Pesticide composition containing nicotine compound and application thereof

Abstract

The invention relates to a pesticide composition containing a nicotine compound and application of the pesticide composition. The pesticide composition is prepared from flufenican amide, acetamiprid, thiamethoxam or clothianidin and the like. The pesticide composition has an obvious synergistic effect, the usage amount of pesticides is reduced, the residual amount of the pesticides on crops is reduced, and the environmental friendliness is enhanced. The pesticide composition disclosed by the invention has an excellent control effect on target pests such as chilo suppressalis, plutella xylostella, green peach aphid, beet armyworm, ostrinia nubilalis, thrips, flea beetle, spider mites, brown planthopper or liriomyza sativae.

Description

Technical Field

[0002] This invention belongs to the field of pesticide technology. More specifically, this invention relates to a pesticide composition containing a neonicotinoid compound, and also to the use of said pesticide composition. Background Technology

[0004] In the agricultural and forestry sectors, crop damage caused by insect pests remains a serious challenge. Currently, agricultural pests are generally developing resistance to traditional chemical insecticides, and most existing pesticides pose environmental risks. Therefore, there is an urgent need to develop new insecticides with higher biological activity, lower dosages, and better environmental compatibility. At present, domestic and international research institutions and enterprises have successfully developed a variety of new insecticide products that combine high efficiency, low dosage, and environmental friendliness. Against this backdrop, the efficient development of novel insecticide compound and mixed formulations has also received high attention. Scientifically formulated compound or mixed formulations can not only effectively broaden the control spectrum, improve control efficacy, reduce pesticide dosage, and reduce the risk of phytotoxicity, but also delay the development of pesticide resistance in target organisms.

[0005] Broflanilide (CAS No. 1207727-04-5) is a m-benzamide-based insecticide jointly developed by Mitsui Agrochemicals and BASF. It is mainly used to control common pests on crops such as lepidopterans, coleopterans, termites, and mosquitoes and flies.

[0006] To further improve the activity of m-benzamide-based insecticides, CN 115925576B discloses a heptafluoroisopropyl diamide compound and its preparation method, which has the following chemical structural formula (II):

[0007]

[0008] (II)

[0009] According to the patent specification, SYN003 (Chinese common name: flubrominamide), which has the following chemical structural formula (I), exhibits excellent high insecticidal activity against resistant populations at low doses. It has insecticidal activity against pests including Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mites, nematodes, mosquitoes, flies, and ants. It has good rapid effect, and the preparation method is simple, efficient, and easy to industrialize. It has broad application prospects in pest control in agriculture, forestry, and horticulture.

[0010] (I)

[0011] Compared to brofentanil, the compound of formula (I) exhibits superior insecticidal activity against rice stem borer, diamondback moth, and fall armyworm, particularly demonstrating outstanding efficacy at low doses and with rapid onset of action. However, despite the widespread interest in compounds of formula (I) due to their novel target, the risk of resistance increases significantly with prolonged use. Therefore, the development of more effective insecticidal compositions remains a priority to meet the needs of the agricultural and forestry sectors.

[0012] On the other hand, there are currently no research reports on compound I combined with nicotine compounds, and this discovery provides a new entry point for the field of pesticide compositions. Summary of the Invention

[0013] The purpose of this invention is to provide a pesticide composition containing neonicotinoid compounds.

[0014] Another object of the present invention is to provide the use of the pesticide composition.

[0015] The idea behind this invention is to further study bromfenac and the compound of formula (I) above, screen appropriate drug combination schemes, and verify the synergistic effect of drug compositions containing the compound of formula (I) through experiments.

[0016] Although existing technologies have yielded some research on drug compositions containing brofenoxam, for example, Chinese invention patent application CN109221127A discloses an insecticidal composition containing brofenoxam and neonicotinoids, and verifies its field control efficacy against various pests. However, the introduction of alkoxy groups usually has a significant impact on the activity of the compounds. The study *Design, Synthesis, and Insecticidal Activities of Novel N-Alkoxyalkyl Meta-Diamides as Potential GABAR Antagonists*, Sha Zhou et al. *Journal of Agricultural and Food Chemistry* 2025 73 (28), 17446-17457 investigated the effect of introducing alkyl or ether bonds at the R5 position on the activity of diamondback moth. The results showed that introducing alkyl groups (Table 2, corresponding to compound le) or alkoxy groups (corresponding to compounds lld or lle) significantly affected resistance. Compound le showed insufficient activity against diamondback moth to meet the insecticide requirements, while compounds lld and lle exhibited excellent performance. Therefore, although the compounds recorded in Table 2 all have the same parent nucleus structure, the insecticidal activity obtained is unpredictable when different groups are introduced at the R5 position.

