A compound synergistic insecticide composition and its application

Abstract

The present invention discloses a compound synergistic insecticide composition and its application. The composition contains two active components, A and B, with the mass ratio of components A to B being (1-5):(5-20). Active component A is selected from compounds represented by formulas a, b, and c; component B is selected from organophosphorus insecticides, pyrethroid insecticides, and neonicotinoid insecticides. The compound synergistic insecticide composition of the present invention has excellent synergistic effects, a simple preparation process, and low cost. It can be used to reduce the amount of chemical insecticides and increase their efficacy, as well as for the green control of aphids. #imgabs0#

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a compound synergistic insecticide composition and an application thereof, and more particularly relates to an application of the composition in aphid prevention and control. Background Art

[0002] Aphids, also known as honey bees and sticky insects, belong to the order Hemiptera and superfamily Aphidoidea. They are characterized by a wide variety of species, rapid reproduction, large numbers, a wide host range, and the tendency to develop pesticide resistance. They pose serious threats to agriculture and the environment and are one of the most destructive agricultural and horticultural pests worldwide (Gong, Q et al. Nature. 2023 , 622: 139–148;Jiang, J et al. J. Pest Sci. 2023, 96: 225–239). As piercing-sucking pests, aphids not only harm crops by feeding directly on plant sap, but also produce honeydew that can breed various fungi and induce a variety of diseases (Dedryver, C.-A et al. C. R. Biol. 2010, 333: 539–553). In addition, aphids are the primary vector insects that transmit plant viruses (Zhang, D et al. J. Agric. Food Chem. 2022, 70: 8598–8608).

[0003] Currently, aphid control still mainly relies on chemical pesticides, including organophosphates, pyrethroids and neonicotinoids (Luo, K et al. Front. Plant Sci. 2022, 12: 790919). However, the long-term and extensive use of chemical pesticides has led to serious aphid resistance problems, environmental pollution, and toxicity to non-target organisms (Zuma, M et al. J. Pest Sci. 2023, 96: 711–721). Therefore, the development of synergistic substances that can enhance biological activity and reduce the amount of insecticides used is of great significance for the control of aphids.

[0004] ( E )-β-farnesene (EBF) is the main or only component of the alarm pheromone of most aphids (FrancisF et al. J. Appl. Entomol. 2005, 129(1): 6-11). It is released from the abdominal tube of aphids when they sense danger signals, which has an alarm and repellent effect on aphids. In addition, EBF has other functions, such as enhancing the activity of imidacloprid against cabbage aphids (Cui, L et al. Crop Prot. 2012, 35: 91–96), regulating the production of winged aphids (De, V. M etal. Natl. Acad. Sci. 2010, 107: 14673–14678) and attracting natural enemies (Gish, M et al. J. Pest Sci. 2021, 94: 1209–1219). However, due to the unstable conjugated double bond at the end of the EBF structure, it is extremely volatile and easily oxidized, which limits the practical application of EBF in the field. Therefore, many researchers at home and abroad have carried out a large number of structural modifications on EBF in order to discover compounds with both activity and stability. The inventors have previously carried out a series of structural modifications and modifications on EBF and discovered many EBF analogs with both activity and stability. For example, the EBF analogs 3e (compound shown in formula a), 4i (compound shown in formula b), and T9 (compound shown in formula c) have been discovered. While having high aphid repellent activity, they also show higher stability than EBF (Qin, Y. G et al. Pest Manag. Sci. 2020, 76:2465–2472; Yang, Z. K et al. Pest Manag. Sci. 2023, 79: 760-770; Pan, S. X et al. Pest Manag. Sci. 2024, 80: 1099-1106). However, whether these highly active and stable EBF analogs exhibit synergistic effects when mixed with insecticides has not been reported. Therefore, studying the synergistic effects of these EBF analogs is of great significance for achieving reduced dosage and increased efficacy of chemical insecticides.

[0005] Summary of the Invention

[0006] One of the purposes of the present invention is to provide a compound synergistic insecticide composition.

