A synergistic pesticidal composition comprising bromopyrrolate

Abstract

The present application relates to a kind of pesticide compositions, the active ingredient of the composition contains bromopyrrol nitrile and high-efficiency chlorfluazuron, the weight ratio of two is 1:2 to 1:20.The composition further comprises an agriculturally acceptable carrier and / or adjuvant, is prepared into the dosage form of agricultural use, such as emulsifiable concentrate, dispersible oil suspension, wettable powder or emulsion in water etc..Another aspect of the present application relates to the use of the composition for controlling agricultural mites.It is proved by indoor and field tests that the reasonable combination of two active ingredients in the present application has obvious 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 high-efficiency cyhalothrin and its application in controlling crop pests. Background Technology

[0002] Bromopyrronitrile (tralopyril), also known as pyrronitrile or tralopyril, has the molecular formula C12H5BrClF3N2 and the chemical name 4-bromo-2-(4-chlorophenyl)-5-trifluoromethyl-1H-pyrroli-3-carboxynitrile. It is a white to off-white powder. It is a metal-free antifouling agent used in antifouling coatings for ship hulls or other marine structures, exhibiting broad activity against both hard-shelled and soft-bodied invertebrate contaminants. Bromopyrronitrile is an arylpyrrole compound synthesized by modifying the natural antibiotic dioxapyrrolomycin. Its mechanism of action is to block oxidative phosphorylation in insect mitochondria, preventing the mitochondria from converting adenosine diphosphate (ADP) to adenosine triphosphate (ATP). This prevents the insect from producing energy normally, ultimately leading to cell and insect death. It possesses excellent insecticidal and acaricidal activity. It can be used to control pests such as diamondback moth, beet armyworm, cabbage looper, cabbage white butterfly, cabbage moth, cabbage aphid, spider mite, and thrips, and is suitable for vegetables, tea trees, and fruit trees.

[0003] Lambda-cyhalothrin, also known as 2,2-dimethyl-(2,2-dichlorovinyl)cyclopropanecarboxylic acid-α-cyano-(3-phenoxy)benzyl ester, is a colorless solid (the technical grade is a brown, odorless powder). It is a pyrethroid insecticide that works by inhibiting nerve conduction at the axonal sites of insects. By altering the gating properties of sodium ion channels on the membrane, it keeps these channels open for extended periods, ultimately leading to over-excitation and death of the pests. Lambda-cyhalothrin exhibits repellent, knockdown, and toxic effects on insects, with a broad insecticidal spectrum. It also shows good inhibitory effects on mites. It can be used to control lepidopteran larvae, some beetles of the coleopteran order, and piercing-sucking pests such as the pear psyllid, and is widely applied in crops such as rice, vegetables, and fruit trees.

[0004] The use of single-agent pesticides in agricultural pest control often has many drawbacks. Long-term, large-scale use of a single agent inevitably leads to resistance in plants and insects, resulting in reduced efficacy, increased dosage, higher costs, and environmental pollution. Combining different active ingredients can effectively overcome these shortcomings. Furthermore, utilizing the synergistic effect of mixing two active ingredients can improve efficacy, reduce the dosage of the active ingredient, save on pesticide costs, delay the development of pesticide resistance in pests, and reduce environmental pollution, making it an important means of integrated pest management.

[0005] In recent years, the cotton two-spotted spider mite has caused serious damage to cotton. Long-term use of pesticides has led to a significant increase in the resistance of the two-spotted spider mite, and there is currently 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 on cotton, the inventors, through extensive screening experiments, proposed a pesticide compound composition of bromoxynil and highly efficient cyhalothrin. This compound composition can effectively control the two-spotted spider mite on cotton, solving the agricultural problem.

[0007] This invention relates to a pesticide composition whose active ingredients include brominated pyrrolidone and lambda-cyhalothrin. Preferably, the active ingredients of the pesticide composition consist only of brominated pyrrolidone and lambda-cyhalothrin.

[0008] In a preferred embodiment of the present invention, the weight ratio of the brominated pyrrolidone to lambda-cyhalothrin is 1:2 to 1:20, preferably 1:10 to 1:20, and more preferably 1:20.

[0009] 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, etc.

[0010] Preferably, the dosage form is an emulsifiable concentrate, a dispersible oil suspension, a wettable powder, or an emulsion, wherein the weight percentage of the active ingredient is 6%-70%, preferably 10-50%.

[0011] 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): 1-4% bromopyrrolidone, 8-40% lambda-cyhalothrin, 1-20% emulsifier, 1-20% wetting agent, and solvent to a final volume of 100%. The preparation method is as follows: the active ingredient and various adjuvants are added to a solvent, and the mixture is stirred until all components are fully dissolved to obtain the emulsifiable concentrate.

[0012] 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): 1-4% bromopyrrolidone, 8-40% lambda-cyhalothrin, 2-20% emulsifier, 2-20% dispersant, 0.5-10% thickener, 0.1-10% stabilizer, and the dispersion medium is made up to 100%.

