Bromofluoride double amide-containing complex agricultural insecticide and application thereof

Abstract

This invention discloses a compound agricultural insecticide containing brofenoxam and its application. The active ingredient of the compound agricultural insecticide composition of this invention is brofenoxam and either 1) or 2) of the following: 1) lufenuron; 2) a cyclophosphamide, wherein the mass ratio of brofenoxam to lufenuron or cyclophosphamide is 1:1 to 50. The insecticide composition of this invention can be formulated as a suspension concentrate, emulsion, dispersible oil suspension, wettable powder, soluble powder, water-dispersible granules, and microemulsion. The compound composition of this invention is used to control Lepidoptera, Coleoptera, and Thysanoptera pests on crops. Compared with single agents, it has a significant synergistic effect, can reduce the dosage, and can delay the development of insecticide resistance in pests, making it particularly suitable for the control of resistant pests.

Description

Technical Field

[0001] This invention relates to a compound agricultural insecticide containing bromoxynil dimethyl methacrylate and its application, belonging to the field of agricultural insecticide technology. Background Technology

[0002] Broflanilide, chemically known as 3-benzamido-N-(4-heptafluoroisopropylaniline-2-methyl)phenyl)benzamide, is a m-benzamidobenzamide insecticide jointly developed by Mitsui Agrochemicals and BASF. It is an allosteric modulator of γ-aminobutyric acid (GABA)-gated chloride ion channels. It binds to the intersubunit allosteric site of the insect's GABA receptor, inhibiting neurotransmission, blocking the insect's inhibitory signal, disrupting the balance of the insect's nervous system, and causing the insect to become continuously excited, convulsed, and eventually die.

[0003] The International Resistancy and Resistance Committee (IRAC) classifies bromutrin dimethyl methacrylate (BMT) as Group 30. It exhibits no cross-resistance with currently marketed insecticides, making it an excellent tool for resistance management. BMT is highly effective, has a broad insecticidal spectrum, and possesses stomach poison, contact, and penetrating action. It is non-systemic, exhibits good rapid and sustained action, and is resistant to rain washout. It is primarily used to control crop pests belonging to Lepidoptera, Coleoptera, and Thysanoptera.

[0004] Insecticidal ring, also known as Easy-Guard, is a selective insecticide with stomach poison, contact, and systemic action. It is translocated atop the grain and has a residual effect on lepidopteran and coleopteran pests for 7-14 days. It can also control parasitic nematodes, such as the rice white-tipped nematode, and has some effect on rust and whitehead disease in some crops. It can control rice stem borers, rice leaf rollers, rice thrips, leafhoppers, rice gall midges, planthoppers, peach aphids, apple aphids, apple spider mites, pear leafminers, citrus leaf miners, and vegetable pests.

[0005] Lufenuron is a benzoylurea insecticide used to control a variety of pests, exhibiting excellent efficacy against resistant lepidopteran and piercing-sucking insects. Its insecticidal mechanism involves inhibiting the formation of chitin synthase in larvae, interfering with chitin deposition in the epidermis, leading to the insect's inability to molt and metamorphose normally, resulting in death. Cypermethrin is a nereistoxin-based insecticide with contact and stomach poison effects, as well as some systemic activity. It is also ovicidal and suitable for controlling various lepidopteran, thalassoptera, and homoptera pests on crops such as rice, corn, vegetables, and fruit trees.

[0006] Pesticide resistance is a global problem. In recent years, due to the long-term use of chemical pesticides and unscientific application methods, the problem of pesticide resistance in agricultural pests has become increasingly serious. The number of resistant pests is continuously increasing, the degree of resistance is high, and the rate of resistance development is relatively fast. Pesticide compounding or mixing can broaden the insecticidal spectrum and delay the development of pesticide resistance, making it one of the more effective methods to solve the problem of pesticide resistance. Therefore, it is necessary to study the compounding effects of bromufenoxam with insecticidal rings. Summary of the Invention

[0007] The purpose of this invention is to provide a compound insecticide containing bromfenac, which combines bromfenac with lufenuron or cyclophosphamide. This compound insecticide has the advantages of significant synergistic effect, low cost, excellent control effect and no resistance. It is mainly used for the control of pests such as lepidopteran, coleopteran and thalassoptera on crops.

[0008] The compound agricultural insecticide composition provided by this invention has the active ingredient being brofentanil diamide, or either 1) or 2) below:

[0009] 1) Lufenuron;

[0010] 2) Insecticidal ring;

[0011] The mass ratio of the bromfenacin to the lufenuron or the insecticidal ring is 1:1 to 50;

[0012] Preferably, the mass ratio of the bromfenac to the lufenuron or the insecticidal ring is 1:1 to 10;

[0013] More preferably, the mass ratio of brofenoxam to lufenuron is 1:1 to 6, and most preferably 1:1 to 2, 1:1 or 1:2.

[0014] More preferably, the mass ratio of the bromfenacin to the insecticidal ring is 1:1 to 6, and most preferably 1:1 to 2, 1:1 or 1:2.

[0015] Based on the compound agricultural insecticide composition, the present invention also provides a compound agricultural insecticide made from the compound agricultural insecticide composition and pesticide formulation-acceptable excipients, wherein the mass percentage of the compound agricultural insecticide composition is 1% to 90%, preferably 24% to 36%.

[0016] The formulation of the compound agricultural insecticide of the present invention can be any one of suspension concentrate, water emulsion, dispersible oil suspension, wettable powder, soluble powder, water-dispersible granules, and microemulsion.