[0007] The compound synergistic insecticide composition comprises component A and component B;

[0008] The component A is any one or more of the compounds represented by formula a, formula b or formula c, and the component B is any one or more of the organophosphorus insecticide, pyrethroid insecticide and neonicotinoid insecticide;

[0009] Furthermore, the structural formula of the compound represented by formula a, formula b or formula c is as follows:

[0010]

[0011] In formula a:

[0012] R1 is H, C1~C10 alkyl, haloalkyl, phenyl (including phenyl substituted by halogen, nitro, C1~10 alkyl and alkoxy), benzyl (including benzyl substituted by halogen, nitro, C1~10 alkyl and alkoxy), phenyl substituted by halogen, nitro, C1~10 alkyl and alkoxy, thiazole, pyridine;

[0013] R2 is H, OH, C1~C10 alkyl, C1~C10 alkoxy, haloalkyl, halogen, or nitro;

[0014] R3 is absent, H, C1~C10 alkyl, halogen, nitro, C1~10 alkyl and alkoxy substituted phenyl;

[0015] X is O, N; Y is O, S.

[0016] Preferably, R1 is H, methyl, ethyl, phenyl, benzyl; R2 is H, OH, methyl, methoxy, Cl, F, CF3, NO2; R3 is absent, H, CH3; X is O, N; and Y is O.

[0017] The compound represented by the above formula a can be any one of the following:

[0018]

[0019]

[0020] In formula b:

[0021] R1 can be a C1~C12 straight chain or linear alkyl group (specifically a C1~C6 straight chain or linear alkyl group, such as -CH3,

[0022] -CH2CH3, -(CH2)2CH3, -(CH2)3CH3, -(CH2)4CH3, -(CH2)5CH3, -CH(CH3)2), any one of a halogenated C1~C12 straight or linear alkyl group, a C1~C12 alkoxy group, a halogenated C1~C12 alkoxy group, a C3~C12 cycloalkyl group (specifically, a C3~C6 cycloalkyl group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl), and an aromatic heterocycle (such as thiophene);

[0023] R2 is monosubstituted or polysubstituted, and R2 is independently selected from any one of the group consisting of H, OH, C1~C12 straight or linear alkyl (specifically C1~C6 straight or linear alkyl), halogenated C1~C12 alkyl (such as trifluoromethyl), C1~C12 alkoxy (specifically C1~C6 alkoxy, such as methoxy), halogenated C1~C12 alkoxy, halogen and nitro;

[0024] X can be O or S, and specifically can be O.

[0025] The compound represented by the above formula b can be any one of the following:

[0026]

[0027]

[0028] In formula c:

[0029] m is an integer from 0 to 2, specifically 0, 1 or 2;

[0030] R1 represents a substituent on the benzene ring, which may be monosubstituted or polysubstituted, and R1 may be independently selected from at least one of the group consisting of hydrogen, halogen, nitro, cyano, alkenyl (such as allyl -CH2CHCH2), C1~C8 alkoxy, acyl (specifically formyl -CHO, acetyl -COCH3), aromatic heteroyl, heterocyclic group, carboxyl, ester group (specifically -COOCH3), C1~C8 straight-chain or branched-chain alkyl, halogen-substituted C1~C8 straight-chain or branched-chain alkyl, and halogen-substituted C1~C8 alkoxy;

[0031] When R1 is a ring structure, R1 is connected to the benzene ring by a single bond or a paraben ring;

[0032] Specifically, R1 is monosubstituted or polysubstituted, and R1 is independently at least one of methyl, isopropyl, formyl (-CHO), ester (-COOCH3), methoxy, allyl-CH2CHCH2, 3,4-methylenedioxy, 3,4-pyrrolyl, acetyl-COCH3, Cl, F, -NO2, -CF3, -OCF3, ethoxy, Br, H, and trifluoromethoxy.

[0033] The compound represented by the above formula c can be any one of the following:

[0034]

[0035] Furthermore, the organophosphorus insecticide includes any one or more of trichlorfon, dichlorvos, phoxim, fenitrothion, fenthion, chlorpyrifos, diazinon, triazophos, malathion, acephate, dimethoate, etc.;

[0036] Furthermore, the pyrethroid insecticide includes any one or more of beta-cypermethrin, deltamethrin, cypermethrin, bifenthrin, cyfluthrin, beta-cyhalothrin, etc.;

[0037] Furthermore, the neonicotinoid insecticides include any one or more of imidacloprid, nitenpyram, acetamiprid, thiacloprid, thiamethoxam, clothianidin, chlorothiazolin, dinotefuran, cycloheximide, flupyradan, and sulfoxaflor.