[0013] The preparation method is as follows: using a wet grinding process, the active ingredients and various additives are mixed with the dispersion medium according to the requirements of the formula, dispersed by high-speed shearing, and then sand-milled in a sand mill to form a highly dispersed and stable suspension system in the dispersion medium, thus obtaining a dispersible oil suspension.

[0014] 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): 1-4% bromopyrrolidone, 8-40% lambda-cyhalothrin, 2-20% dispersant, 2-20% wetting agent, and solid carrier to make up to 100%.

[0015] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0016] 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): 1-4% bromopyrrolidone, 8-40% lambda-cyhalothrin, 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 make up to 100%.

[0017] 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.

[0018] In the embodiments described in this invention, wherein,

[0019] 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.

[0020] The emulsifier may be selected from one or more of the following: nonylphenol polyoxyethylene ether phosphate, 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, sorbitan anhydride monostearate, dehydrated sorbitan monostearate polyoxyethylene ether, dehydrated sorbitan fatty acid ester polyoxyethylene ether, mineral oil, and AEO-7.

[0021] 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.

[0022] The wetting agent may be selected from one or more of the following: sodium oleoyl methyl taurate, 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, sorbitan fatty acid ester, etc.

[0023] The thickener may be selected from one or more of the following: magnesium aluminum silicate, sodium alginate, sodium carboxymethyl cellulose, gum arabic, polyvinyl alcohol, xanthan gum, gelatin, polyvinyl acetate, silica, and organobentonite.

[0024] The defoamer may be selected from one or more of n-octanol, isobutyl phosphate, butyl phosphate, and silicone.

[0025] The antifreeze agent may be selected from one or more of ethylene glycol, propylene glycol, and glycerol.

[0026] The stabilizer may be selected from one or more of N-soybean oil-based trimethylenediamine, triphenyl phosphite, epichlorohydrin, butyl glycidyl ether, potassium dihydrogen phosphate, etc.

[0027] The carrier can be selected from one or more of the following: attapulgite, kaolin, silica, bentonite, sepiolite, diatomite, montmorillonite, light calcium carbonate, talc, and clay.

[0028] 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.

[0029] Another aspect of the present invention relates to the use of the aforementioned pesticide composition for the control of agricultural pests. The agricultural pest is preferably the cotton two-spotted spider mite.

[0030] This invention addresses the serious damage caused by the cotton two-spotted spider mite, the significant increase in drug resistance due to long-term pesticide use, and the current lack of existing technologies for effective control. This invention has screened out a pesticide composition that can effectively control the cotton two-spotted spider mite. Indoor and field trials have demonstrated that the rational combination of the two acaricides in this invention has a significant synergistic effect. Detailed Implementation

[0031] 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.

[0032] Unless otherwise specified, all percentages mentioned in the following examples are weight percentages.

[0033] I. Indoor Bioassay

[0034] Test insect: Two-spotted spider mite

[0035] Test reagents: Bromopyrrolidone and high-efficiency cyhalothrin were provided by Tianjin Xins Biochemical Technology Co., Ltd. and Shanghai Hulian Biopharmaceutical (Xiayi) Co., Ltd., respectively.

[0036] Experimental Design:

[0037] Two-spotted spider mites reared indoors were transferred to cowpea leaves and then immersed in prepared solutions of varying concentrations for 5 seconds. Excess solution was blotted off with absorbent paper, and the mites were placed in agar-containing petri dishes and reared at 25°C. Each treatment was repeated three times, with 20 mites used per replicate. A blank control was also included. Mortality was checked after 48 hours, and the mortality rate and corrected mortality rate were calculated.

[0038]

[0039]

[0040] 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):

[0041]

[0042]

[0043] Theoretical toxicity index (TTI) of M = TI of brompyrrolidone × P 溴代吡咯腈 +High-efficiency cyhalothrin TI×P 高效氯氟氰菊酯

[0044]

[0045] In the formula:

[0046] M represents mixtures in different proportions.

[0047] P 溴代吡咯腈 The proportion of bromopyrrolidinone in the composition

[0048] P 高效氯氟氰菊酯 The proportion of high-efficiency cyhalothrin in the composition

[0049] The results are shown in Table 1 below.

[0050] Table 1. Toxicity determination of different ratios of bromoxynil and lambda-cyhalothrin against cotton two-spotted spider mite.

[0051]

[0052]

[0053] Indoor toxicity tests on *Tetranychus syringae* against cotton spider mites, conducted with bromoxynil and lambda-cyhalothrin in a ratio of 1:20 to 1:2, revealed a co-toxicity coefficient greater than 120, indicating a significant synergistic effect. This synergistic effect was particularly pronounced at ratios of 1:20 to 1:10. The co-toxicity coefficient was highest and the synergistic effect most significant when the ratio was 1:20. Therefore, bromoxynil:lambda-cyhalothrin exhibits a synergistic effect against cotton spider mites in a ratio between 1:20 and 1:2.

[0054] II. Formulation Examples

[0055] Example 1

[0056] 4% bromopyrrolidone, 8% lambda-cyhalothrin, 4% sodium lignosulfonate, 3% castor oil polyoxyethylene ether, and cyclohexanone to bring the total to 100%.