[0017] When the compound agricultural insecticide is a suspension concentrate, its mass percentage composition is as follows: 1-40% bromofenac, 1-40% lufenuron or chlorpyrifos, 2-10% dispersant, 1-5% wetting agent, 2-10% antifreeze agent, 0.1-1% defoamer, 0.1-3% thickener, 0.1-2% preservative, and the balance being water;

[0018] Preferably, its composition by weight percentage is as follows: 1-25% brofenoxam, 1-25% lufenuron or chlorpyrifos, 2-6% dispersant, 1-2% wetting agent, 2-5% antifreeze agent, 0.1-0.2% defoamer, 0.1-0.2% thickener, 0.1-0.2% preservative, and the balance being water;

[0019] More preferably, its composition by weight percentage is as follows: 10% brofenoxam, 20% chlorpyrifos, 3% dispersant, 1% wetting agent, 5% antifreeze, 0.5% defoamer, 0.1% thickener, 0.1% preservative, and the balance being water; or 8% brofenoxam, 8% lufenuron, 3% dispersant, 1% wetting agent, 5% antifreeze, 0.5% defoamer, 0.1% thickener, 0.1% preservative, and the balance being water.

[0020] When the compound agricultural insecticide is a dispersible oil suspension, its mass percentage composition is as follows: 1-40% brofenoxam, 1-40% lufenuron or cyclophosphamide, 1-5% dispersant, 5-20% emulsifier, 1-5% thickener, and the balance being an oil medium;

[0021] Preferably, its composition by weight percentage is as follows: 1-25% brofenoxam, 1-25% lufenuron or chlorpyrifos, 1-5% dispersant, 5-15% emulsifier, 1-5% thickener, and the balance being an oil-based medium;

[0022] More preferably, its composition by weight percentage is as follows: 8% brofenoxam, 16% chlorpyrifos, 2% dispersant, 11% emulsifier, 3% thickener, and the balance being an oil-based medium; or 10% brofenoxam, 10% lufenuron, 1% dispersant, 12% emulsifier, 2% thickener, and the balance being an oil-based medium.

[0023] When the compound agricultural insecticide is a wettable powder, its mass percentage composition is as follows: 1-40% bromofenozide, 1-40% lufenuron or chlorpyrifos, 3-10% dispersant, 1-5% wetting agent, and the balance being filler.

[0024] Preferably, its composition by weight percentage is as follows: 1-25% brofenoxam, 1-25% lufenuron or chlorpyrifos, 5-10% dispersant, 1-5% wetting agent, and the balance being filler;

[0025] More preferably, its mass percentage composition is as follows: 12% brofenoxam, 24% chlorpyrifos, 7% dispersant, 3% wetting agent, and the balance filler; or 10% brofenoxam, 10% lufenuron, 5% dispersant, 5% wetting agent, and the balance filler.

[0026] When the compound agricultural insecticide is a soluble powder, its mass percentage composition is as follows: 1-40% bromofenac, 1-40% lufenuron or chlorpyrifos, 3-10% dispersant, 1-5% wetting agent, and the balance being soluble filler;

[0027] Preferably, its composition by weight percentage is as follows: 1-25% bromofenopram, 1-25% lufenuron or chlorpyrifos, 5-10% dispersant, 1-5% wetting agent, and the balance being soluble filler;

[0028] More preferably, its composition by weight percentage is as follows: 12% bromofenopram, 24% insecticidal ring, 7% dispersant, 3% wetting agent, and the balance being soluble filler.

[0029] When the compound agricultural insecticide is a water-dispersible granule, its mass percentage composition is as follows: 1-40% bromonitrile diamide, 1-40% insecticidal ring, 1-10% dispersant, 1-5% wetting agent, and the balance being filler;

[0030] Preferably, its composition by weight percentage is as follows: 1-25% bromofenac, 1-25% insecticidal ring, 1-10% dispersant, 1-5% wetting agent, and the balance being filler;

[0031] More preferably, its composition by weight percentage is as follows: 12% bromofenopram, 24% insecticidal ring, 7% dispersant, 4% wetting agent, and the balance being filler.

[0032] When the compound agricultural insecticide is a microemulsion, it consists of the following components by mass percentage: 1-40% bromonitrile dimethoate, 1-40% lufenuron, 5-25% organic solvent, 15-25% emulsifier, and the balance being water.

[0033] Preferably, its composition by weight percentage is as follows: 1-25% bromofenopram, 1-25% lufenuron, 5-25% organic solvent, 15-25% emulsifier, and the balance being water;

[0034] More preferably, its composition by weight percentage is as follows: 8% bromofenopram, 8% lufenuron, 25% organic solvent, 20% emulsifier, and the balance being water.

[0035] The adjuvants in the above formulation are as follows:

[0036] The dispersant is selected from one or more of the following: naphthaldehyde condensate sulfonate, alkyl naphthaldehyde condensate sulfonate, fatty alcohol ethylene oxide adduct sulfonate, alkylphenol polyoxyethylene ether sulfonate, lignin and its derivative sulfonate, polymerized alkyl aryl sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol ethane adduct phosphate, alkylphenol polyoxyethylene phosphate, alkylphenol polyoxyethylene phosphate ester, polyacrylate, polyacrylic acid and maleic anhydride copolymer salt (or ester), EO-PO block copolymer, hydroxystearic acid and alkyl ethylene glycol block copolymer.

[0037] The wetting agent is selected from one or a mixture of two or more of the following: sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium triisopropylnaphthalene sulfonate, sodium diisobutylnaphthalene sulfonate, sodium dioctyl succinate sulfonate, fatty alcohol polyoxyethylene ether sulfate, alkylphenol polyoxyethylene ether sulfosuccinate, and fatty alcohol polyoxyethylene ether (normal or isomer).

