Synergistic insecticide composition and application thereof

Abstract

The invention discloses a synergistic insecticidal composition which comprises an effective component A and an effective component B. The effective component A is imidaclothiz, and the effective component B is ethiprole. The weight ratio of the effective component A to the effective component B in the insecticidal composition is 3: 1 and 28: 1, and the effective components of the insecticidal composition are matched according to the ratio to achieve a certain synergistic effect, so that the use amount of the pesticide active components can be reduced, and the generation of drug resistance of a controlled object is delayed.

Description

Technical Field

[0001] This invention belongs to the field of agricultural pest and disease control technology, specifically relating to an insecticidal composition containing chlorothiazoline and acetamiprid and its application. Background Technology

[0002] Rice is a staple crop in China, with an average annual planting area of ​​approximately 30 million hectares, playing a vital role in ensuring food security. Brown planthopper *Nilaparvata lugens* The brown planthopper, belonging to the family Plantipodidae in the order Hemiptera, is a major piercing-sucking pest of rice. It is prevalent in major rice-producing areas of Asia and has been listed as a Class I pest in my country. The brown planthopper completes its entire life cycle on rice and its wild relatives, making it a typical monophagous pest. The main damage caused by the brown planthopper to rice includes: 1) feeding damage by sucking nutrients from the base of the rice stem; 2) oviposition damage caused by adults laying eggs inside the leaf sheaths, damaging the rice's vascular tissue; and 3) transmitting rice viral diseases such as toothed leaf dwarf disease and inducing the spread of diseases such as sheath blight and sooty mold.

[0003] To ensure rice yield, chemical control remains the primary means of controlling rice pests. However, the unscientific, widespread, and intensive use of chemical pesticides has led to resistance in brown planthoppers to different types of pesticides, gradually increasing the pressure on field control. Simultaneously, the large-scale application of chemical pesticides in rice paddies also impacts natural enemies of pests such as spiders, disrupting the balance of the rice paddy ecosystem and causing further pest infestations. Faced with increasing pest resistance and the slow pace of new single-agent pesticide development, the development of pesticide combination formulations can not only effectively suppress the rise in pesticide resistance but also reduce production and usage costs, be more environmentally friendly, and achieve more significant control effects. Achieving highly efficient control of brown planthoppers and reducing pesticide use through pesticide combination is the primary technical problem this invention aims to solve.

[0004] Imidaclothiz is a thiazole heterocyclic neonicotinoid insecticide independently developed and officially registered in my country. Its chemical name is 1-octanolphenol-3-(2-flufenoxuronyl)-4-methyl-1H-thiazolyl-5-amine, and its structural formula is:

[0005]

[0006] CAS No. 105843-36-5, Molecular formula: C7H8ClN5O2S, Molecular weight: 261.69, Soluble in water and most organic solvents.

[0007] Chlorthiazoline selectively inhibits nicotinic acid acetylcholinesterase receptors in the insect nervous system, blocking nerve conduction and causing insects to become excited, spasm, paralyzed, and die. Its insecticidal activity is 10-20 times that of common neonicotinoid pesticides (such as imidacloprid), and it is not limited by temperature. Chlorthiazoline has a very broad insecticidal spectrum, controlling not only rice leafhoppers, planthoppers, and thrips, but also lepidopteran, dipteran, and coleopteran pests, especially showing good control of rice stem borers. Chlorthiazoline has a short half-life in crops (0.58-4.39 days in vegetables), and the residue risk is controllable, meeting the requirements of pollution-free agricultural production.

[0008] Ethiprole is a benzylpyrazole insecticide. Its molecular structure contains a chiral sulfur atom. Its chemical name is 5-amino-1-(2,6-dichloro-α,α,α-(trifluoro-p-tolyl)-4-ethylsulfinylpyrazole-3-carboxynitrile), and its structural formula is:

[0009]

[0010] Molecular formula: C 13 H9C l2 F3N4OS, CAS No. 181587-01-9, relative molecular mass 397.2.