[0057] 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.

[0058] Example 2

[0059] 4% bromopyrrolidone, 20% lambda-cyhalothrin, 8% sodium dodecyl sulfate, 6% sodium isooctyl succinate sulfonate, and cyclohexanone to bring the total to 100%.

[0060] 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.

[0061] Example 3

[0062] 1% bromopyrrolidone, 20% high-efficiency cyhalothrin, 18% mineral oil, 2% AEO-7, 10% P6, 1% silica, 1% organo-bentonite, 0.5% potassium dihydrogen phosphate, and soybean oil to make up to 100%.

[0063] The preparation method is as follows: Bromopyrrolidone, high-efficiency cyhalothrin and other components are mixed with soybean oil, dispersed by high-speed shearing and milled by sand mill to form a highly dispersed and stable suspension system, thus obtaining a dispersible oil suspension.

[0064] Example 4

[0065] 2% bromopyrrolidone, 20% high-efficiency cyhalothrin, 15% fatty alcohol polyoxyethylene ether, 8% sodium naphthalenesulfonic acid formaldehyde condensate, 5% sodium carboxymethyl cellulose, 0.5% triphenyl phosphite, and soybean oil to make up to 100%.

[0066] The preparation method is as follows: Bromopyrrolidone, high-efficiency cyhalothrin and other components are mixed with soybean oil, dispersed by high-speed shearing and milled by sand mill to form a highly dispersed and stable suspension system, thus obtaining a dispersible oil suspension.

[0067] Example 5

[0068] 2% bromopyrrolidone, 40% lambda-cyhalothrin, 12% polyoxyethylene sorbitan fatty acid ester, 4% sodium dodecyl sulfate, and kaolin to make up to 100%.

[0069] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0070] Example 6

[0071] Bromopyrrolidone 3%, High-efficiency cyhalothrin 30%, Sodium naphthalenesulfonic acid formaldehyde condensate 8%, Castor oil polyoxyethylene ether 8%, Kaolin to make up to 100%.

[0072] The preparation method is as follows: the components are mixed, ground and pulverized to obtain a wettable powder.

[0073] Example 7

[0074] 1% bromopyrrolidone, 12% lambda-cyhalothrin, 15% cyclohexanone, 7% sodium lignosulfonate, 5% glycerol fatty acid polyoxyethylene ether, 5% xanthan gum, 0.5% butyl phosphate, 5% ethylene glycol, water to 100%.

[0075] The preparation method is as follows: Bromopyrrolidone and high-efficiency cyhalothrin are dissolved in dimethylformamide 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 a water emulsion.

[0076] Example 8

[0077] 4% bromopyrrolidone, 20% lambda-cyhalothrin, 25% cyclohexanone, 8% calcium dodecylbenzenesulfonate, 7% fatty alcohol polyoxyethylene ether phosphate, 5% xanthan gum, 0.5% silicone, 5% ethylene glycol, and water to bring the total to 100%.

[0078] The preparation method is as follows: Bromopyrrolidone and high-efficiency cyhalothrin are dissolved in dimethylformamide 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 a water emulsion.

[0079] III. Field Trials

[0080] Cotton fields with severe and relatively uniform infestation of the two-spotted spider mite were selected 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. The control efficacy was assessed 7 days post-treatment 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:

[0081]

[0082]

[0083] Table 2 Results of field trials

[0084] Example 1 12 83.1 Example 3 15 92.6 Example 6 16.5 90.2 Example 8 18 86.3 5% High-efficiency cyhalothrin emulsifiable concentrate 20 70.1 50% Bromopyrrolidone Emulsifiable Concentrate 12 85.3

[0085] The above field trial results show that, compared with single-agent 5% high-efficiency cyhalothrin EC and 50% bromoxynil EC, the formulation of the present invention still has a significantly improved control efficacy, with Examples 3 and 6 showing the most significant improvement, especially Example 3. In other words, field trials have demonstrated that the composition of the present invention has a significant synergistic effect against the two-spotted spider mite on cotton.

[0086] 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 pesticide composition, characterized in that, The active ingredients of the composition contain brominated pyrrolidone and lambda-cyhalothrin, wherein the weight ratio of brominated pyrrolidone to lambda-cyhalothrin is 1:10 to 1:

20.

2. The pesticide composition according to claim 1, characterized in that, The weight ratio of the brominated pyrrolidone to the high-efficiency cyhalothrin is 1:

20.

3. The pesticide 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 pesticide 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 pesticide composition according to claim 3, characterized in that, The active ingredient has a weight percentage of 6%-70%.

6. The pesticide composition according to claim 5, characterized in that, The active ingredient has a weight percentage of 10-50%.

7. The pesticide composition according to claim 4, characterized in that, The active ingredient has a weight percentage of 6%-70%.

8. The pesticide composition according to claim 7, characterized in that, The active ingredient has a weight percentage of 10-50%.

9. Use of the pesticide 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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