[0038] The emulsifier is selected from one or a mixture of two or more of the following: alkylphenol polyoxyethylene ether, benzylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, phenethylphenol polyoxyethylene ether polyoxypropylene ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate, polyoxyethylene dehydrated sorbitan monooleate, dehydrated sorbitan fatty acid ester, polyethylene glycol oleate, sorbitan polyoxyethylene ether oleate, and dodecylbenzene sulfonate (calcium salt or isopropylamine salt).

[0039] The antifreeze is selected from one or more of the following: ethylene glycol, propylene glycol, glycerol, polyethylene glycol, urea, sorbitol, and inorganic salts.

[0040] The defoamer is selected from one or more of the following: organosilicone compounds, C8-10 fatty alcohols, C19-20 saturated aliphatic carboxylic acids and their esters, and ester-ether compounds.

[0041] The thickener is selected from one or more of xanthan gum, gum arabic, methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, sodium acrylate, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyvinyl acetate, dispersible silica, fumed silica, fumed silica, organobentonite, and magnesium aluminum silicate.

[0042] The preservative is selected from one or more of sodium benzoate, sorbic acid, sodium salicylate, Kathon, thiamethoxam, and phenoxyethanol.

[0043] The organic solvent is selected from one or more of the following: cyclohexanone, N,N-dimethylformamide, N,N-dimethyldecamide, N,N-dimethyloctadecanamide, N-methylpyrrolidone, N-octylpyrrolidone, divalent esters, and aromatic solvent oils.

[0044] The oil medium is selected from one or more of the following: soybean oil, rapeseed oil, cottonseed oil, corn oil, castor oil, palm oil, epoxidized soybean oil, diesel oil, methylated vegetable oil, engine oil, and mineral oil.

[0045] The filler is selected from one or more of the following: diatomaceous earth, attapulgite, light calcium carbonate, sepiolite, kaolin, silica, talc, montmorillonite, corn starch, inorganic salts, and sugars.

[0046] The compound agricultural insecticide provided by this invention can be used to control pests of crops such as Lepidoptera, Coleoptera, and Thysanoptera.

[0047] The Lepidoptera pests are diamondback moth and beet armyworm; the Coleoptera pests are striped flea beetles; and the Thysanoptera pests are thrips.

[0048] When applied, the compound agricultural insecticide is sprayed onto the stems and leaves of crops and the surface of the target.

[0049] Based on extensive research and numerous experiments, the inventors have discovered that the combination of brofenoxam and chlorpyrifos for the control of thrips (a Thysanoptera pest) and flea beetle (a Coleoptera pest) exhibits a significant synergistic effect compared to the corresponding single agents, with no resistance development. Furthermore, there are very few published reports on the combination of brofenoxam and chlorpyrifos; this application is of great significance for expanding the application of brofenoxam-containing compound products.

[0050] Compared with existing technologies, the beneficial effects are:

[0051] This invention provides a compound insecticidal composition containing bromfenac, which combines bromfenac with lufenuron or cyclophosphamide. This combination maintains the insecticidal advantages of the two active components, exhibits a significant synergistic effect, and can significantly improve the control efficacy of treatment and protection. It reduces the number of applications, has high crop safety, and lowers the cost of use. Furthermore, the combination of two components with different mechanisms of action delays the development and progression of pesticide resistance in pests. Detailed Implementation

[0052] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0053] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.

[0054] Bioactive Examples

[0055] This embodiment illustrates the synergistic effect of the compound insecticide composition containing bromfenac provided by the present invention. Through extensive screening experiments, the inventors used the Sun Yunpei method to analyze the synergistic effect of different ratios of the binary compound insecticide composition of bromfenac and chlorpyrifos. The results showed that within a certain ratio range, the composition of bromfenac and chlorpyrifos exhibits a significant synergistic effect against the thrips, a pest of the order Thysanoptera. This synergistic effect is not a simple addition of the two agents; the following bioassay examples illustrate this.

[0056] Example 1: Indoor bioassay of bromfenac combined with lufenuron as a lepidopteran pest, diamondback moth.

[0057] Experimental subject: 3rd instar larvae of the diamondback moth Plutella xylostella (Linnaeus), the selected strain being a sensitive strain raised in the laboratory.

[0058] Test reagents: 99% brofenoxam technical grade, 98% lufenuron technical grade. Both technical grades were provided by Zhongnong Lihua Biotechnology Co., Ltd.

[0059] Brombutazone and lufenuron were mixed in ratios of 2:1, 1.5:1, 1:1, 1:1.5 and 1:2, respectively, for determination of formulations.

[0060] Experimental Methods: The formal experiment was designed based on references and preliminary experimental results. Referring to "NY / T1154.14-2008 Guidelines for Indoor Bioassays of Pesticides, Part 14: Leaf Immersion Method," the test pesticides were first weighed and dissolved in dimethylformamide (DMF), then diluted with 0.05% Triton X-100 aqueous solution to prepare seven test concentrations (see Table 1). Untreated cabbage leaves were prepared into leaf shapes approximately 5 cm in diameter using a punch. The leaves were immersed in the pesticide solution for 10 seconds, then air-dried indoors. The leaves were then placed in 9 cm diameter plastic petri dishes, with moistened filter paper at the bottom for humidity control. Third-instar diamondback moths were inoculated onto the leaves, and the dishes were placed in a constant temperature incubator (temperature: 25℃, relative humidity: 60%, photoperiod:dark period = 16:8h).

[0061] Approximately 15 insects were treated at each concentration, with four replicates. A 0.05% Triton X-100 aqueous solution was used as a blank control. Results were recorded after 48 hours. Insects were considered dead if they did not move or exhibited abnormal activity when lightly touched with a brush. The experimental results were statistically analyzed using SPSS software to calculate the toxicity regression equation and LC-100. 50 Values ​​and 95% confidence limits, etc.