[0011] Ethyleneprol has a broad insecticidal spectrum, primarily acting by interfering with the normal function of chloride ion channels in pests by affecting the γ-aminobutyric acid receptor (GABAR), thereby disrupting the normal functioning of the pest's central nervous system and ultimately leading to pest death. It does not exhibit cross-resistance with organophosphates, pyrethroids, carbamates, or neonicotinoids. Ethyleneprol is mainly a contact insecticide, with little or no systemic activity, and can be used to control various piercing-sucking pests (such as brown planthoppers, thrips, and aphids).

[0012] In the process of applying insecticides to control pests, long-term, continuous, and high-dose use of a single type or single mode of action of chemical insecticide can easily lead to problems such as the evolution of insecticide resistance in pests. The rational combination or mixing of different types of insecticide compounds has advantages such as reducing the amount of pesticide used, improving control efficacy, and delaying the development of insecticide resistance in pests, and is one of the effective methods to solve the above problems. To date, there have been no reports on the combined use of chlorothalonil and acetamiprid for the control of piercing-sucking pests such as brown planthoppers, white-backed planthoppers, aphids, thrips, whiteflies, citrus psyllids, and leafhoppers. Summary of the Invention

[0013] The purpose of this invention is to address the shortcomings of existing technologies by providing an synergistic composition containing chlorothiazoline and acetamiprid as the main active ingredients. This composition is suitable for agricultural use, has no cross-resistance, is safe, can extend the pesticide's lifespan, and has excellent control effects on piercing-sucking pests.

[0014] Given that single agents are difficult to meet the increasingly serious needs for the control of rice pests in agriculture, in order to achieve the purpose of this invention, the inventors conducted a large number of compound screening experiments and unexpectedly discovered that chlorothiazoline and acetamiprid, when combined in a certain proportion, have a significant synergistic effect on brown planthopper.

[0015] Based on the above findings, and through quantitative analysis of the combined effects of the compositions, the technical solution of this invention was formulated:

[0016] The synergistic insecticidal composition includes active ingredient A and active ingredient B; wherein, active ingredient A is chlorothiazoline and active ingredient B is acetamiprid.

[0017] Preferably, as a preferred embodiment, the weight ratio of active ingredient A to active ingredient B ranges from 3:1 to 28:1.

[0018] Based on the above scheme, the weight ratio of active ingredient A to active ingredient B is 3:1.

[0019] Based on the above scheme, the weight ratio of active ingredient A to active ingredient B is 28:1.

[0020] Within a defined weight ratio, active ingredient A and active ingredient B are mixed to achieve a synergistic effect.

[0021] Based on the above scheme, the mass percentage of active ingredient A and active ingredient B in the insecticide composition accounts for 1-95% of the total.

[0022] Based on the above scheme, the insecticide composition contains 1-20% by mass of active ingredient A and active ingredient B.

[0023] Based on the above scheme, the synergistic insecticidal composition also includes conventional pesticide adjuvants, which may be carriers, surfactants, etc.

[0024] The carrier refers to an organic or inorganic, natural or synthetic substance. They facilitate the application of the active ingredient and are generally inert and must be agriculturally acceptable, particularly to the treated plant. The carrier can be solid, such as clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or waxy hydrocarbons, chlorinated hydrocarbons, liquefied gas, etc.

[0025] The surfactant may include emulsifiers, dispersants, or wetting agents, and may be ionic or nonionic. Examples include salts of polyacrylic acid, lignin sulfonates, salts of phenol sulfonic acid or naphthalene sulfonic acid, polymers of ethylene oxide with aliphatic alcohols or with aliphatic acids or with aliphatic amines and substituted phenols (especially alkylphenols or arylphenols), sulfosuccinates, taurine derivatives (especially alkyl taurine esters), and phosphate esters of alcohols or polyhydroxyethylated phenols, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated hexadecyl, heptadecanols, and octadecyl alcohols, as well as sulfated fatty alcohol glycol ethers, and naphthalene or naphthalene sulfonic acid with phenol and formaldehyde. Condensations, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl polyethylene glycol ether, tributylphenyl polyethylene glycol ether, tripearylphenyl polyethylene glycol ether, alkylaryl polyether alcohol, alcohols and fatty alcohols / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl polyethylene glycol ether acetal, sorbitan ester, lignin sulfite waste liquid, and proteins, denatured proteins, polysaccharides (e.g., methylcellulose), hydrophobically modified starch, polyvinyl alcohol, polycarboxylates, polyalkoxylated compounds, polyethyleneamine, polyvinylpyrrolidone and copolymers thereof. At least one surfactant is required to facilitate the dispersion of the active ingredients in water and to facilitate their proper application to plants.