[0017] To further investigate the activity differences between bromoxynil and compound (I), the inventors commissioned a third party in 2024 to conduct bioassays on the yellow-striped flea beetle in Guangdong Province. The test crop was 50-day-old Mingyuan pointed-leaf beet heart. The results are as follows:

[0018]

[0019] In 2024, the inventor commissioned a third party to conduct bioassay experiments on the two compounds against rice stem borers in Jiangsu Province, in accordance with the Ministry of Agriculture and Rural Affairs' "Field Efficacy Test Guidelines - Insecticide Control of Rice Stem Borer". The test crop was rice variety Weiliangyou 8612, and the control effects were as follows:

[0020] medicine Dosage Repeat 1 Repeat 2 Repeat three times total Prevention 5% difference Compound SC of formula (I) 10ml / mu 4 3 0 7 85.93 BCc Compound SC of formula (I) 15ml / mu 3 0 1 4 90.24 Cc Compound EC of formula (I) 10ml / mu 2 0 2 4 90.24 Cc Brombutamide SC 30ml / mu 8 6 6 20 51.22 Bb Blank control / 13 19 9 41 0 Aa

[0021] In 2024, the inventors commissioned a third party to conduct bioassay experiments on the two compounds against rice leaf folder in Jiangsu Province, in accordance with the Ministry of Agriculture and Rural Affairs' "Field Efficacy Test Guidelines - Insecticide Control of Rice Leaf Folder". The test crop was rice variety Yinliangyou 836, and the control effects were as follows:

[0022] medicine Dosage Repeat 1 Repeat 2 Repeat three times total Prevention 5% difference Compound SC of formula (I) 6ml / mu 53 46 34 133 86.01 d Compound SC of formula (I) 10ml / mu 33 27 40 100 89.48 e Brombutamide SC 15ml / mu 207 244 206 657 30.91 b Blank control / 297 343 311 951 0.00 a

[0023] The above experimental results show that although bromoxynil and compound (I) have the same parent nucleus structure and are therefore similar, the inventors have confirmed through early research that their insecticidal activities are significantly different. This difference is difficult to predict and can only be confirmed through experiments.

[0024] To address this, the present invention provides a pesticide composition containing a neonicotinoid compound. This pesticide composition comprises a first active ingredient and a second active ingredient, wherein the first active ingredient is a compound having the following structural formula (I):

[0025]

[0026] (I)

[0027] The second active ingredient is acetamiprid, thiamethoxam, thiamethoxam, thiamethoxam, imidacloprid, acetamiprid, dinotefuran, epoxim, or flonicamid.

[0028] According to a preferred embodiment of the present invention, the second active ingredient is acetamiprid, thiamethoxam, acetamiprid, or flonicamid.

[0029] According to another preferred embodiment of the present invention, the weight ratio of the first active ingredient to the second active ingredient is 1~50:1~50.

[0030] This invention relates to an agricultural insecticide containing 0.5 to 95.0% by weight of the above-described pesticide composition and the balance being agriculturally acceptable adjuvants.

[0031] According to a preferred embodiment of the present invention, the additive is selected from surface wetting agents, dispersants, emulsifiers, activators, defoamers, thickeners, preservatives, antifreeze agents, or carriers.

[0032] According to another preferred embodiment of the present invention, the carrier is one or more solid carriers selected from silicates, carbonates, sulfates, oxides, alkali metal salts or plant-based carriers, or one or more liquid carriers selected from water, aromatics, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones, vegetable oils or methylated vegetable oils.

[0033] According to another preferred embodiment of the present invention, the formulation of the agricultural insecticide is a wettable powder, suspension concentrate, suspension emulsion, microemulsion, water emulsion, water-dispersible granules, emulsifiable concentrate, or microcapsule suspension.

[0034] The present invention also relates to the use of the pesticide composition or the agricultural insecticide in the control of agricultural and forestry pests.

[0035] According to a preferred embodiment of the present invention, the agricultural and forestry pests are peach aphids, yellow-striped flea beetles, cotton aphids, western flower thrips, broad bean aphids, rice brown planthoppers, or tobacco whiteflies.

[0036] The invention will now be described in more detail.

[0037] This invention provides a pesticide composition containing nicotinic compounds.

[0038] The pesticide composition consists of a first active ingredient and a second active ingredient, wherein the first active ingredient is a compound having the following structural formula (I):

[0039]

[0040] (I)

[0041] In this invention, the first active ingredient is flubrominamide, which is prepared according to the method described in CN 115925576B as 2-fluoro-3-{[(4-fluorophenyl)carbonyl](2-methoxyethyl)amino}-N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropane-2-yl)-6-(trifluoromethyl)phenyl]benzamide (also written in the prior art as N-[2-bromo-4-(1,1,1,2,3,3,3-heptafluoropropane-2-yl)-6-(trifluoromethyl)phenyl]-2-fluoro-3-[4-fluoro-N-(2-methoxyethyl)benzamido]benzamide).

[0042] According to its instructions, based on indoor bioactivity tests on the diamondback moth, this compound achieved a 60% kill rate against resistant populations and a 70% kill rate against susceptible populations at a concentration of 0.05 mg / L, while achieving a 100% kill rate against both resistant and susceptible populations at concentrations of 0.1–0.2 mg / L. Based on indoor bioactivity tests on the rice stem borer, this compound achieved an 83.6% kill rate against the rice stem borer at a concentration of 0.125 mg / L, while achieving a 100% kill rate at concentrations of 0.25 mg / L and above. Based on indoor bioactivity tests on the fall armyworm, this compound achieved a 100% kill rate against the fall armyworm at concentrations of 0.125 mg / L and above, demonstrating good insecticidal activity.