[0062] Drug mixture activity assay: Based on the LC-100 of the two drugs mentioned above... 50 Following the principle of prioritizing the primary pesticide, and mainly considering the efficacy of brofenoxam, brofenoxam and lufenuron were diluted to six test concentrations using different pesticide ratios (2:1, 1.5:1, 1:1, 1:1.5, 1:2) using the same method, as detailed in Table 2. The testing method was the same as for single-agent formulations. The toxicity of the mixture was then determined, and its toxicity regression equation and LC-12 were calculated using SPSS. 50 The values ​​and 95% confidence limits are then used to calculate the co-toxicity coefficient of the compound agent according to the following formula, and the synergistic effect is compared.

[0063] Calculate LC 50 The cotoxicity coefficient (CTC) was calculated using Sun Yunpei's method. The formula for calculating the cotoxicity coefficient (CTC) is as follows:

[0064] (Using brofenoxam (A) as the standard agent with a toxicity index of 100, and chlorfenapyr (B) as the standard agent): Statistical analysis was performed using DPS statistical analysis software to calculate the LC50 of each agent. 50 The co-toxicity coefficient (CTC value) of the mixture was calculated according to Sun Yunpei's method.

[0065] Actual Toxicity Index (ATI) = (LC50 of Standard Reagent) 50 / LC of the test reagent 50 )×100.

[0066] Theoretical Toxicity Index (TTI) = Toxicity Index of Agent A × Percentage of A in the Mixture + Toxicity Index of Agent B × Percentage of B in the Mixture

[0067] Co-toxicity coefficient (CTC) = [Actual toxicity index (ATI) of mixture / Theoretical toxicity index (TTI) of mixture] × 100.

[0068] According to the NY / T11547.7-2006 standard for classifying the combined effects of insecticides: a co-toxicity coefficient (CTC) ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and 80 < CTC < 120 indicates an additive effect.

[0069] Table 1. Bioactivity assay of bromofenofibrate (A) and lufenuron (B) against diamondback moth in cabbage.

[0070]

[0071] Table 2. Bioactivity assay of bromfenac (A) and lufenuron (B) against diamondback moth in cabbage.

[0072]

[0073] Table 3 Bioassays of brofentanil (A) and lufenuron (B) and their mixtures on diamondback moth in cabbage.

[0074]

[0075] As shown in Table 3, within the range of bioassay ratios of brofenoxam and lufenuron against diamondback moth in cabbage, the co-toxicity coefficients of the mixture of brofenoxam and lufenuron ranged from 222.98 to 583.5, all showing good synergistic effects. Among them, the synergistic effect of the 1:1 ratio was the most significant and the strongest.

[0076] Example 2: Indoor bioassay of brofenoxam and insecticidal ring against thrips, a pest of the order Thysanoptera.

[0077] Experimental subject: leek thrips (Thrips alliorum), which were raised in the laboratory and bred for multiple generations. First-instar nymphs were selected as experimental subjects.

[0078] Test reagents:

[0079] 99% brofenoxam technical grade and 90% chlorpyrifos technical grade. Both technical grades were supplied by Zhongnong Lihua Biotechnology Co., Ltd.

[0080] Test method: Refer to "NY / T 1154.6-2006 Guidelines for Indoor Bioassay of Pesticides - Part 6: Insecticidal Activity Test - Immersion Method".

[0081] Setting the ratio: First, dissolve the original drug in dimethyl sulfoxide to prepare a single-dose stock solution, then dilute it with a 0.1% Tween-80 aqueous solution. Set up multiple ratios. Each single drug and each ratio mixture is set with 7 gradient mass concentrations according to the proportional method, with 50 mL of drug solution for each mass concentration.

[0082] Treatment of test insects: First-instar nymphs of scallion thrips were immersed in the drug solution for 10 seconds. After removing excess drug solution with filter paper, they were transferred to normal conditions for rearing. Each treatment was repeated 4 times, with 20 insects immersed in each replicate. A blank control was set up with only dimethyl sulfoxide and 0.1% Tween-80.

[0083] Data Processing: The mortality of the test insects was observed 24 hours after treatment. The total number of insects and the number of dead insects for each treatment were recorded, and the corrected mortality rate for each treatment was calculated. DPS software was used to perform regression analysis on the logarithmic values ​​of the pesticide concentrations and the corrected mortality rate probabilities for each treatment to calculate the LC50 of the pesticide for each treatment. 50 The co-toxicity coefficient (CTC value) of the mixture was calculated according to Sun Yunpei's method.

[0084] P = (K / N) × 100, where P is the mortality rate (%), K is the number of dead insects, and N is the total number of insects treated;

[0085] P1=(P t -P0) / (1-P0), where P1 is the corrected mortality rate (%), P t To account for mortality rate (%), P0 represents the mortality rate (%) in the blank control group;

[0086] Actual Toxicity Index (ATI) = (LC50 of Standard Reagent) 50 / LC of the test reagent 50 )×100.

[0087] Theoretical Toxicity Index (TTI) = Toxicity Index of Agent A × Percentage of A in the Mixture + Toxicity Index of Agent B × Percentage of B in the Mixture

[0088] Co-toxicity coefficient (CTC) = [Actual toxicity index (ATI) of mixture / Theoretical toxicity index (TTI) of mixture] × 100.

[0089] According to the NY / T11547.7-2006 standard for classifying the combined effects of insecticides: a co-toxicity coefficient (CTC) ≥ 120 indicates a synergistic effect; a CTC ≤ 80 indicates an antagonistic effect; and 80 < CTC < 120 indicates an additive effect.

