Composition containing alanine-isoxazoline compound and acaricides
By combining alanine-isoxazoline compounds with various acaricide active ingredients in a specific ratio, an insecticidal and acaricidal composition is formed, which solves the problem of pest resistance caused by single active ingredients, and achieves highly efficient and low-dose pest control, suitable for agricultural and urban pest control.
Patent Information
- Application Number
- CN202410976336.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-20
- Publication Date
- 2026-01-20
AI Technical Summary
Existing single-active-component insecticides and acaricides are prone to leading to insecticide resistance in pests with long-term use, and existing mixtures are difficult to predict in terms of expanding the insecticidal spectrum and achieving both pest and disease control effects when selecting components.
A specific ratio of alanine-isoxazoline compounds and various acaricide active ingredients is used to form an insecticidal and acaricidal composition, including CHS1 inhibitors, ATP synthase inhibitors, mitochondrial electron transport complex inhibitors, etc. The mixing ratio is 1:100 to 100:1, and different formulations are prepared for agricultural and urban pest control.
It delays the development of pesticide resistance in pests, improves control efficacy, reduces dosage, minimizes environmental pollution, enhances control of resistant species, and lowers pesticide application costs for farmers.
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Figure CN121359720A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application belongs to the field of insecticide and acaricide, and relates to a composition containing alanine-isoxazoline compound and acaricide. BACKGROUND
[0002] In crop production such as agriculture and horticulture, the damage caused by pests and diseases is still very significant. Due to the diversity of biological species and the simultaneous occurrence of various pests and diseases, the field of plant protection has been in need of developing new insecticides and acaricides with better activity, lower dosage and more environmentally friendly. Insecticides and acaricides containing a single active ingredient are prone to cause pesticide resistance of pests when used continuously in pest control. Mixing two or more active ingredients into a mixed component can play an important role in expanding the insecticidal spectrum, controlling pests and vectors, controlling viral diseases, reducing the cost of pesticide application, and delaying the development of pesticide resistance. SUMMARY
[0003] In view of the deficiencies of the prior art, the present application aims to meet the increasing demand for insecticides and acaricides in the fields of agriculture, forestry and urban sanitation, and to provide a composition containing alanine-isoxazoline compound and acaricide.
[0004] To achieve the above-mentioned purpose, the technical solution adopted by the present application is as follows:
[0005] An insecticide and acaricide composition, the composition contains active ingredient A and active ingredient B, the weight ratio of active ingredient A to active ingredient B is 1:100-100:1; active ingredient B is selected from the group consisting of inhibitors affecting the growth of chitin synthase 1 (CHS1) mites, mitochondrial adenosine triphosphate (ATP) synthase inhibitors, mitochondrial electron transport complex (III) inhibitors, mitochondrial electron transport complex (I) inhibitors, acetyl coenzyme A carboxylase inhibitors, mitochondrial electron transport complex (II) inhibitors, trifluoroethyl sulfide acaricides or other insecticides and acaricides; the active ingredient A is selected from compound I, compound II or stereoisomers thereof or a mixture of stereoisomers thereof, the structures of compound I and compound II or stereoisomers thereof are as follows:
[0006]
[0007]
[0008] In some embodiments, the inhibitors affecting the growth of chitin synthase 1 (CHS1) mites are selected from the group consisting of clofentezine, flucycloxuron, hexythidene or etoxazole.
[0009] In some typical embodiments, the class of inhibitors affecting chitin synthase 1 (CHS1) mite growth is selected from clofentezine.
[0010] In some embodiments, the class of mitochondrial adenosine triphosphate (ATP) synthase inhibitors is selected from diafenthiuron, azocyclotin, cyhexatin, fenbutatin oxide, propargite, or clofentezine.
[0011] In some typical embodiments, the class of mitochondrial adenosine triphosphate (ATP) synthase inhibitors is selected from diafenthiuron or propargite.
[0012] In some embodiments, the class of mitochondrial electron transport complex (III) inhibitors is selected from hydramethylnon, acequinocyl, fluacyprim, or bifenazate.
[0013] In some typical embodiments, the class of mitochondrial electron transport complex (III) inhibitors is selected from bifenazate.
[0014] In some embodiments, the class of mitochondrial electron transport complex (I) inhibitors is selected from quinalphos, azocyclotin, pyridaben, pyrimidifen, pyriminostine, fenpyroximate, or rotenone.
[0015] In some typical embodiments, the class of mitochondrial electron transport complex (I) inhibitors is selected from pyridaben.
[0016] In some embodiments, the class of acetyl-CoA carboxylase inhibitors is selected from spirodiclofen, spiromesifen, methylobarbital, or spirotetramat.
[0017] In some typical embodiments, the class of acetyl-CoA carboxylase inhibitors is selected from spirodiclofen or spiromesifen.
