-0.5% defoamer, and water to make up to 100%.

[0015] The preparation method is as follows: the active ingredients are pre-pulverized separately using an air jet mill. Each component is weighed according to the experimental design ratio, mixed thoroughly with water, and then an equal mass of zirconia beads (0.8–1.0 mm) is added. The mixture is then added to a grinding mill and ground until the average particle size D of the suspension system is reached. 90 ≤5μm, to obtain a suspension.

[0016] In one embodiment of the present invention, the pesticide composition of the present invention is prepared into a dispersible oil suspension, the formulation of which is (by weight percentage): 5-50% bromopyrrolidone, 0.1-5% abamectin, 2-5% dispersant, 10-20% emulsifier, 0.1-3% thickener, and made up to 100% with a dispersion medium.

[0017] The preparation method is as follows: A wet sand milling process is used. Materials are added in proportion and mixed by high-speed shearing to obtain a uniform slurry. The prepared slurry is poured into the milling hopper of a vertical sand mill, and an appropriate amount of abrasive beads are added for sand milling until the particle size D is reached. 90 Once the particle size is less than 5 μm, a dispersible oil suspension can be prepared.

[0018] In one embodiment of the present invention, the pesticide composition of the present invention is prepared into a wettable powder, the formulation of which is (by weight percentage): 0.5-50% bromopyrrolidone, 0.1-5% abamectin, 2-20% dispersant, 2-20% wetting agent, and solid carrier to 100%.

[0019] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0020] In one embodiment of the present invention, the pesticide composition of the present invention is prepared into an emulsion, the formulation of which is (by weight percentage): 0.5-50% bromopyrrolidone, 0.1-5% abamectin, 1-30% solvent, 2-20% emulsifier, 2-20% dispersant, 1-10% thickener, 0.5-10% defoamer, 0.1-10% antifreeze, 0-5% stabilizer, and water to 100%.

[0021] The preparation method is as follows: the active ingredient is dissolved in a solvent to prepare an oil phase, and the other components are added to water and stirred evenly to prepare an aqueous phase. Then, while stirring, the oil phase is added to the aqueous phase and stirred evenly to obtain a water emulsion.

[0022] In the embodiments described in this invention, wherein,

[0023] The solvent may be selected from one or more of dimethylformamide, ethanol, diethyl ether, chloroform, acetone, toluene, xylene, cyclohexanone, dimethyl sulfoxide, petroleum ether, cyclohexane, cyclohexanol, ethyl acetate, and mineral oil.

[0024] The emulsifier may be selected from one or more of the following: nonylphenol polyoxyethylene ether phosphate, alkyl aryl polyoxyethylene ether polyoxypropylene ether, polyoxyethylene dehydrated sorbitan monooleate, castor oil polyoxyethylene ether, nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, calcium dodecylbenzene sulfonate, polyoxyethylene fatty amide, lignin sulfonate, naphthalene sulfonate formaldehyde condensate, benzyl dimethylphenol polyoxyethylene ether, styrene phenyl polyoxyethylene ether, fatty alcohol polyoxyethylene ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, mineral oil emulsifier, sorbitan monostearate, and dehydrated sorbitan monostearate polyoxyethylene ether.

[0025] The dispersant may be selected from one or more of the following: naphthalene sulfonate formaldehyde condensate, sodium naphthalene sulfonate formaldehyde condensate, lignin sulfonate, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerol monofatty acid ester, sodium p-hydroxyphenyl lignin sulfonate, fatty alcohol polyoxyethylene ether, fatty alcohol polyoxyethylene ether phosphate, nonylphenol polyoxyethylene ether, glycerol fatty acid polyoxyethylene ether, polyoxyethylene alkyl aryl ether, polyoxyethylene lanolin alcohol, alkylolamide, and polyoxyethylene alkylamine.