[0090] Table 4. Indoor bioactivity of bromoxynil and chlorpyrifos combined with chlorpyrifos in first instar nymphs of scallion (24h).

[0091]

[0092] As shown in Table 4, when the ratio of brofentanil and chlorpyrifos to thrips on scallions was between 1:1 and 1:6, the co-toxicity coefficient was above 120, indicating a synergistic effect; while at a ratio of 1:2, the co-toxicity coefficient reached 177.87, showing the most significant synergistic effect.

[0093] Formulation Examples

[0094] Formulation Example 1: 16% Brombutamide·Lufenuron Suspension

[0095] Weigh out the following ingredients by weight percentage: 8% brofenoxam, 8% lufenuron, 3% dispersant Supragil MNS / 90 (alkylnaphthalene formaldehyde condensate sulfonate, Solvay), 1% wetting agent TERGITOL W-600 (isomeric alcohol polyoxyethylene ether, DOW), 5% 1,2-propanediol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% Kathon (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% SAG 1522 (organosilicone defoamer, Momentive Advanced Materials Group), and make up to 100% with deionized water (self-made). Mix the above ingredients, mill them using a sand mill until the particle size is less than 5 μm, and filter to obtain a 16% brofenoxam·lufenuron suspension.

[0096] Formulation Example 2: 10% Brombutamide·Lufenuron-methyl aqueous emulsion

[0097] The following components were weighed by weight: 5% brofenoxam, 5% lufenuron, 15% N,N-dimethyloctyldecanoate (Nantong Zhongkai Chemical Co., Ltd.), 3% dispersant Dispersogen LFS (alkylphenol polyoxyethylene phosphate, Solvay), 3% emulsifier EL-40 (castor oil polyoxyethylene ether, Jiangsu Deyi Chemical Co., Ltd.), 5% antifreeze urea (Sinochem Fertilizer Holdings Co., Ltd.), 0.2% defoamer Sag 630 (silicone, Momentive Advanced Materials Group), 0.2% thickener xanthan gum (Shanghai Wanhua Chemical Trade Co., Ltd.), 0.2% preservative Kathon (Beijing Guangyuan Yinong Chemical Co., Ltd.), and water to make up to 100%. First, brofenoxam and lufenuron were dissolved in an organic solvent to form an oil phase. Then, the remaining components were mixed with water to form an aqueous phase. Finally, the oil phase was slowly added in batches to the aqueous phase under high-speed shear. After homogenization and emulsification, and filtration, a 10% brofenoxam·lufenuron water-in-oil emulsion was obtained.

[0098] Formulation Example 3: 20% Brombutamide·Lufenuron Dispersible Oil Suspension

[0099] Weigh out the following ingredients by weight percentage: 10% brofenoxam, 10% lufenuron, 6% emulsifier Emulsogen EL360 (castor oil polyoxyethylene ether, Clariant), 5% emulsifier Phenylsulfonat CAL (calcium dodecylbenzenesulfonate, Clariant), 2% dispersant OF-3498D (polyacrylate, Jiangsu Qingyu Chemical Co., Ltd.), 3% thickener SK-04 (organo-earth, Suzhou Guojian Huitou Mineral New Materials Co., Ltd.), and methyl oleate 0295 (Suzhou Fengbei Biotechnology Co., Ltd.). Make up to 100%. Mix the above ingredients, mill them using a sand mill until the particle size is less than 5 μm, and filter to obtain a 20% brofenoxam·lufenuron dispersible oil suspension.

[0100] Formulation Example 4: 16% Brombutamide·Lufenuron Microemulsion

[0101] Weigh out 8% brofenoxam and 8% lufenuron by weight, 25% solvent N,N-dimethyloctyldecanoate (Hubei Chengfeng Chemical Co., Ltd.), 20% emulsifier Tween-20 (polyoxyethylene dehydrated sorbitan monooleate, Jiangsu Haian Petrochemical Plant), and water to make up to 100%. Dissolve brofenoxam and lufenuron in the organic solvent, add the emulsifier and stir until homogeneous, and finally add water and stir until homogeneous to obtain a 16% brofenoxam·lufenuron microemulsion.

[0102] Formulation Example 5: 20% Brombutamide·Lufenuron Wettable Powder

[0103] Weigh out 10% brofenoxam, 10% lufenuron, 5% dispersant Morwet D-425 (alkyl naphthalene sulfonate, Nouryon), 5% wetting agent K12 (sodium dodecyl sulfate, Dongming Jujin Chemical Co., Ltd.), 8% filler SIPERNAT 22LS (white carbon black, EVONIK), and filler MXK201 (calcined kaolin, Inner Mongolia Mengxi Kaolin Co., Ltd.) to make up 100% by mass percentage. After mixing the above raw materials, pulverize them using an air jet mill and mix them evenly to obtain 20% brofenoxam·lufenuron wettable powder.

[0104] Formulation Example 6: 24% Brofenoxam·Insecticidal Dispersible Oil Suspension

[0105] The following ingredients, by weight percentage, are weighed: 8% brofenoxam, 16% chlorpyrifos, 6% emulsifier Emulsogen TS200 (phenethylphenol polyoxyethylene ether phosphate, Clariant), 6% emulsifier Zephrym 3300B (isopropylamine dodecylbenzene sulfonate, Croda), 1% dispersant YUS-EP60P (alkylphenol polyoxyethylene ether sulfosuccinate, TAKEMOTO), 2% thickener AEROSIL R974 (white carbon black, EVONIK), and soybean oil (Yihai Kerry Group) to make up to 100%. The above ingredients are mixed, milled in a sand mill until the particle size is less than 5 μm, and filtered to obtain a 24% brofenoxam·chlorpyrifos dispersible oil suspension.