[0026] The insecticidal composition may also contain various other components, such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, film-forming agents, dyes, colorants, and polymers.

[0027] The insecticidal composition can be diluted or used directly by the user before application. It can be prepared using conventional processing methods, which involve mixing the active substance with a liquid solvent or solid carrier, and then adding one or more surfactants such as dispersants, stabilizers, wetting agents, binders, and defoamers.

[0028] Based on the above scheme, the specific formulation of the insecticidal composition is a suspension, microemulsion, suspension emulsion, water emulsion, dispersible oil suspension, wettable powder, water-dispersible granules, or suspension seed coating agent.

[0029] For example, a suspension product is prepared by using water as the dispersion medium and processing the active ingredients and adjuvants (wetting agents, dispersants, thickeners, antifreeze agents, pH adjusters, defoamers, etc.) in the above formula through three wet ultra-fine pulverization processes: shearing, colloid milling, and sand milling, followed by treatment with a high-speed mixer and homogenizer.

[0030] In short, the compositions of the present invention can be mixed with solid and liquid additives conventionally used in prior art formulations.

[0031] The above-mentioned synergistic insecticide composition is used to control piercing-sucking pests in field crops, vegetables, and fruit trees.

[0032] Based on the above scheme, the piercing-sucking pests are brown planthoppers, white-backed planthoppers, aphids, thrips, whiteflies, citrus psyllids, and small green leafhoppers.

[0033] Compared with existing inventions, this invention has the following beneficial effects: (1) Compared with single agents, this insecticidal composition has a significant synergistic effect on piercing-sucking pests, which significantly improves the control effect; (2) It has low toxicity, can replace highly toxic pesticides, and greatly reduces the amount of pesticides used in the field, effectively reducing environmental pollution and pesticide residues; (3) Compared with single agents, the production and use costs are reduced and the effect is more significant; (4) The main active ingredients have different toxic mechanisms against pests, and the compound can effectively inhibit the increased resistance of piercing-sucking pests to pesticides. Detailed Implementation

[0034] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0035] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described below with reference to specific embodiments. However, this invention is by no means limited to these examples. The following descriptions are merely preferred embodiments of the invention and are only used to explain the invention. They should not be construed as limiting the scope of this patent.

[0036] Combining the active ingredients of different pesticides to create new pesticides is currently an effective and rapid method for developing and researching new pesticides. When different pesticides are mixed, they typically exhibit three types of effects: additive, synergistic, and antagonistic. However, the specific type of effect is unpredictable and can only be determined through extensive testing. Well-formulated, highly synergistic compounds can significantly improve actual control efficacy, reduce pesticide usage, and thus help delay the development of pesticide resistance in pests, making them an important means of integrated pest management.

[0037] I. Example 1

[0038] The control effect of a combination of active ingredient A (chlorothiazoline) and active ingredient B (one of acetamiprid or phoxim) on pests was studied by indoor toxicity assays.

[0039] 1. Experimental Materials

[0040] 1.1 Test insect source

[0041] The brown planthopper population tested was originally collected from rice fields of the Hunan Academy of Agricultural Sciences and was continuously raised indoors for 3 years without any contact with pesticides.

[0042] 1.2 Test reagents

[0043] 93% Chlorpyrifos technical grade (Shandong Zouping Pesticide Co., Ltd.), 90% Phoxim technical grade (Hubei Jiahuixingcheng Biotechnology Co., Ltd.), 95% Ethiophanate-methyl technical grade (Hubei Jiahuixingcheng Biotechnology Co., Ltd.).