[0043] The second active ingredient is acetamiprid, thiamethoxam, thiamethoxam, thiamethoxam, imidacloprid, nitenpyram, dinotefuran, epoxim, or flonicamid. Their main function in this pesticide composition is to interfere with nerve signal transmission by acting on the nicotinic acetylcholine receptors (nAChR) in the insect nervous system, causing the pest to become excited, spasm, and ultimately paralyzed and die. The second active ingredient used in this invention is a commercially available product, such as nitenpyram (E)-N-(6-chloro-3-pyridylmethyl)-N-ethyl-N'-methyl-2-nitromethylenediamine sold by Lianyungang Liben Crop Technology Co., Ltd., and nitenpyram (from Nanjing...). Clothiadin ((E)-1-(2-chloro-1,3-thiazo-5-ylmethyl)-3-methyl-2-nitroguanidine) sold by Kelang Technology Co., Ltd., sulfoxaflor ([1-6-(trifluoromethyl)pyridin-3-yl]ethyl]-λ4-mercaptoaminonitrile) sold by Tianjin Alta Technology Co., Ltd., Cycloxaprid sold by Shanghai Zhenzhun Biotechnology Co., Ltd., and Acetamiprid (EN-[(6-chloro-3-pyridinyl)]-N2-cyano-N-methylacetamide) sold by Yancheng Limin Agrochemical Co., Ltd.

[0044] Preferably, the second active ingredient is thiamethoxam, acetamiprid, or flonicamid.

[0045] According to the present invention, the weight ratio of the first active ingredient to the second active ingredient is 1~50:1~50. When the content of the second active ingredient is within the aforementioned range, if the content of the first active ingredient is less than 1, its core control effect against its target pests (such as chewing pests, lepidopteran larvae, etc., depending on the specific type of the first active ingredient) is difficult to exert, causing these pests to continue feeding on crops due to lack of effective inhibition, resulting in damage such as leaf notching and fruit breakage; at the same time, the synergistic effect of the compound system is completely lost, and relying solely on the second active ingredient (neonicotinoids) to act on piercing-sucking pests will accelerate the development of resistance in aphids, planthoppers, etc., and cannot cover scenarios where multiple pests occur together in the field, resulting in a significant reduction in overall control efficacy; if the content of the first active ingredient is greater than 50, Excessive input will significantly increase the production cost of the formulation, weakening the product's market competitiveness. If the first active ingredient has a cumulative effect of contact or stomach poison toxicity, an excessively high proportion may cause phytotoxicity to sensitive crop tissues (such as young buds and flowers), manifested as necrosis of the growing point, flower and fruit drop, etc. In addition, an excessively high proportion will destroy the colloidal stability of the formulation (such as abnormal viscosity of suspension concentrates and decreased wettability of wettable powders), and increase its residual risk in soil or water bodies, increasing toxicity to non-target organisms (such as earthworms and fish), which does not meet the environmental protection requirements of reducing pesticide use and increasing efficiency. Therefore, a content of 1 to 50% of the first active ingredient is reasonable, preferably 12 to 40%, and more preferably 20 to 32%.

[0046] When the content of the first active ingredient is within the specified range, if the content of the second active ingredient is less than 1, its systemic insecticidal effect against piercing-sucking pests (aphids, whiteflies, planthoppers, etc.) is essentially ineffective. This leads to secondary damages such as viral diseases and sooty mold caused by these pests spreading through sap sucking. Furthermore, due to the lack of synergistic effects from neonicotinoid components, the first active ingredient must act alone against all targets, accelerating the evolution of resistance. The systemic conductivity of the formulation is also significantly reduced, failing to protect newly formed crop tissues (such as tender shoots and new leaves). If the content of the second active ingredient is less than 1, its systemic insecticidal effect against piercing-sucking pests (such as aphids, whiteflies, planthoppers, etc.) is essentially ineffective. If the content of the second active ingredient is higher than 50%, the excessive amount of neonicotinoids will significantly increase the risk of acute toxicity to pollinating insects (such as bees and bumblebees), which goes against the development direction of eco-friendly pesticides. At the same time, an excessively high proportion will increase the residue of this type of ingredient in crops, which may exceed food safety standards (especially for leafy vegetables and fruit and vegetable crops). In addition, an excessive amount of the second active ingredient will crowd out the proportion space of the first active ingredient, making it less effective against the core target pests, creating new loopholes in control, and may cause the formulation to separate and clump due to the conflict of physicochemical properties between the components (such as pH incompatibility). Therefore, the content of the second active ingredient is appropriate at 1 to 50%, preferably 10 to 38%, and more preferably 18 to 30%.

[0047] Preferably, the weight ratio of the first active ingredient to the second active ingredient is 12~40:10~38.

[0048] More preferably, the weight ratio of the first active ingredient to the second active ingredient is 20~32:18~30.

[0049] This invention relates to an agricultural insecticide containing 0.5 to 95.0% by weight of the above-described pesticide composition and the balance being agriculturally acceptable adjuvants.