[0106] Formulation Example 7: 30% Brombutamide·Insecticidal Suspension Concentrate

[0107] Weigh out the following ingredients by weight percentage: 10% brofenoxuron-methyl, 20% chlorpyrifos, 3% dispersant ATLOX 4913 (polyacrylate, CRODA), 1% wetting agent Genapol X 080 (isomeric alcohol polyoxyethylene ether, Clariant), 5% 1,2-propanediol (antifreeze, Shandong Guohua Chemical Co., Ltd.), 0.1% xanthan gum (thickener, Hebei Pengyu Biotechnology Co., Ltd.), 0.1% Kathon (preservative, Beijing Guangyuan Yinong Chemical Co., Ltd.), 0.5% SAG 1522 (organosilicone defoamer, Momentive Advanced Materials Group), and make up to 100% with deionized water (self-made). Mix the above ingredients, grind them in a sand mill until the particle size is less than 5 μm, and filter to obtain a 30% brofenoxuron-methyl·chlorpyrifos suspension.

[0108] Formulation Example 8: 36% Brombutamide·Insecticidal Wettable Powder

[0109] By weight percentage, weigh out 12% brofenoxam, 24% chlorpyrifos, 7% dispersant Geropon T / 36 (polyacrylic acid and maleic anhydride copolymer salt, Solvay), 3% wetting agent Geropon L-Wet / P (sodium dodecylbenzenesulfonate, Solvay), 8% filler SIPERNAT 22LS (white carbon black, EVONIK), and filler Celite C350 (diatomaceous earth, Imerys) to make up to 100%. After mixing the above raw materials, pulverize them using an air jet mill and mix them evenly to obtain 36% brofenoxam·chlorpyrifos wettable powder.

[0110] Formulation Example 9: 36% Brombutamide·Insecticidal Cyclopyralid Water Dispersible Granules

[0111] By weight percentage, weigh out 12% brofenoxam, 24% chlorpyrifos, 7% dispersant Suparex Kpowder (naphthaldehyde condensate sulfonate dispersant, Angco Chemicals, Switzerland), 4% wetting agent sodium dodecyl sulfate (Dongming Jujin Chemical Co., Ltd.), 20% corn starch (filler, Linyi Tailong Industrial Co., Ltd.), and filler MXK201 (calcined kaolin, Inner Mongolia Mengxi Kaolin Co., Ltd.) to make up 100%. After mixing the above raw materials, pulverize them evenly using an air jet mill, knead them, and then granulate, dry, and sieve to obtain 36% brofenoxam·chlorpyrifos water-dispersible granules.

[0112] Formulation Example 10: 36% Brombutamide·Insecticidal Soluble Powder

[0113] By weight percentage, weigh out 12% brofenoxam, 24% chlorpyrifos, 7% dispersant Geropon Ultrasperse (polycarboxylate salt, Solvay), 3% wetting agent Geropon L-Wet / P (sodium dodecylbenzenesulfonate, Solvay), 8% filler glucose (Zibo Ruixue Sugar Industry Co., Ltd.), and filler ammonium sulfate (Shandong Juweitai Biotechnology Co., Ltd.) to make up 100%. After mixing the above raw materials, pulverize them using an air jet mill and mix them evenly to obtain 36% brofenoxam·chlorpyrifos soluble powder.

[0114] Field efficacy examples:

[0115] Field efficacy example 1: Field control efficacy example against diamondback moth in cabbage

[0116] Test reagent: The mixture of bromfenac and lufenuron prepared in Examples 1-5;

[0117] 5% Brombutamide Suspension Concentrate (Mitsui Chemicals AGRO Corporation, Japan);

[0118] 5% Lufenuron Suspension Concentrate (Hailier Pharmaceutical Group Co., Ltd.);

[0119] This experiment followed the guidelines in GB / T 17980.13-2000 "Field Efficacy Test Guidelines for Pesticides (I) Insecticides for the Control of Lepidoptera Larvae in Cruciferous Vegetables". The experimental pesticide, control pesticide, and blank control were randomly assigned to plots of 50 m². 2 Use a 3WBD-20 backpack electric sprayer to spray evenly, applying the pesticide at a rate of 1:1 per 667m². 2 30 kg of water was used to spray evenly on each plot. No other agents were used during the experiment, and each treatment was repeated 4 times.

[0120] Survey and statistical methods: Five diagonal sampling points were taken in each plot before pesticide application, with 10 plants selected at each point to investigate the initial population of diamondback moths. The number of live diamondback moths was investigated on days 3, 7, and 14 after pesticide application. The population reduction rate and control effect were calculated.

[0121] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0122] Control efficacy (%) = {(Pest population reduction rate in the treated area - Pest population reduction rate in the blank control area) / (100 - Pest population reduction rate in the blank control area)} × 100

[0123] Safety investigation and effects on other organisms: The effects of each pesticide treatment on cabbage growth and other organisms were observed on the first day after each spraying and several days after the spraying.

[0124] Table 5. Field control efficacy of brofenoxam and dicofol combination against diamondback moth in cabbage.

[0125]

[0126] Table 5 shows the efficacy results, indicating that the 1:1 mass ratio of brofenoxam and lufenuron exhibits a significant synergistic effect. The control efficacy of each compound against the diamondback moth on cabbage remained above 90% at 3, 7, and 14 days post-application, significantly higher than that of brofenoxam and lufenuron alone. No phytotoxicity was observed during the application period, indicating safety for cabbage growth.

[0127] Example 2: Field efficacy of pesticide against beet armyworm in lettuce.