[0038] There is no special restriction on the ratio of the two active components of the compound synergistic insecticide composition of the present invention when they are used, and the two components can be compounded and used in any ratio.

[0039] In order to better exert the efficacy, in the above-mentioned compound synergistic insecticidal composition, the mass ratio of component A to component B is preferably (1~50):(1~100), more preferably (1~20):(1~50), and further preferably (1~5):(5~20); that is, when the two components are compounded and used in the above ratio, they have a better synergistic effect.

[0040] A second object of the present invention is to provide the use of the above-mentioned compound synergistic insecticide composition in aphid prevention and control.

[0041] In the application, the aphids include any one or more of peach aphid, pea aphid, soybean aphid, cotton aphid, apple yellow aphid, rose aphid, wheat aphid (wheat aphid, cereal aphid, wheat aphid), vegetable aphid, and netless aphid.

[0042] The compound synergistic insecticide composition is used on crops, vegetables, fruit trees, flowers and Chinese herbal medicine plants.

[0043] The compound synergistic insecticidal composition of the present invention has an excellent synergistic effect, can enhance the efficacy of insecticides, and at the same time reduce the number of applications and usage of pesticides, reduce farmers' drug costs, and reduce the impact on the environment. It has a simple preparation process and low cost, and has good application prospects and practical significance in reducing the amount of chemical insecticides and increasing their efficacy, as well as in the green control of aphids. DETAILED DESCRIPTION

[0044] The present invention will be further described in detail below in conjunction with specific embodiments. The examples provided are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a guide for further improvements by those skilled in the art and are not intended to limit the present invention in any way.

[0045] Unless otherwise specified, the experimental methods in the following examples are conventional methods and were performed according to the techniques or conditions described in the literature in the field or according to the product instructions. The materials and reagents used in the following examples, unless otherwise specified, were all commercially available.

[0046] In order to demonstrate that component A of the present invention has a synergistic effect, representative compounds (a-07, a-15, b-17 and c-37) were selected from component A (Formula a, Formula b and Formula c), and representative insecticides were selected from component B, including organophosphorus insecticides (chlorpyrifos, triazophos, acephate), pyrethroid insecticides (beta-cypermethrin, bifenthrin, beta-cyhalothrin) and neonicotinoid insecticides (imidacloprid, thiamethoxam, sulfoxaflor), as illustrated by the following examples.

[0047] Among them, the compound represented by a-07 was prepared by referring to the method described in Example 1 of Chinese Patent (ZL201510076763.9);

[0048] The compound shown in a-15 was prepared by referring to the method described in Example 1 of Chinese Patent (ZL201510076763.9);

[0049] The compound shown in b-17 was prepared by referring to the method described in Example 4 of Chinese Patent (ZL202111271583.8);

[0050] The compound shown in c-37 was prepared by referring to the method described in Example 2 of Chinese patent (ZL202111273217.6).

[0051] Example 1: Preparation of Synergistic Insecticide Compositions with Different Mass Ratios

[0052] The nine pesticides were prepared into 2000 mg / L stock solutions using acetone. Subsequently, each stock solution of the pesticide was serially diluted using 0.05% Triton X-100 dilution solution to produce at least five concentrations. All the solutions were refrigerated at 4°C until use. Subsequently, a-07, a-15, b-17, and c-37 (component A) were mixed with the pesticide (component B) solutions of various concentrations at a component A:component B (mass ratio) of 1:(5-20) to prepare mixtures of the compounds a-07, a-15, b-17, and c-37 with the nine pesticides.

[0053] Example 2: Indoor toxicity determination of synergistic insecticide compositions with different mass ratios against green peach aphids

[0054] Test insects: Myzus persicae, provided by the College of Plant Protection, China Agricultural University.