[0050] In this invention, agriculturally acceptable adjuvants are selected from wetting agents, dispersants, emulsifiers, surfactants, defoamers, thickeners, preservatives, antifreeze agents, or carriers; the surface wetting agents are, for example, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl ethers, alkylbenzene sulfonates, or alkylnaphthalene sulfonates; the dispersants are, for example, sodium sulfate, sodium chloride, alkylnaphthalene sulfonates, alkylphenol polyoxyethylene ethers; the emulsifiers are, for example, polyoxyethylene esters and ethers, sodium dodecylbenzene sulfonate; the surfactants are surfactants used in emulsifiers, dispersants, or wetting agents, and are selected from anionic surfactants. The surfactants are nonionic, amphoteric, or natural polymeric surfactants; the defoamer is selected from defoaming agents, silicones, C8-C10 fatty alcohols, C10-C20 saturated fatty acids, or amide defoamers; the thickener is selected from carboxymethyl alcohol, polyvinyl alcohol, polyvinyl acetate, xanthan gum, gelatin, gum arabic, polyvinylpyrrolidone, magnesium aluminum silicate, polyethylene glycol, phenolic resin, shellac, carboxymethyl cellulose, or sodium alginate; the preservative is selected from sodium benzoate, Kathon, potassium sorbate, parabens, etc.; the antifreeze is selected from glycerin, urea, ethylene glycol, or propylene glycol. The carrier is one or more solid carriers selected from silicates, carbonates, sulfates, oxides, alkali metal salts, or plant-based carriers, or one or more liquid carriers selected from water, aromatics, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones, vegetable oils, or methylated vegetable oils.

[0051] The agricultural insecticide formulations of this invention include soluble concentrates, soluble powders, soluble granules, emulsifiable concentrates, wettable powders, water-in-oil emulsions, suspension concentrates, dispersible oil suspensions, water-dispersible granules, microcapsule suspensions, granules, microemulsions, suspension emulsions, microcapsule suspension-suspension concentrates, ultra-low volume liquids, thermal fogging agents, film-spreading oils, suspension seed coating agents, seed treatment dry powders, seed treatment suspensions, seed treatment soluble powders, seed treatment dispersible powders, seed treatment emulsions, or seed treatment liquids. The pesticide compositions or agricultural insecticides are applied via conventional spraying, soil treatment, or seed treatment.

[0052] Preferably, the pesticide composition formulation is a soluble concentrate, soluble granule, suspension concentrate, emulsifiable concentrate, wettable powder, water emulsion, water-dispersible granule, dispersible oil suspension, microcapsule suspension, ultra-low volume liquid, thermal fogging agent, suspension seed coating agent, or seed treatment dispersible powder.

[0053] The preparation method of the formulation will be described below. For example, when the agricultural insecticide of the present invention is a wettable powder, its preparation method is as follows: 0.5% to 80% by weight of pesticide composition, 2% to 10% of wetting agent, 5% to 10% of dispersant, and the balance to 100% of filler are thoroughly mixed, and then pulverized using an ultrafine pulverizer or air jet mill commonly used in the art to obtain the wettable powder. The filler used in the present invention is kaolin, diatomaceous earth, mica powder, bentonite, attapulgite, or light calcium carbonate; the wetting agents and other adjuvants mentioned here are as described above, and will not be repeated here.

[0054] When the agricultural insecticide of the present invention is a suspension, its preparation method is as follows: 0.5% to 50% by weight of pesticide composition, 1% to 5% wetting agent, 1% to 8% dispersant, 0.1% to 2% thickener, 2% to 5% antifreeze agent, 0.2% to 1% defoamer are mixed evenly with water to make up to 100%, and then the mixture is ground in a sand mill to a particle size of 2 to 5 micrometers. The mixture is then transferred to a preparation kettle, thickener is added, and the mixture is sheared and stirred evenly to obtain the suspension.

[0055] When the agricultural insecticide of this invention is a microemulsion, its preparation method is as follows: 0.5%–40% (by weight) of the pesticide composition, 1%–30% of the emulsifier, 0%–50% of the solvent, and water to a final volume of 100% are added to a mixing vessel. The mixture is stirred until completely dissolved, and stirred continuously until homogeneous, thus obtaining the microemulsion. The solvents used in the preparation of the microemulsion in this invention are, for example, isopropanol and cyclohexanone, both commercially available products, such as isopropanol sold by Shandong Jinan Guotai Chemical Co., Ltd., or cyclohexanone sold by Nanjing DSM Co., Ltd.

[0056] When the agricultural insecticide of the present invention is a water-in-oil emulsion, its preparation method is as follows: 0.5% to 40% by weight of pesticide composition, 1% to 20% of emulsifier, 1% to 15% of co-solvent, and 10% to 40% of solvent are added to a preparation vessel, stirred and dissolved, and then added to a high-shear stirring vessel that has been weighed and replenished to 100% water. The mixture is stirred at high shear while being added, and stirred until it is uniformly mixed to obtain the water-in-oil emulsion.

[0057] When the agricultural insecticide of this invention is a suspension emulsion, its preparation method is as follows: Take 0.5%–40% (by weight) of the pesticide composition, 1%–5% of the solvent, 1%–5% of the dispersant, 1%–10% of the emulsifier, 1%–5% of the wetting agent, 1%–5% of the antifreeze agent, 0.1%–1% of the thickener, 0.1%–1% of the defoamer, and add water to 100%. Then, prepare the neonicotinoid compound into a water-emulsion according to the above-described method for preparing a water-emulsion, and simultaneously prepare the flufenoxuron into a suspension according to the above-described method for preparing a suspension. Then, stir and mix the water-emulsion and the suspension evenly to obtain the suspension emulsion. Alternatively, prepare the flufenoxuron into a water-emulsion according to the above-described method for preparing a water-emulsion, and simultaneously prepare the neonicotinoid compound into a suspension according to the above-described method for preparing a suspension. Then, stir and mix the water-emulsion and the suspension evenly to obtain the suspension emulsion.