[0026] The wetting agent may be selected from one or more of the following: sodium oleoyl methyl taurate, alkylphenol polyoxyethylene ether, sodium polyoxyethylene lauryl ether carboxylate, calcium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium isooctanol succinate sulfonate, sodium lauroyl sarcosinate, sodium N-lauroyl glutamate, trisiloxane polyoxyethylene ether, castor oil polyoxyethylene ether, fatty alcohol polyoxyethylene ether, succinate sulfonate, sorbitan fatty acid ester, sodium oleylaminopropionate, etc.

[0027] The thickener may be selected from one or more of the following: magnesium aluminum silicate, sodium alginate, sodium carboxymethyl cellulose, organobentonite, hydrophilic silica, oleophilic silica, gum arabic, polyvinyl alcohol, xanthan gum, gelatin, and polyvinyl acetate.

[0028] The defoamer may be selected from one or more of n-octanol, isobutyl phosphate, butyl phosphate, silicone oil, and silicone.

[0029] The antifreeze agent may be selected from one or more of ethylene glycol, propylene glycol, and glycerol.

[0030] The stabilizer may be selected from one or more of N-soybean oil-based trimethylenediamine, triphenyl phosphite, epichlorohydrin, butyl glycidyl ether, etc.

[0031] The carrier can be selected from one or more of the following: kaolin, silica, bentonite, diatomaceous earth, light calcium carbonate, talc, and clay.

[0032] The preservative can be selected from one or more of sodium benzoate, Kathon, potassium sorbate, and sodium diacetate.

[0033] The dispersion medium can be selected from one of mineral oil, soybean oil, corn oil, rapeseed oil, castor oil, coconut oil, palm oil, turpentine oil, and methyl oleate.

[0034] Another aspect of the present invention relates to the use of the aforementioned pesticide composition for controlling agricultural mites. Preferably, the agricultural mite is the two-spotted spider mite.

[0035] This invention addresses the serious damage caused by the two-spotted spider mite to cotton. Long-term use of pesticides has led to a significant increase in the mite's resistance. Currently, there is a lack of existing technologies for effective control of the mite on the market. This invention has screened out a pesticide composition that can effectively control the two-spotted spider mite. Indoor and field trials have proven that the rational combination of the two acaricides in this invention has a significant synergistic effect. Detailed Implementation

[0036] The present invention will be further described below with reference to embodiments and applications. The percentages in the embodiments are all weight percentages, but the present invention is not limited thereto.

[0037] Unless otherwise specified, all percentages mentioned in the following examples are weight percentages.

[0038] I. Indoor Bioassay

[0039] Test insects: adult female two-spotted spider mites, which were reared for multiple generations in an insect rearing room, and healthy and consistent adult female mites were selected for use.

[0040] Test reagents: bromopyrrolidone and abamectin, purchased from Tianjin Xins Biochemical Technology Co., Ltd. and Guangdong Maoming Lvyin Agricultural Chemical Co., Ltd., respectively.

[0041] Experimental Design:

[0042] Indoor bioassays employed the immersion method. Test insects were selected and placed on untreated cowpea leaves, then immersed in different concentration gradients of pesticide solutions for 10 seconds each. After immersion, the insects were removed and air-dried, then reared at 25°C. Each treatment was repeated three times, with 20 insects used per replicate. A blank control was also included. Mortality was assessed after 48 hours, and mortality and corrected mortality rates were calculated.

[0043]

[0044]

[0045] The corrected mortality rate was converted into a probability value (y), and the treatment concentration (mg / L) was converted into logarithmic form. The toxicity regression equation was obtained, and the LC ratio was calculated. 50 The value is then calculated using Sun Yunpei's formula for co-toxicity coefficient (CTC). CTC < 80 indicates antagonism, 80 ≤ CTC ≤ 120 indicates additive effect, and CTC > 120 indicates synergistic effect. The calculation formula is as follows (using bromopyrrolidone as the standard reagent, with a toxicity index of 100):

[0046]

[0047]

[0048] Theoretical toxicity index (TTI) of M = TI of brompyrrolidone × P 溴代吡咯腈 +Avermectin's TI×P 阿维菌素

[0049]

[0050] In the formula:

[0051] M represents mixtures in different proportions.