[0018] In some embodiments, the class of mitochondrial electron transport complex (II) inhibitors is selected from cyanofenpham, ethyl tetrazoxide, cyflumetofen, or pyrazolynate;
[0019] In some typical embodiments, the class of mitochondrial electron transport complex (II) inhibitors is selected from ethyl tetrazoxide.
[0020] In some embodiments, the class of trifluoroethyl sulfide acaricides is selected from bentioflumin, bisulflufen, sulfiflumin, or flupentiofenox.
[0021] In some typical embodiments, the class of trifluoroethyl sulfide acaricides is selected from bentioflumin.
[0022] In some embodiments, the other class of insecticidal acaricides is selected from azadirachtin, dry ice, boric acid, sulphuryl fluoride, formetanate, sulcofuron-sodium, amitraz or veratridine.
[0023] In some typical embodiments, the other class of insecticidal acaricides is selected from veratridine.
[0024] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from hexythiazox; the weight ratio of the two active components is 30:1-1:30.
[0025] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from diafenthiuron or propargite; the weight ratio of the two active components is 30:1-1:100, preferably 1:100.
[0026] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from bifenazate; the weight ratio of the two active components is 30:1-1:30, preferably 1:15.
[0027] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from pyridaben; the weight ratio of the two active components is 30:1-1:30.
[0028] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from spirodiclofen or spiromesifen; the weight ratio of the two active components is 30:1-1:30, preferably 1:30.
[0029] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from ethyl (Z)-3-ethoxy-3-(2,2- dimethyl- vinyl)pyridazine-4-yl acetate; the weight ratio of the two active components is 30:1-1:30, preferably 1:2.
[0030] In some embodiments, the active component A is selected from compound I, compound II or a stereoisomer thereof, and the active component B is benzylaminobenzoate; the weight ratio of the two active components is 1:4.
[0031] In some embodiments, the active component A is compound I, compound II or a stereoisomer thereof, and the active component B is selected from veratridine; the weight ratio of the two active components is 30:1-1:30.
[0032] Further, the composition is mixed with a carrier and any one of the auxiliary agents to prepare a preparation containing the composition. The active ingredient of the composition in the preparation is accumulated at 0.5 wt% to 95 wt%. Preferably, the active ingredient in the preparation is accumulated at 1% to 85%.
[0033] The carrier of the present application can be solid or liquid, and any carrier commonly used for formulating pesticide compositions can be used. Suitable solid carriers include minerals, plants, synthetic fillers and inorganic salts. The minerals include silicates, carbonates, sulfates and oxides. The silicates are, for example, kaolin, meerschaum, permutite, montmorillonite, mica, vermiculite, pyrophyllite, talc. The carbonates are, for example, calcium carbonate, dolomite. The sulfates are, for example, ammonium sulfate, sodium sulfate, calcium sulfate. The oxides are, for example, quicklime, magnesia, diatomite. The plants are, for example, citrus pulp, corn cob core, chaff powder, rice hull, soybean straw powder, tobacco powder, walnut shell, sawdust. The synthetic fillers are, for example, precipitated calcium carbonate hydrate, precipitated calcium carbonate, white carbon black. The inorganic salts are, for example, potassium chloride, sodium chloride.
[0034] The liquid carriers include water and organic solvents. When the active ingredient is a suspoemulsion, the organic solvents play the role of solubilization and antifreezing. Suitable organic solvents include aromatic hydrocarbons, such as benzene, xylene, toluene, alkylbenzene, alkylnaphthalene and chlorinated aromatic hydrocarbons; chlorinated aliphatic hydrocarbons, such as chloroethylene, trichloromethane, dichloromethane, chloroform, carbon tetrachloride and polychloroethane; aliphatic hydrocarbons, such as petroleum distillate, cyclohexane, light mineral oil and paraffin wax. Alcohols, such as methanol, ethanol, isopropyl alcohol, butanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerol, fatty alcohol and the like; ethers, such as methyl glycol ether, ethyl glycol ether, petroleum ether. Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isofuroin, N-methyl-pyrrolidone; special solvents, such as dimethylformamide, dimethyl sulfoxide, polyethylene glycol, hexanitrile; vegetable oil and methylated vegetable oil. The above-mentioned organic solvents can be used alone or in combination, and can be used in combination with water.
[0035] The auxiliary agents of the present application can include one or more of surfactants, antifoaming agents, thickening agents, suspending agents and antifreezing agents, and can include other auxiliary agents commonly used in the industry as needed.