[0058] When the agricultural insecticide of this invention is a water-dispersible granule, its preparation method is as follows: 0.5%–70% by weight of pesticide composition, 1%–15% wetting agent, 1%–15% dispersant, 1%–10% disintegrant, and filler to 100% are mixed and pulverized using an air jet mill, then water is added and kneaded, granulated in a granulator, dried, and sieved to obtain the water-dispersible granules. The disintegrant used in this invention is ammonium sulfate or sodium carboxymethyl cellulose; the filler used in this invention is kaolin, diatomaceous earth, or corn starch.

[0059] When the agricultural insecticide of the present invention is a microcapsule suspension, its preparation method is as follows: take 0.5% to 40% pesticide composition, 1% to 20% emulsifier, 1% to 20% solvent, 1% to 10% dispersant, 1% to 5% wetting agent, 3% to 5% capsule material, 1% to 2% initiator, 1% to 5% pH adjuster, 0.1% to 1% thickener, 1% to 5% antifreeze, 0.1% to 1% defoamer, 0.1% to 1% preservative, and add water to 100%. According to the microcapsule suspension manufacturing method, one active component of the pesticide composition of the present invention is dissolved in a solvent, and an emulsifier and capsule shell material are added and mixed evenly to form an oil phase. In another preparation vessel, a dispersant and water are added to prepare an aqueous phase, and the oil phase is dispersed in the aqueous phase to form a water-emulsion state. An initiator is added to carry out a capsule formation reaction, and the mixture is kept at a temperature of about 50°C for 2-3 hours to solidify the capsule shell. The pH value is adjusted to obtain a semi-finished product for later use. The other active component is manufactured according to the suspension manufacturing method, with the addition of dispersant, wetting agent, antifreeze, and other adjuvants, and then sheared and milled until the suspension meets the quality standards before being discharged. The microcapsule suspension and the suspension are mixed evenly according to the proportion of the pesticide composition to obtain the microcapsule suspension-suspension. The capsule shell material used in this invention is a modified isocyanate.

[0060] When the agricultural insecticide of the present invention is an emulsifiable concentrate, its preparation method is as follows: 0.5% to 40% by weight of the pesticide composition, 1% to 30% of the emulsifier, 0% to 20% of the co-solvent, and solvent to be added to 100% are added to a preparation vessel, stirred until uniform and completely dissolved, and mixed evenly to obtain the emulsifiable concentrate. The co-solvents used in the preparation of the emulsifiable concentrate in this invention include, for example, isopropanol, cyclohexanone, and N-methylpyrrolidone.

[0061] The preparation processes, additives, and excipients for these dosage forms are all existing technologies in this field and are knowledge already mastered by those skilled in the art, so they will not be elaborated here.

[0062] The present invention also relates to the use of the pesticide composition or the agricultural insecticide in the control of agricultural and forestry pests.

[0063] In this invention, the pesticide composition is used to prepare agricultural insecticides for controlling pests on fruit trees, vegetables, ornamental plants, tea, cotton, cereal crops, shrubs, broad-leaved trees, evergreen trees, or urban sanitary pests. The composition can also be used to prepare agricultural insecticides for preventing or controlling pests including Lepidoptera, Coleoptera, Hemiptera, Thysanoptera, Diptera, Orthoptera, Homoptera, Isoptera, Hymenoptera, spider mites, nematodes, mosquitoes, flies, ants, and their larvae and eggs. Specifically, the agricultural and forestry pests are peach aphids, yellow-striped flea beetles, cotton aphids, western flower thrips, broad bean aphids, rice brown planthoppers, or tobacco whiteflies.

[0064] The plants to which the pesticide compositions and agricultural insecticides of this invention can be applied mainly include the following categories: vegetables, such as cucumber, loofah, watermelon, cantaloupe, pumpkin, gourd, spinach, celery, cabbage, Chinese cabbage, gourd, pepper, eggplant, tomato, onion, ginger, garlic, leek, lettuce, green beans, kidney beans, broad beans, radish, carrot, potato, and yam; cereals, such as wheat, barley, corn, rice, and sorghum; fruit trees, such as apple, pear, banana, citrus, grape, lychee, and mango; flowers, such as peony, rose, and flamingo flower; oil crops, such as peanut, soybean, rapeseed, sunflower, and sesame; sugar crops, such as sugar beet and sugarcane; and other crops, such as strawberry, potato, sweet potato, tobacco, and tea. The pesticide compositions of this invention can also be applied in horticulture, forestry, household hygiene, and / or public health fields.

[0065] The beneficial technical effects of this invention are as follows: Through experiments, the inventors have demonstrated that the binary composition obtained by combining flufenoxuron with a neonicotinoid insecticide in a suitable ratio has a significant synergistic effect, thereby improving control efficacy, reducing pesticide dosage, and broadening the insecticidal spectrum. The composition of this invention exhibits excellent control effects against target pests such as rice stem borer, diamondback moth, peach aphid, beet armyworm, corn borer, thrips, flea beetles, spider mites, rice brown planthopper, and American leafminer. Detailed Implementation

[0067] The invention will be better understood through the following examples.

[0068] In this invention, unless otherwise specified, "%" used to explain concentration refers to weight percentage, and ":" refers to weight ratio.