[0128] Test reagent: The mixture of bromfenac and lufenuron prepared in Examples 1-5;

[0129] 5% Brombutamide Suspension Concentrate (Mitsui Chemicals AGRO Corporation, Japan);

[0130] 5% Lufenuron Suspension Concentrate (Hailier Pharmaceutical Group Co., Ltd.);

[0131] This experiment followed the guidelines in GB / T 17980.13-2000 "Field Efficacy Test Guidelines for Pesticides (I) Insecticides for the Control of Lepidoptera Larvae in Cruciferous Vegetables". The experimental pesticide, control pesticide, and blank control were randomly assigned to plots of 50 m². 2 Use a 3WBD-20 backpack electric sprayer to spray evenly, applying the pesticide at a rate of 1:1 per 667m². 2 30 kg of water was used to spray evenly on each plot. No other pesticides were used during the experiment. Each treatment was replicated four times.

[0132] Survey and statistical methods: Five diagonal sampling points were taken in each plot before pesticide application, with 10 plants selected at each point to investigate the initial population of beet armyworm. The number of live diamondback moths was investigated on days 1, 3, and 7 after pesticide application. The population reduction rate and control effect were calculated.

[0133] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0134] Control efficacy (%) = {(Pest population reduction rate in the treated area - Pest population reduction rate in the blank control area) / (100 - Pest population reduction rate in the blank control area)} × 100

[0135] Safety investigation and effects on other organisms: The effects of each pesticide treatment on lettuce growth and other organisms were observed on the first day after each spraying and several days after the spraying.

[0136] Table 6. Field control efficacy of bromoxynil and chlorfenapyr combined with lettuce and beet armyworm.

[0137]

[0138] Table 6 shows the efficacy results, indicating that the 1:1 mass ratio of brofenoxam and lufenuron exhibits a significant synergistic effect. The control efficacy of each compound agent against the beet armyworm on lettuce reached over 95% one and three days after application, and over 90% seven days after application, representing a substantial improvement compared to the control efficacy of brofenoxam and lufenuron alone. No phytotoxicity was observed during the application period, indicating safety for lettuce growth.

[0139] Example 3: Field efficacy of herbicide against thrips on scallions

[0140] Test reagent: The mixture of bromoxynil dimethyl methacrylate and chlorpyrifos prepared in Examples 6-10 of the formulation;

[0141] 5% Brombutamide Suspension Concentrate (Mitsui Chemicals AGRO Corporation, Japan);

[0142] 50% insecticidal ring soluble powder (Nippon Kayaku Co., Ltd.);

[0143] This experiment followed the guidelines in "NY / T 1464.6-2007 Field Efficacy Test Guidelines for Pesticides Part 6: Insecticides for the Control of Thrips in Vegetables". The experimental pesticide, control pesticide, and blank control were randomly assigned to plots of 40 m². 2 The number of thrips nymphs should be no less than 300 per 15-30 leaves of each scallion. Use a 3WBD-20 backpack electric sprayer to spray evenly, applying the pesticide at a rate of [per unit area] per 667 m². 2 30 kg of water was used to spray evenly on each plot. No other agents were used during the experiment, and each treatment was repeated 4 times.

[0144] Survey and statistical methods: 15 to 30 scallion leaves were selected from each plot. The initial insect population was surveyed before pesticide application, and the number of residual insects was surveyed on days 1, 3, 7, and 14 after pesticide application. The control effect was calculated.

[0145] Control efficacy (%) = {1 - [(Number of live nymphs before application in the blank control area × Number of live nymphs after application in the pesticide-treated area) / (Number of live nymphs after application in the blank control area × Number of live nymphs before application in the pesticide-treated area)]} × 100

[0146] Safety investigation and effects on other organisms: The effects of each treatment on scallion growth and on other organisms were observed on the first day after each spraying and several days after the spraying.

[0147] Table 7. Field control efficacy of bromofenac and chlorpyrifos combined with thrips onion.

[0148]

[0149] Table 2 shows the efficacy results, indicating that the combination of brofenoxam and chlorpyrifos at a mass ratio of 1:2 has a significant synergistic effect. The control efficacy of each compound against thrips on scallions reached over 95% one day after application, and remained above 90% at three, seven, and fourteen days after application, significantly improving upon the control efficacy of either brofenoxam or chlorpyrifos alone. No phytotoxicity was observed during the application period, indicating safety for scallion growth.

[0150] Example 4: Field efficacy of pesticides against the yellow-striped flea beetle in cabbage

[0151] Test reagent: The mixture of bromoxynil dimethyl methacrylate and chlorpyrifos prepared in Examples 6-10 of the formulation;

[0152] 5% Brombutamide Suspension Concentrate (Mitsui Chemicals AGRO Corporation, Japan);

[0153] 50% insecticidal ring soluble powder (Nippon Kayaku Co., Ltd.);

[0154] This experiment followed the guidelines in GB / T 17980.18-2000 "Field Efficacy Test Guidelines for Pesticides (I) Insecticides for the Control of Yellow-striped Flea Beetles on Cruciferous Vegetables". The experimental pesticide, control pesticide, and blank control were randomly assigned to plots of 40 m². 2 Protective measures were implemented along the perimeter of the residential area. A 3WBD-20 backpack electric sprayer was used for uniform spraying, with each application of pesticide applied at a rate of [percentage missing] per 667m². 2 30 kg of water was used to spray evenly on each plot. No other agents were used during the experiment, and each treatment was repeated 4 times.

[0155] Survey and statistical methods:

[0156] Adult insect survey: At least 20 cabbage plants were randomly selected from each plot to investigate the number of live adults.

[0157] Larval survey: During the last survey after the pesticide application, at least three fixed points should be set up in each plot, and two plants should be surveyed at each point. The soil around the plant roots should be dug up and rinsed with clean water to count the number of live larvae in the soil.