[0044] 2 Experimental Methods

[0045] 2.1 Rice seedling soaking method

[0046] Referring to the "Technical Specification for Monitoring Resistance of Brown Planthopper in Rice" (Y / T1708-2009), the indoor bio-activation assay for enhanced efficacy was conducted using the rice seedling immersion method. The prepared emulsifiable concentrate was diluted with 0.1% Triton X-100 aqueous solution to prepare a series of concentrations, with 5-7 concentration gradients for each experiment. Using the 0.1% Triton X-100 aqueous solution as a control, 10-15 healthy rice seedlings of similar growth were immersed in the series of concentrations of the solution for 30 seconds, then removed and air-dried. The roots of the seedlings were wrapped with absorbent cotton, and the bottom was submerged in water before being placed in disposable plastic cups. Each cup was inoculated with 15 standard, uniformly sized mid-3rd instar nymphs, and sealed with fine gauze. Each concentration was repeated 3-4 times. After inoculation, the seedlings were placed in an intelligent artificial climate chamber with a temperature of (28±1)℃, a relative humidity of 75%±5%, and a photoperiod of 16L:8D. After 96 hours of treatment, the mortality rate of each treatment insect was checked. The standard for death was that the insect did not move when lightly touched with a brush. The corrected mortality rate was then calculated.

[0047] 2.2 Screening for the optimal ratio of active ingredients

[0048] First, the bioactivity of two single agents, A and B, was determined using the rice seedling immersion method, and the LC ratios of the two single agents were obtained. 50 The values ​​were then compared with the LC values ​​of the two single agents. 50 The concentration was set to 100%, and the sample was divided into 10 equal parts. Then, LC-12 was performed according to the following ratio. 50 Concentrations were achieved by mixing agents A and B in the following ratios: (10:0), (9:1), (7:3), (5:5), (3:7), (1:9), and (0:10). The mortality rate of the test insects was determined using the rice seedling immersion method at these different ratios. The expected mortality rate and toxicity-efficacy ratio were calculated using the following formulas to determine the optimal ratio. A toxicity-efficacy ratio greater than 1.25 indicates a synergistic effect, while a ratio less than 0.75 indicates an antagonistic effect.

[0049] Expected mortality rate (%) = LC of pesticide A 50 Actual mortality rate × Proportion of pesticide A

[0050] +B pesticide LC 50 Actual mortality rate × Proportion of pesticide B

[0051]

[0052] The LC-1 of the optimal ratio of the mixed pesticides was determined using the rice seedling immersion method. 50 And calculate the co-toxicity coefficient.

[0053] 2.3 Data Analysis

[0054] The data were processed and analyzed using Microsoft Excel (2016) and SPSS 12.0 software to calculate the slope of the indoor bioactivity assay and the lethal final concentration (LC). 50 The co-toxicity coefficient (CTC) was calculated according to Sun Yunpei's method (1960), and the synergistic effect of the compound was evaluated based on the magnitude of the CTC.

[0055] ATI = 100 × S / M

[0056] In the formula:

[0057] ATI – Actual Measured Toxicity Index of Mixtures

[0058] S---LC of standard insecticides 50 The unit is milligrams per liter (mg / L).

[0059] M---LC of the mixture 50 The unit is milligrams per liter (mg / L).

[0060] TTI = TIA × PA + TIB × PB

[0061] In the formula:

[0062] TTI – Theoretical Toxicity Index of Mixtures;

[0063] TIA – Drug Toxicity Index;

[0064] PA---Percentage content of agent A in the mixture, expressed as a percentage.

[0065] TIB---B drug toxicity index;

[0066] PB --- The percentage content of agent B in the mixture, expressed as a percentage.

[0067] CTC = 100 × ATI / TTI

[0068] In the formula:

[0069] CTC --- Cotoxicity coefficient;

[0070] ATI – Actual Measured Toxicity Index of Mixtures;

[0071] TTI – Theoretical Toxicity Index of Mixtures.

[0072] The co-toxicity coefficient (CTC) of the compound is ≥120, which shows a synergistic effect; CTC≤80 shows an antagonistic effect; and 80<CTC<120 shows an additive effect.

[0073] 3. Results and Analysis

[0074] Please refer to Tables 1-4 for the experimental results.

[0075] Table 1. Results of toxicity assays of three pesticides against brown planthoppers.

[0076]

[0077] Table 2. Determination of the toxicity ratio of different mixtures of chlorothiazoline and acetamiprid against brown planthopper.