[0052] P 溴代吡咯腈 The proportion of bromopyrrolidinone in the composition

[0053] P 阿维菌素 The proportion of avermectin in the composition

[0054] The results are shown in Table 1 below.

[0055] Table 1. Toxicity determination of different ratios of bromopyrrolidone and abamectin against two-spotted spider mites.

[0056]

[0057] Indoor toxicity tests on *Tetranychus bismuth subtilis* using bromopyrrolidone, avermectin, and their combination revealed that when the ratio of bromopyrrolidone to avermectin was 1:8 to 8:1, the co-toxicity coefficient was greater than 120, indicating a significant synergistic effect. The synergistic effect was particularly pronounced when the ratio was 1:1 to 4:1; especially when the ratio was 1:1, the co-toxicity coefficient was the highest, and the synergistic effect was most significant. Therefore, bromopyrrolidone:avermectin exhibits a synergistic effect against *Tetranychus bismuth subtilis* in the ratio of 1:8 to 8:1.

[0058] II. Formulation Examples

[0059] Example 1

[0060] 20% bromopyrrolidone, 5% abamectin, 5% benzyl dimethylphenol polyoxyethyl ether, 6% sodium isooctyl succinate sulfonate, and cyclohexanone to bring the total to 100%.

[0061] The preparation method is as follows: each component is added to cyclohexanone, and the components are stirred to fully dissolve them to obtain an emulsifiable concentrate.

[0062] Example 2

[0063] 40% bromopyrrolidone, 5% abamectin, 8% sorbitan monostearate polyoxyethylene ether, 7% calcium dodecylbenzenesulfonate, and cyclohexanone to bring the total to 100%.

[0064] The preparation method is as follows: each component is added to cyclohexanone, and the components are stirred to fully dissolve them to obtain an emulsifiable concentrate.

[0065] Example 3

[0066] 5% bromopyrrolidone, 5% abamectin, 3% sodium naphthalenesulfonic acid formaldehyde condensate, 4% alkylphenol polyoxyethylene ether, 5% ethylene glycol, 0.5% magnesium aluminum silicate, 0.3% sodium benzoate, 0.2% silicone oil, and water to 100%.

[0067] The preparation method is as follows: after mixing the components evenly, add an equal mass of zirconia beads, and grind them in a grinding mill until the average particle size D90 of the suspension system is ≤5μm to obtain the suspending agent.

[0068] Example 4

[0069] 5% bromopyrrolidone, 5% abamectin, 10% mineral oil emulsifier, 2% fatty alcohol polyoxyethylene ether, 4% P6 dispersant, 3% organic bentonite, and mineral oil to make up the balance.

[0070] The preparation method is as follows: A wet grinding and pulverizing process is used. The active ingredient, dispersant, emulsifier, and thickener are weighed according to the formula. Finally, mineral oil is added to bring the total to 100%, ensuring the material is fully wetted and flowable. The mixture is then sheared for 2-3 minutes using a high-shear emulsifier. The sheared sample is poured into a sand mill, and the amount of beads added is fixed. The mixture is then milled to a particle size D. 90 Once the particle size is less than 5 μm, a dispersible oil suspension can be prepared.

[0071] Example 5

[0072] Bromopyrrolidone 7.2%, abamectin 1.8%, fatty alcohol polyoxyethylene ether phosphate 4.5%, sodium lauroyl sarcosinate 3%, kaolin to make up to 100%.

[0073] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0074] Example 6

[0075] 40% bromopyrrolidone, 5% abamectin, 6% sodium p-hydroxyphenyl lignin sulfonate, 8% trisiloxane polyoxyethylene ether, and kaolin to make up to 100%.

[0076] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0077] Example 7

[0078] Bromopyrrolidone 0.6%, Avermectin 5%, Cyclohexanone 12%, Castor oil polyoxyethylene ether 5%, Sodium p-hydroxyphenyl lignin sulfonate 5%, Xanthan gum 4%, Isobutyl phosphate 0.5%, Ethylene glycol 5%, Water to 100%.