[0069] Example 1: Preparation of 55% Flufenoxam·Acetamiprid wettable powder

[0070] The implementation steps of this embodiment are as follows:

[0071] Weigh out 15% of the total weight of the wettable powder, including flubrominamide (chemical formula I), 40% acetamiprid, 4% aryl sulfonate, 6% alkyl sulfate, 4% ammonium sulfate, and supplement to 100% silica, and obtain the wettable powder according to the preparation method described in this application.

[0072] Example 2: Preparation of 30% Flufenoxam·Acetaminophen water-dispersible granules

[0073] The implementation steps of this embodiment are as follows:

[0074] Weigh out 5% of the chemical structure (I) flubromamide, 25% acetamiprid, 4% potassium dodecyl phosphate, 2% polycarboxylate, 2% sodium carboxymethyl starch, and 3% light calcium carbonate, and add up to 100% kaolin, according to the preparation method described in this application, to obtain the water-dispersible granules.

[0075] Example 3: Preparation of 25% Flufenoxam·Thiamethoxam suspension

[0076] The implementation steps of this embodiment are as follows:

[0077] Weigh out 15% of the chemical formula (I) flufenoxuron, 10% thiamethoxam, 3% polycarboxylate, 2% fatty alcohol polyoxyethylene ether, 1% E0-PO block copolymer, 2% sodium lignosulfonate, 0.2% xanthan gum, 1% magnesium aluminum silicate, 1% silica fume, 0.2% sodium benzoate, 0.4% defoamer, and 4% propylene glycol, and add water to 100% to obtain the suspending agent according to the preparation method described in this application.

[0078] Example 4: Preparation of 12% flufenoxuron·acetamiprid EC

[0079] The implementation steps of this embodiment are as follows:

[0080] Weigh out 4% of flubrominamide (chemical formula (I)), 8% acetamiprid, 2% polyoxyethylene sorbitan alkyl ester, 15% calcium dodecylbenzenesulfonate and phenethylphenol polyoxyethyl polyoxypropyl ether mixture, 8% cyclohexanone, 5% N-methylpyrrolidone, and add to 100% S-200 aromatic solvent, according to the preparation method described in this application, to obtain the emulsifiable concentrate.

[0081] Example 5: Preparation of 22% Flufenoxam·Acetaminophen Emulsion

[0082] The implementation steps of this embodiment are as follows:

[0083] Weigh out 2% of the chemical formula (I) flubrominamide, 20% acetamiprid, 4% N-methylpyrrolidone, 10% cyclohexanone, 2% fatty acid polyoxyethylene ester, 3% triphenylethylphenol polyoxyethylene ether sulfate, 5% sodium dodecylbenzenesulfonate, 0.2% defoamer, 5% ethylene glycol, and 18% aromatic solvent, and add deionized water to 100% according to the preparation method described in this application.

[0084] Example 6: Preparation of 15% flufenoxuron·flufenoxuron-methyl microemulsion

[0085] The implementation steps of this embodiment are as follows:

[0086] Weigh out 5% of the chemical formula (I) flufenoxuron, 10% flonicamid, 10% dimethyl sulfoxide, 5% cyclohexanone, 5% n-butanol, 6% propylene glycol, 4% polyoxyethylene fatty alcohol ether, 4% alkylbenzene sulfonate, and 2% dialkyl sulfosuccinate, and add water to 100% according to the preparation method described in this application, and obtain the microemulsion.

[0087] Example 7: Preparation of 18% Flufenoxuron·Thiamethoxam suspension emulsion

[0088] The implementation steps of this embodiment are as follows:

[0089] Weigh out 3% of the chemical formula (I) flubrominamide, 5% solvent oil, 4% cyclohexanone, 6% N-methylpyrrolidone, 2% fatty alcohol polyoxyethylene ether, 2% alkylphenol polyoxyethylene ether, 3% dodecylbenzene sulfonate, 5% ethylene glycol and an appropriate amount of deionized water, based on the total weight of the suspension emulsion; 15% thiamethoxam, 3% polycarboxylate, 2% EO-PO block polyether, 2% sodium lignosulfonate, 1.5% magnesium aluminum silicate, 1% silica fume, 0.2% xanthan gum, 5% glycerol, 0.2% sodium benzoate, 0.5% defoamer and an appropriate amount of deionized water, and obtain the suspension emulsion according to the preparation method described in this application.

[0090] Example 8: Preparation of 10% Flufenoxuron·Flupyridine microcapsule suspension-suspension

[0091] The implementation steps of this embodiment are as follows:

[0092] Weigh out 10% of the total weight of the microcapsule suspension-suspending agent (chemical formula (I) flufenoxuron), 10% of the solvent, 3% of the carboxylic acid ester, 3% of the polyoxyethylene octylphenyl ether, 4% of the modified isocyanate, 1% of the initiator, 1% of the pH adjuster, and add 100% of deionized water to obtain the microcapsule suspension-suspending agent according to the preparation method described in this application; weigh out 10% of the flufenoxuron, 2% of the polycarboxylate, 3% of the sodium lignosulfonate, 0.2% of the xanthan gum, 1% of the magnesium aluminum silicate, 1% of the silica, 0.2% of the fumed silica, 0.2% of the sodium benzoate, 0.4% of the silicone defoamer, 5% of the propylene glycol, and add 100% of the deionized water to obtain the suspending agent according to the preparation method described in this application. Mix the two in proportion to obtain the microcapsule suspension-suspending agent.

[0093] The following will describe in detail the implementation examples of the biological testing experiment.