[0158] A baseline survey was conducted before application. The second survey was conducted 2 days after application. The third survey was conducted 7 days after application.

[0159] Insect population reduction rate (%) = {(number of insects before application - number of insects after application) / number of insects before application} × 100;

[0160] Adult insect control efficacy (%) = {(insect population reduction rate in the pesticide-treated area - insect population reduction rate in the blank control area) / (100 - insect population reduction rate in the blank control area)} × 100;

[0161] Larval control efficacy (%) = {(Number of larvae in the blank control area - Number of larvae in the pesticide-treated area) / Number of larvae in the blank control area} × 100

[0162] Safety investigation and effects on other organisms: The effects of each pesticide treatment on cabbage growth and other organisms were observed on the first day after each spraying and several days after the spraying.

[0163] Table 8. Field control efficacy of bromofenac and chlorpyrifos combined with flea beetle in cabbage.

[0164]

[0165] Table 8 shows the efficacy results, indicating that the combination of brofenoxam and chlorpyrifos at a mass ratio of 1:2 has a significant synergistic effect. The combined formulations achieved over 90% control efficacy against adult flea beetles on cabbage at both 2 and 7 days post-application, and over 95% control efficacy against larvae, demonstrating a significant improvement compared to the control efficacy of brofenoxam and chlorpyrifos alone. No phytotoxicity was observed during the application period, indicating safety for cabbage growth.

[0166] In summary, the insecticidal combination containing bromufenoxam of this invention exhibits excellent control efficacy against pests of the Coleoptera, Thysanoptera, and other Thysanoptera orders in crops, and is safe for the target crops. This compound formulation not only improves efficacy but also reduces dosage and cost, making it an ideal agent for controlling agricultural pests. Therefore, the invention and promotion of this compound formulation are of great social significance.

Claims

1. A compound agricultural insecticide, comprising a compound agricultural insecticide composition and excipients acceptable for pesticide formulation. Cheng, among which, The compound agricultural insecticide composition has a mass percentage of 1% to 90%; The active ingredients of the compound agricultural insecticide composition are bromfenac and insecticidal ring; The mass ratio of the bromoxynil diamide to the insecticidal ring is 1:2; The formulation of the compound agricultural insecticide is any one of the following: suspension concentrate, dispersible oil suspension concentrate, wettable powder, soluble powder, and water-dispersible granules. When the compound agricultural insecticide is a suspension concentrate, its mass percentage composition is as follows: 1-40% bromofenac, 1-40% insecticidal ring, 2-10% dispersant, 1-5% wetting agent, 2-10% antifreeze agent, 0.1-1% defoamer, 0.1-3% thickener, 0.1-2% preservative, and the balance being water; When the compound agricultural insecticide is a dispersible oil suspension, its mass percentage composition is as follows: 1-40% bromonitrile diamide, 1-40% insecticidal ring, 1-5% dispersant, 5-20% emulsifier, 1-5% thickener, and the balance being an oil medium. When the compound agricultural insecticide is a wettable powder, its mass percentage composition is as follows: 1-40% bromonitrile dimethamide, 1-40% insecticidal ring, 3-10% dispersant, 1-5% wetting agent, and the balance being filler; When the compound agricultural insecticide is a soluble powder, its mass percentage composition is as follows: 1-40% bromonitrile diamide, 1-40% insecticidal ring, 3-10% dispersant, 1-5% wetting agent, and the balance being soluble filler. When the compound agricultural insecticide is a water-dispersible granule, its mass percentage composition is as follows: 1-40% bromofenac, 1-40% insecticidal ring, 1-10% dispersant, 1-5% wetting agent, and the balance being filler. The dispersant is selected from one or more of the following: naphthaldehyde condensate sulfonate, alkyl naphthaldehyde condensate sulfonate, fatty alcohol ethylene oxide adduct sulfonate, alkylphenol polyoxyethylene ether sulfonate, lignin and its derivative sulfonate, polymerized alkyl aryl sulfonate, alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, fatty alcohol polyoxyethylene ether sulfate, fatty alcohol ethane adduct phosphate, alkylphenol polyoxyethylene phosphate, alkylphenol polyoxyethylene phosphate ester, polyacrylate, polyacrylic acid and maleic anhydride copolymer salt (or ester), EO-PO block copolymer, hydroxystearic acid and alkyl ethylene glycol block copolymer; The emulsifier is selected from one or a mixture of two or more of the following: alkylphenol polyoxyethylene ether, benzylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, phenethylphenol polyoxyethylene ether polyoxypropylene ether, castor oil polyoxyethylene ether, alkylphenol polyoxyethylene ether formaldehyde condensate, polyoxyethylene dehydrated sorbitan monooleate, dehydrated sorbitan fatty acid ester, polyethylene glycol oleate, sorbitan polyoxyethylene ether oleate, and dodecylbenzene sulfonate. The thickener is selected from one or more of xanthan gum, gum arabic, methylcellulose, sodium carboxymethyl cellulose, hydroxypropyl cellulose, sodium acrylate, polyvinyl alcohol, polyvinylpyrrolidone, sodium polyacrylate, polyvinyl acetate, dispersible silica, fumed silica, fumed silica, organobentonite and magnesium aluminum silicate. The oil medium is selected from one or more of the following: soybean oil, rapeseed oil, cottonseed oil, corn oil, castor oil, palm oil, epoxidized soybean oil, diesel oil, methylated vegetable oil, engine oil, and mineral oil.

2. The application of the compound agricultural insecticide of claim 1 in the control of Coleoptera and Thysanoptera pests of crops; The Coleoptera pest in question is the yellow-striped flea beetle. The pests mentioned are thrips.

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