[0055] Experimental Methods: The bioassay was conducted using a modified leaf dip method from the original design. Newly grown, blank radish seedlings were selected to ensure they had not been exposed to any pesticides during their growth and were free of aphids on their leaves and shoots. The previously prepared insecticide solution and the mixed solution were poured into separate 50 mL beakers and the radish seedlings were immersed in the test solution for 10 seconds. Three plants per group were placed in a 2.0 mL centrifuge tube filled with water to maintain the seedlings and then placed in a Petri dish. Twenty adult peach aphids, starved for 1–2 hours, were randomly selected and placed on the treated leaves. The insects were then cultured in a constant-temperature artificial climate incubator for 24 hours. Three replicates were used for each treatment. Finally, the number of aphid deaths was recorded, and the sublethal concentration of each insecticide mixture was calculated.

[0056] Death standard for peach aphids: If the peach aphids do not respond after their antennae are touched with a brush, they are considered dead.

[0057] The results of the indoor toxicity test of the synergistic insecticidal composition against aphids are shown in Tables 1, 2 and 3, respectively.

[0058] Table 1 Results of indoor toxicity tests on Myzus persicae of organophosphorus insecticides mixed with representative compounds

[0059]

[0060] Table 2 Results of indoor toxicity tests on Myzus persicae of mixtures of pyrethroid insecticides and representative compounds

[0061]

[0062] Table 3 Results of indoor toxicity tests on green peach aphids after mixing neonicotinoid insecticides with representative compounds

[0063]

[0064] From the results of indoor toxicity tests on aphids in Tables 1, 2 and 3, it can be seen that after the representative insecticides were mixed with a-07, a-15, b-17 and c-37 in different mass ratios, the overall toxicity against aphids was better than the toxicity when the insecticides were used alone. This indicates that the compounds represented by a-07, a-15, b-17 and c-37 have a significant synergistic effect after being mixed with insecticides.

[0065] To further demonstrate the synergistic effect of Component A of the present invention under field conditions, representative compound a-07 was selected from Component A (Formulas a, b, and c), and the representative insecticide imidacloprid was selected from Component B, as further illustrated in Examples 3 and 4 below. The application scenarios of the insecticidal combination of Components A and B are not limited to the cotton and wheat field aphid control applications described in Examples 3 and 4, but also include the green control of aphids on other crops, vegetables, fruit trees, flowers, and Chinese herbal medicines described in the present invention.

[0066] Example 3: Field efficacy test of the insecticide composition of a-07 and imidacloprid against cotton aphids

[0067] Experimental subjects and crops: cotton aphid and cotton.

[0068] Experimental environment: The experimental field was sandy loam with an organic matter content of 16.9 g / kg and a pH of 7.9.

[0069] Test agents: 70% imidacloprid water dispersible granules (component B), 12.5% ​​a-07 microemulsion + 70% imidacloprid water dispersible granules (component A + component B).

[0070] The above-mentioned 12.5% ​​a-07 microemulsion was prepared by referring to the method described in Example 2 of Chinese Patent (ZL202111271585.7);

[0071] Application method: Liquid spray, using Singapore Jacto HD300 backpack sprayer for spraying.

[0072] Survey time and number: Field efficacy surveys were conducted 4 times in total. The first survey was on the base number of insect population before the application of the drug; the second survey was on the number of insect population one day after the application of the drug; the third survey was on the number of insect population three days after the application of the drug; and the fourth survey was on the number of insect population five days after the application of the drug.

[0073] Survey Method: Use a five-point Z-shaped sampling method, with three plants at each point. Take one leaf from each plant, from the top, middle, and bottom, and count the number of aphids on each plant. Before applying the pesticide, conduct a baseline survey and mark the survey points. After application, continue surveying and counting these plants. Use fixed personnel, plants, and locations to ensure more accurate data.

[0074] Calculation method of drug efficacy:

[0075] Pest reduction rate (%) = (base number of insects in the treated area before treatment - number of insects remaining in the treated area after treatment) / base number of insects in the treated area before treatment × 100

[0076] Corrected control effect (%) = (pest population reduction rate in treated area - insect population reduction rate in blank area) / (100 - insect population reduction rate in blank area) × 100

[0077] The results of the field efficacy test of the insecticide composition of a-07 mixed with imidacloprid against cotton aphids are shown in Table 4.

[0078] Table 4 Test results of the insecticide composition of a-07 mixed with imidacloprid for controlling cotton aphids

[0079]

[0080] The test results in Table 4 indicate that a-07, when combined with imidacloprid (1g + 3g active ingredient / mu), exhibited superior control efficacy against cotton aphids, surpassing imidacloprid alone. Five days after application, the control efficacy reached 93%, exceeding that of imidacloprid alone. Field efficacy tests demonstrate that the representative compound a-07 exhibits synergistic effects when combined with imidacloprid.