[0094] Example 1 of the biological test: Indoor combined toxicity assay of Amorphophallus flammatorium

[0095] The implementation steps of this embodiment are as follows:

[0096] Test target: Yellow striped flea beetle.

[0097] Experimental Method: A series of pesticide solutions with varying concentrations were prepared. Clean cabbage leaves were immersed in the solutions for 10 seconds, then removed and allowed to air dry naturally. The leaves were then placed in 9cm diameter petri dishes lined with filter paper for moisture retention. Twenty CO2-anesthetized adult flea beetles were added. The petri dishes were immediately covered and secured with rubber bands to prevent escape. Each treatment was repeated three times. Distilled water served as a blank control. The treated materials were placed in an observation room where temperature, humidity, and light were adjustable as needed. The number of dead and live insects was counted after 48 hours, and the mortality rate for each pesticide treatment was calculated. The co-toxicity coefficient of each mixture was calculated using the Suny-P method to evaluate the combined effects. The experimental results are listed in Table 1.

[0098] Calculate the co-toxicity coefficient (CTC value) of the mixture using the following formula:

[0099]

[0100] In the formula:

[0101] ATI stands for the measured toxicity index of the mixture;

[0102] S represents the LC50 of the standard reagent. 50 ;

[0103] M represents the LC of the mixture.50 .

[0104] The theoretical toxicity index (TTI value) is calculated using the following formula:

[0105]

[0106] In the formula:

[0107] TTI stands for theoretical toxicity index of the mixture;

[0108] TIA stands for the toxicity index of drug A;

[0109] PA represents the percentage content of drug A in the mixture;

[0110] TIB stands for the toxicity index of drug B;

[0111] PB represents the percentage content of drug B in the mixture.

[0112] Calculate the cotoxicity coefficient (CTC value) using the following formula:

[0113]

[0114] In the formula:

[0115] CTC represents the cotoxicity coefficient;

[0116] ATI stands for the measured toxicity index of the mixture;

[0117] TTI stands for Theoretical Toxicity Index of Mixtures.

[0118] When the co-toxicity coefficient is greater than 120, it indicates that the mixture has a synergistic effect; when the co-toxicity coefficient is less than 80, it indicates that the mixture has an antagonistic effect; and when the co-toxicity coefficient is greater than 80 but less than 120, it indicates that the mixture has an additive effect.

[0119] The results of the combined toxicity assay of flufenoxuron and acetamiprid in the laboratory for the striped flea beetle are listed in Table 1.

[0120] Table 1: Results of Indoor Combined Toxicity Assay Test for Yellow-striped Flea Beetle

[0121] medicine <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Flufenoxam (A) 0.0412 18225.0000 - - Acetamiprid (B) 7.5087 100.0000 - - A:B (1:50) 1.3305 564.3517 455.3922 123.9265 A:B (1:20) 0.6223 1206.6045 963.0952 125.2840 A:B (1:10) 0.2888 2599.9654 1747.7273 148.7626 A:B (1:5) 0.1591 4719.4846 3120.8333 151.2251 A:B (1:1) 0.0505 14868.7129 9162.5000 162.2779 A:B (5:1) 0.0252 29796.4286 15204.1667 195.9754 A:B (10:1) 0.0291 25803.0928 16577.2727 155.6534 A:B (20:1) 0.0322 23318.9441 17361.9048 134.3110 A:B (50:1) 0.0301 24945.8472 17869.6078 139.5993

[0122] Table 1 lists the results of indoor toxicity tests, clearly showing that the mixture of flufenoxuron and acetamiprid exhibits a synergistic effect against the striped flea beetle in a weight ratio range of 1:50 to 50:1, with the synergistic effect being more pronounced in a weight ratio range of 1:10 to 10:1. These experimental results clearly demonstrate that the combination of flufenoxuron and acetamiprid for the control of the striped flea beetle is reasonable and feasible.

[0123] Example 2: Indoor Combined Toxicity Assay of Western Flower Thrips

[0124] Test target: western flower thrips nymphs.

[0125] Experimental Methods: A series of pesticide solutions with varying concentrations were prepared. Bean leaves were immersed in the prepared solutions for 10 seconds, allowed to air dry naturally, and then placed in 9cm diameter petri dishes containing filter paper. Healthy insects were introduced into each treatment (approximately 20-30 insects per treatment), with three replicates per treatment. A blank control was also included. The treated materials were placed in an observation room, with temperature, humidity, and light adjusted as needed. After 72 hours, the number of dead and live insects was recorded, and the mortality rate for each pesticide treatment was calculated. The co-toxicity coefficient of each mixture was calculated using the Suny-P method to evaluate the combined effects. The results of the indoor combined toxicity test of flufenoxuron and acetamiprid on western flower thrips are listed in Table 2.