[0036] The surfactant can be an emulsifier, dispersant, stabilizer or wetting agent; it can be ionic or non-ionic. Suitable surfactants include: sodium and calcium salts of polyacrylic acid and lignin sulfonic acid; condensation products of fatty acids or fatty amines with ethylene oxide and / or propylene oxide containing at least 12 carbon atoms in the molecule; fatty acid esters of glycerol, dodecanol-1, tetradecanol-1, sorbitol, sucrose or pentaerythritol; and condensation products thereof with ethylene oxide and / or propylene oxide; sulfuric acid or sulfonic acid salts of their condensation products; alkali or alkaline earth metal salts of sulfuric acid or sulfonic acid containing at least 10 carbon atoms in the molecule, preferably sodium salts, such as sodium dodecyl sulfate, sodium secondary alkyl sulfate, sodium salts of sulfonated castor oil, sodium alkyl aryl sulfonates and sodium dodecyl benzene sulfonate; polymers of ethylene oxide, copolymers of ethylene oxide and propylene oxide.
[0037] The emulsifier includes non-ionic emulsifiers and anionic emulsifiers. The non-ionic emulsifiers are preferably nonylphenol polyoxyethylene ether, fatty alcohol polyoxyethylene ether, styryl phenyl polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styryl phenol formaldehyde resin polyoxyethylene polyoxypropylene ether, castor oil polyoxyethylene ether. The anionic emulsifiers mainly include calcium dodecyl benzene sulfonate, triphenyl ethyl phenol polyoxyethylene ether phosphate amine salt, nonylphenol polyoxyethylene ether phosphate amine salt, castor oil polyoxyethylene ether phosphate amine salt.
[0038] The dispersant described in the present application includes one or more of the following: acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalene sulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenyl ethyl phenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphoric acid, p-hydroxyphenyl lignin sulfonic acid sodium salt.
[0039] The wetting agent described in the present application includes one or more of the following: fatty alcohol polyoxyethylene ether, naphthalene sulfonate, sodium dodecyl sulfate, alkylphenol resin polyoxyethylene ether sulfate.
[0040] The thickening agent described in the present application includes one or more of the following: xanthan gum, magnesium aluminum silicate, sodium alginate, sodium carboxymethyl cellulose, gum arabic, gelatin, polyvinyl alcohol.
[0041] The defoaming agent described in the present application includes one or more of the following: Antifoam, silicone, C8-10 fatty alcohol, C10-20 saturated fatty acid and amide.
[0042] The bactericidal and insecticidal agent of the present application can be formulated into any of the agriculturally acceptable dosage forms, such as powdery formulation, granular formulation, dispersible powdery formulation, dispersible granular formulation, dispersible tablet formulation, soluble solid formulation, soluble liquid formulation, oil formulation, ultra-low volume formulation, dispersible liquid formulation, emulsion formulation, suspension formulation, suspoemulsion formulation, or seed coating formulation, as needed.
[0043] Use of a pesticidal and miticidal composition for the preparation of a pesticidal and miticidal agent for controlling agricultural pests or urban sanitary pests.
[0044] The agricultural pests include armyworm, beet armyworm, bollworm, cabbage moth, cabbage moth, codling moth, rice leaf roller, corn borer, rice borer, diamondback moth, cabbage worm, gypsy moth, fall armyworm, eastern tent caterpillar, subterranean pest, leaf miner, spotted leaf miner, aphid, leafhopper, flower scale insect, potato beetle, flea beetle, thrips, stink bug, red spider mite, hawthorn spider mite, citrus red mite, citrus rust mite, apple spider mite, two-spotted spider mite, gall mite, and acarid, and the urban pests include termite, cockroach, ant, fly, and mosquito. When used for controlling agricultural pests, the present application can be used for fruit trees, cereals, legumes, vegetables, and flowers, and for fruit trees such as apple, pear, citrus, litchi, cereals such as wheat, rice, legumes such as soybean, and beans, cotton, and vegetables such as cabbage, cauliflower, Chinese cabbage, rape, tomato, and pepper. When used for controlling urban pests, the present application can be used for homes, various public places, office places, and trees and dikes damaged by termites.
[0045] Further, the present application provides a method for using the pesticidal and miticidal composition, wherein the prepared pesticidal and miticidal agent is applied to pests to be controlled or a medium where the pests grow in an effective amount. The effective amount is usually selected from 10 g to 500 g per hectare, and preferably from 15 g to 100 g per hectare.
[0046] The present application has the following advantages: 1. The present application uses compounds having different mechanisms of action in insecticidal and miticidal activities in a specific ratio, and the compounds are mutually coordinated to delay the occurrence of pest resistance and improve the control effect on resistant populations, and the present application shows obvious synergistic effect in insecticidal and miticidal activities, and improves the control effect of single active ingredient compound in the composition on pests, and the synergistic effect of the present application is not linearly related to single agent.
[0047] 2. The application amount of the present application in the use of insecticidal and miticidal activities is obviously lower than that of single compound in the composition, thereby reducing the use cost and environmental pollution. DETAILED DESCRIPTION
[0048] The following examples can provide a more complete understanding of the application to those of ordinary skill in the art, but the application is not limited to the described examples.