[0079] The preparation method is as follows: Bromopyrrolidone and abamectin are dissolved in cyclohexanone to prepare an oil phase. Other components are added to water and stirred evenly to prepare an aqueous phase. Then, the oil phase is added to the aqueous phase while stirring, and stirred evenly to obtain an emulsion.

[0080] Example 8

[0081] 5% bromopyrrolidone, 5% abamectin, 16% cyclohexanone, 4% sodium dodecylbenzenesulfonate, 6% fatty alcohol polyoxyethylene ether, 4% xanthan gum, 0.5% isobutyl phosphate, 5% ethylene glycol, and water to 100%.

[0082] The preparation method is as follows: Bromopyrrolidone and abamectin are dissolved in cyclohexanone to prepare an oil phase. Other components are added to water and stirred evenly to prepare an aqueous phase. Then, the oil phase is added to the aqueous phase while stirring, and stirred evenly to obtain an emulsion.

[0083] III. Field Trials

[0084] Cotton fields with severe and relatively uniform infestation of the two-spotted spider mite were used as experimental fields. Field efficacy trials were conducted in designated plots, with each treatment randomly assigned and replicated three times. A blank control was also included. Before treatment, a pre-treatment insect population survey was conducted in each plot. Then, conventional spraying was performed using a manual sprayer. Seven days after treatment, the control efficacy was assessed using a five-point sampling method. The corrected control efficacy was calculated using the following formula, and the results are shown in Table 2 below:

[0085]

[0086]

[0087] Table 2 Results of field trials

[0088] Example 1 10 90.7 Example 3 12 93.3 Example 5 10 85.1 Example 7 12 82.9 40% Bromopyrrolidone Wettable Powder 12 83.4 5% Avermectin EC 15 59.3

[0089] The above field trial results show that, compared with single-agent 40% brompyrrolidone wettable powder and 5% abamectin emulsifiable concentrate, Examples 1 and 3 have better control effects against two-spotted spider mites, especially Example 3. In other words, field trials have demonstrated that the composition of this invention has a significant synergistic effect against two-spotted spider mites on cotton in the field.

[0090] This invention has been described through specific embodiments. Those skilled in the art can refer to the content of this invention and appropriately modify the raw materials, process conditions, and other aspects to achieve other corresponding objectives. Such modifications do not depart from the scope of this invention, and all similar substitutions and alterations are obvious to those skilled in the art and are considered to be included within the scope of this invention.

Claims

1. A mite-killing composition containing bromoxypyrrolidone and abamectin, characterized in that, The active ingredients of the acaricide composition contain bromopyrrolidone and abamectin, wherein the weight ratio of bromopyrrolidone to abamectin is 1 to 4:

1.

2. The acaricide composition according to claim 1, characterized in that, The weight ratio of the bromopyrrolidone to abamectin is 1:

1.

3. The acaricide composition according to claim 1 or 2, characterized in that, The composition further comprises an agriculturally acceptable carrier and / or adjuvant, and is prepared into an agriculturally usable formulation.

4. The acaricide composition according to claim 3, characterized in that, The dosage form is an emulsifiable concentrate, a dispersible oil suspension, a wettable powder, or an emulsion.

5. The acaricide composition according to claim 3, characterized in that, The active ingredient has a weight percentage of 5%-50%.

6. The acaricide composition according to claim 5, characterized in that, The active ingredient has a weight percentage of 10-40%.

7. The acaricide composition according to claim 4, characterized in that, The active ingredient has a weight percentage of 5%-50%.

8. The acaricide composition according to claim 7, characterized in that, The active ingredient has a weight percentage of 10-40%.

9. Use of the acaricidal composition according to any one of claims 1-8 for the control of agricultural mites.

10. The use according to claim 9, characterized in that, The agricultural pest is the two-spotted spider mite.

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