[0126] Table 2: Results of Indoor Combined Toxicity Test of Western Flower Thrips

[0127] medicine <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Flufenoxam (A) 3.0878 50.2558 - - Acetamiprid (B) 1.5518 100.0000 - - A:B (1:50) 1.2081 128.4496 99.0246 129.7148 A:B (1:20) 1.0205 152.0627 97.6312 155.7521 A:B (1:10) 0.8888 174.5950 95.4778 182.8644 A:B (1:5) 0.8501 182.5432 91.7093 199.0455 A:B (1:1) 0.9005 172.3265 75.1279 229.3774 A:B (5:1) 1.3152 117.9897 58.5465 201.5314 A:B (10:1) 1.5201 102.0854 54.7780 186.3619 A:B (20:1) 1.8888 82.1580 52.6246 156.1208 A:B (50:1) 2.0087 77.2539 51.2312 150.7947

[0128] Table 2 lists the results of indoor toxicity tests, clearly showing that the mixture of flufenoxuron and acetamiprid exhibits a synergistic effect against western flower thrips in a weight ratio range of 1:50 to 50:1, with the synergistic effect being more pronounced in the weight ratio range of 1:20 to 50:1. These experimental results clearly demonstrate that the combination of flufenoxuron and acetamiprid for the control of western flower thrips is reasonable and feasible.

[0129] Example 3: Indoor Combined Toxicity Determination Test of Cotton Aphid

[0130] Test target: cotton aphid nymphs, a sensitive strain raised indoors.

[0131] Experimental Methods: A series of pesticide solutions with varying concentrations were prepared. Cotton leaves with uniformly distributed aphids were selected, with approximately 30-40 aphids per leaf. 1.5 mL of each solution was sprayed evenly onto each leaf sequentially. Each treatment was repeated three times, with a blank control included. The treated materials were placed in an observation room, with temperature, humidity, and light adjusted as needed. After 72 hours, the number of dead and live aphids was recorded, and the mortality rate for each pesticide treatment was calculated. The co-toxicity coefficient of each pesticide mixture was calculated using the Suny-P method to evaluate the combined effects. The results of the indoor combined toxicity test of flufenoxuron and acetamiprid on cotton aphids are listed in Table 3.

[0132] Table 3: Results of Indoor Combined Toxicity Test of Cotton Aphid

[0133] medicine <![CDATA[LC 50 (mg / L)]]> ATI TTI Cotoxicity coefficient (CTC) Flufenoxam (A) 2.5151 13.1247 - - Acetaminophen (B) 0.3301 100.0000 - - A:B (1:50) 0.2501 131.9872 98.2966 134.2745 A:B (1:20) 0.2605 126.7179 95.8631 132.1863 A:B (1:10) 0.1882 175.3985 92.1022 190.4389 A:B (1:5) 0.2007 164.4743 85.5208 192.3209 A:B (1:1) 0.3025 109.1240 56.5624 192.9268 A:B (5:1) 0.8332 39.6183 27.6039 143.5242 A:B (10:1) 1.0201 32.3596 21.0225 153.9284 A:B (20:1) 1.5008 21.9949 17.2616 127.4209 A:B (50:1) 1.8087 18.2507 14.8282 123.0812

[0134] Table 3 lists the results of indoor toxicity tests, showing that the mixture of flufenoxuron and acetamiprid exhibits a synergistic effect against cotton aphids in a weight ratio range of 1:50 to 50:1, with the synergistic effect being more pronounced in a weight ratio range of 1:10 to 10:1. These experimental results clearly demonstrate that the combination of flufenoxuron and acetamiprid for the control of cotton aphids is reasonable and feasible.

[0135] This invention experimentally verifies that the combination of flufenoxuron with various neonicotinoid compounds can delay the development of pesticide resistance in pests, broaden the insecticidal spectrum, reduce pesticide usage, reduce pesticide residues on crops, and enhance environmental friendliness.

Claims

1. A pesticide composition containing a neonicotinoid compound, characterized in that... The pesticide composition comprises a first active ingredient and a second active ingredient, wherein the first active ingredient is a compound having the following chemical structural formula (I): （I） The second active ingredient is acetamiprid, thiamethoxam, thiamethoxam, thiamethoxam, imidacloprid, acetamiprid, dinotefuran, epoxim, or flonicamid.

2. The pesticide composition according to claim 1, characterized in that... The second active ingredient is acetamiprid, thiamethoxam, acetamiprid, or flonicamid.

3. The pesticide composition according to claim 1, characterized in that... The weight ratio of the first active ingredient to the second active ingredient is 1~50:1~50.

4. An agricultural insecticide, characterized in that... It contains 0.5 to 95.0% by weight of the pesticide composition according to any one of claims 1-3 and the balance being agriculturally acceptable adjuvants.

5. The agricultural insecticide according to claim 4, characterized in that... The additives are selected from surface wetting agents, dispersants, emulsifiers, activators, defoamers, thickeners, preservatives, antifreeze agents, or carriers.

6. The agricultural insecticide according to claim 5, characterized in that... The carrier is one or more solid carriers selected from silicates, carbonates, sulfates, oxides, alkali metal salts or plant-based carriers, or one or more liquid carriers selected from water, aromatics, chlorinated aliphatic hydrocarbons, aliphatic hydrocarbons, alcohols, ethers, ketones, vegetable oils or methylated vegetable oils.

7. The agricultural insecticide according to claim 4, characterized in that... The formulation of the agricultural insecticide is a wettable powder, suspension, suspension emulsion, microemulsion, water emulsion, water-dispersible granules, emulsifiable concentrate, or microcapsule suspension.

8. Use of the pesticide composition according to any one of claims 1-3 or the agricultural insecticide according to claim 4 in the control of agricultural and forestry pests.

9. The use according to claim 8, characterized in that... The agricultural and forestry pests mentioned are peach aphid, yellow-striped flea beetle, cotton aphid, western flower thrips, broad bean aphid, rice brown planthopper, or tobacco whitefly.

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