[0081] Example 4: Field efficacy test of the insecticide composition of a-07 and imidacloprid against wheat aphids

[0082] Experimental subjects and crops: Aphididae avenae, Aphididae graminearum, and wheat.

[0083] Experimental environment: The experimental field is loamy, the soil is fertile and irrigation is convenient.

[0084] Test agents: 10% imidacloprid wettable powder (component B), 12.5% ​​a-07 microemulsion + 10% imidacloprid microemulsion (components A + B).

[0085] Application method: Liquid spray, use a manual backpack sprayer for spraying.

[0086] Results Survey time and number: Field efficacy surveys were conducted 4 times in total. The first survey was conducted before the test spraying. The second, third and fourth surveys were conducted 1, 3 and 5 days after spraying respectively.

[0087] Results Survey method: In each plot, 5 points of "Z" shape sampling were adopted, and 3 wheat plants with about 40 insects per plant were selected at each point. The insect population was recorded and tagged, and the number of living insects or remaining living insects was recorded.

[0088] Calculation method of drug efficacy:

[0089] Pest reduction rate (%) = (base number of insects in the treated area before treatment - number of insects remaining in the treated area after treatment) / base number of insects in the treated area before treatment × 100

[0090] Corrected control effect (%) = (pest population reduction rate in treated area - insect population reduction rate in blank area) / (100 - insect population reduction rate in blank area) × 100

[0091] The results of the field efficacy test of the insecticide composition of a-07 mixed with imidacloprid against wheat aphids in wheat fields are shown in Table 5.

[0092] Table 5 Test results of the insecticide composition of a-07 mixed with imidacloprid for controlling wheat aphids in wheat fields

[0093]

[0094] The test results in Table 5 show that the field control effect of the mixed composition of imidacloprid and a-07 is generally better than that of using imidacloprid alone, indicating that the representative compound a-07 has a synergistic effect after being combined with imidacloprid.

[0095] The present invention has been described in detail above. For those skilled in the art, without departing from the purpose and scope of the present invention, and without the need to carry out unnecessary experimental conditions, the present invention can be implemented in a wide range under equivalent parameters, concentrations and conditions. Although the present invention provides specific embodiments, it should be understood that further improvements can be made to the present invention. In short, according to the principles of the present invention, this application is intended to include any changes, uses or improvements to the present invention, including changes that depart from the disclosed scope in this application and are made using conventional techniques known in the art.

Claims

1. An insecticide composition comprising component A and component B; in, Component A is selected from: 、 、 and Any of the following; The component B is selected from any one of beta-cypermethrin, bifenthrin and beta-cyhalothrin; The mass ratio of component A to component B is 1:5-20.

2. An insecticide composition comprising component A and component B; in, Component A is selected from: 、 、 and Any of the following; The component B is selected from any one of chlorpyrifos, triazophos, and acephate; The mass ratio of component A to component B is 1:5-20.

3. An insecticide composition comprising component A and component B; in, Component A is selected from: 、 、 and Any of the following; The component B is selected from any one of imidacloprid, thiamethoxam and sulfoxaflor; The mass ratio of component A to component B is 1:5-20.

4. Use of the insecticidal composition according to any one of claims 1 to 3 in controlling aphids.

5. The use according to claim 4, characterized in that In the application, the aphids are selected from any one or more of peach aphid, pea aphid, soybean aphid, cotton aphid, apple yellow aphid, rose aphid, wheat aphid, cabbage aphid, and netless aphid.

6. The use according to claim 4, characterized in that The insecticide composition is used on crops, vegetables, fruit trees, flowers and Chinese herbal medicine plants.

7. Use of compound a-07, compound a-15, compound b-17 or compound c-37 as an insecticide synergist, in, The insecticide is selected from any one of beta-cypermethrin, bifenthrin, beta-cyhalothrin, chlorpyrifos, triazophos, acephate, imidacloprid, thiamethoxam, and sulfoxaflor; The mass ratio of compound a-07, compound a-15, compound b-17 or compound c-37 to the insecticide is 1:5-20.

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