[0078]

[0079] Table 3. Determination of the toxicity ratio of different mixtures of chlorothiazoline and phoxim against brown planthoppers.

[0080]

[0081] Table 4. Toxicity determination of chlorothiazoline and acetamiprid at the optimal ratio (3:1) against brown planthopper.

[0082]

[0083] Table 2 shows that chlorothiazoline and acetaminophen only exhibit synergistic effects when mixed at active ingredient mass ratios of 3:1 and 28:1 (ratios near these ratios may also have synergistic effects), with 3:1 showing the best effect. Further experiments indicate that the co-toxicity coefficient of chlorothiazoline·acetaminophen (3:1) is 160.58 (Table 4), exceeding the criterion of 120, indicating a good synergistic effect. However, chlorothiazoline and acetaminophen mixed in other ratios shown in Table 2 exhibit antagonistic or additive effects, without any synergistic effect.

[0084] Although chlorthiazoline and phoxim have different mechanisms of action and belong to different categories of insecticides, their combination is basically antagonistic and has no synergistic effect (Table 3).

[0085] II. Example 2

[0086] 1. Preparation method and application of 20% chlorothiazoline·acetonitrile suspension concentrate

[0087] The composition is as follows (each component is expressed as a percentage by weight):

[0088] 15% chlorothiazoline, 5% acetamiprid, 5% sodium alkylnaphthalene sulfonate formaldehyde condensate (dispersant), 3% castor oil polyoxyethylene ether (emulsifier), 5% fatty alcohol polyoxyethylene ether (emulsifier), 3% sodium methylene bisnaphthalene sulfonate (wetting agent), 2% xanthan gum (thickener), 4% glycerol (antifreeze agent), water to 100%.

[0089] The preparation method is as follows: Mix all active ingredients, various additives and water in proportion, put them into a sand mill and grind them to a particle size of 5μm to obtain 20% acetamiprid·malathion suspension.

[0090] This insecticide composition is used to control brown planthoppers. It should be applied during the peak hatching period or when young larvae are abundant, and different concentrations should be diluted with water for spraying. The control effect 7 days after application is shown in Table 5.

[0091] Table 5. Field efficacy of the mixture of chlorothiazoline and acetamiprid in controlling brown planthoppers.

[0092]

[0093]

[0094] As shown in Table 5, the combination of chlorthiazoline and acetamiprid has a significant synergistic effect. With a lower dosage of active ingredient, the control effect on brown planthopper is significantly better than that of chlorthiazoline alone, and similar to that of acetamiprid alone.

[0095] The present invention and its embodiments have been described above. This description is not restrictive, and actual embodiments are not limited thereto. In conclusion, if those skilled in the art are inspired by this description and, without departing from the spirit of the invention, design similar structures and embodiments to this technical solution, such designs should fall within the protection scope of the present invention.

Claims

1. A synergistic insecticidal composition, characterized in that, It includes active ingredient A and active ingredient B; where active ingredient A is chlorothiazoline and active ingredient B is acetamiprid.

2. The synergistic insecticidal composition according to claim 1, characterized in that, The weight ratio of active ingredient A to active ingredient B is 3:

1.

3. The synergistic insecticidal composition according to claim 1, characterized in that, The weight ratio of active ingredient A to active ingredient B is 28:

1.

4. The synergistic insecticide composition according to claim 1, characterized in that, The active ingredients A and B account for 1-95% of the total mass.

5. The synergistic insecticide composition according to claim 4, characterized in that, The active ingredients A and B account for 1-20% of the total mass.

6. The synergistic insecticide composition according to claim 1, characterized in that, The specific formulation of the synergistic insecticidal composition is any one of the following: suspension concentrate, microemulsion, suspension emulsion, water emulsion, dispersible oil suspension, wettable powder, water-dispersible granules, and suspension seed coating agent.

7. The use of the synergistic insecticide composition according to any one of claims 1 to 6 in the control of piercing-sucking pests in field crops, vegetables, and fruit trees.

8. The application according to claim 7, characterized in that, The piercing-sucking pests are brown planthoppers, white-backed planthoppers, as well as aphids, thrips, whiteflies, citrus psyllids, and small green leafhoppers.

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