[0049] Compound source and quality analysis:
[0050] Compound I was synthesized in the laboratory, and other compounds were extracted and purified by column chromatography after purchasing laboratory preparations.
[0051] Compound I: chiral HPLC analysis showed that it was a mixture containing stereoisomers I-1 and I-2, with a ratio of 95.766%:3.247%. Stereoisomers I-3 and I-4 were less than the detection limit.
[0052] 1 H NMR (400 MHz, DMSO-d6) δ 8.74-8.52 (m, 2H), 7.82 (d, J = 6.1 Hz, 2H), 7.59 (dd, J = 5.8, 2.0 Hz, 2H), 7.48 (d, J = 8.4 Hz, 1H), 4.48 (p, J = 7.2 Hz, 1H), 4.43-4.25 (m, 2H), 4.09-3.71 (m, 2H), 2.37 (s, 3H), 1.31 (d, J = 7.2 Hz, 3H).
[0053]
[0054] 3.71 (m, 2H), 2.37 (s, 3H), 1.31 (d, J = 7.2 Hz, 3H).
[0055] Laboratory bioactivity determination
[0056] Example 1: Determination of the synergistic effect of compositions containing compound I on Tetranychus cinnabarinus
[0057] Test object: Tetranychus cinnabarinus, adult mites, sensitive strain raised indoors.
[0058] Test conditions: temperature: 24-26°C, relative humidity: 60%, light: L:D = 14:10.
[0059] Preparation of liquid medicine: according to different test needs, the test samples (different ratio compositions of the application and technical material) were accurately weighed by an electronic analytical balance, among which the technical material was dissolved in acetone, and then diluted with 0.1% Tween 80 water to a certain concentration of liquid medicine according to the test design dose.
[0060] Test method: The pot seedling spray method was used to determine the activity of the compounds on T. cinnabarinus adults. First, 40-90 T. cinnabarinus adults of uniform size were attached to the first pair of fully expanded leaves of bean seedlings (one leaf was left), and the base number was counted after the adults were stable. Then, the test materials were treated with the pesticide solution using the Airbrush method, 1.5 mL per plant, and a blank control was set up.
[0061] After natural air drying, the treated test materials were placed in an observation room with adjustable temperature, humidity, and light. After 72 h, the number of live mites was investigated, and the mortality rate was calculated. The Bliss method was used for evaluation, which is one of the classic methods for evaluating the effects of mixtures. According to the independent joint action concept proposed by Bliss, the theoretical mortality rate P of insecticides and miticides when mixed can be calculated as follows:
[0062] P = P m + P n (1-P m )
[0063] P m is the mortality rate (%) of the target at a concentration of m for the first active component; P n is the mortality rate (%) of the target at a concentration of n for the second active component.
[0064] If the actual mortality rate of the target after mixing the two active components at a certain concentration is greater than the theoretical mortality rate P, it is determined that the two active components have a synergistic effect when used in the specified concentration, otherwise it is an antagonistic effect.
[0065] The results are shown in Table 1.
[0066] Table 1 Synergistic effect of compound I mixed with 5 pesticides such as ethylazocyclotin on T. cinnabarinus adults
[0067]
[0068] As shown in the above table, the compound I mixed with ethylazocyclotin, spirodiclofen, propargite, bifenthrin, and fenbutatin-oxide has a significant synergistic effect on T. cinnabarinus adults.
Claims
1. A pesticidal acaricidal composition, the composition comprising an active ingredient A and an active ingredient B, the weight ratio of the active ingredient A to the active ingredient B being 1:100-100:1; the active ingredient B being selected from the group consisting of inhibitors of chitin synthase 1 mite growth, mitochondrial ATP synthase inhibitors, mitochondrial electron transport complex (III) inhibitors, mitochondrial electron transport complex (I) inhibitors, acetyl-CoA carboxylase inhibitors, mitochondrial electron transport complex (II) inhibitors, trifluoromethylsulphide acaricides or other pesticidal acaricides; the active ingredient A being selected from the group consisting of compound I, compound II or stereoisomers thereof, the structures of the compound I, the compound II or the stereoisomers thereof being as follows:
2. The pesticidal acaricidal composition according to claim 1, characterized in that: the inhibitors of chitin synthase 1 mite growth in the active ingredient B are selected from the group consisting of clofentezine, flucycloxuron, hexythidene or etoxazole; the mitochondrial ATP synthase inhibitors are selected from the group consisting of diafenthiuron, azocyclotin, fenbutatin oxide, propargite or clofentezine; the mitochondrial electron transport complex (III) inhibitors are selected from the group consisting of hydramethylnon, acequinocyl, pyridaben or bifenazate; the mitochondrial electron transport complex (I) inhibitors are selected from the group consisting of quimacryl, clofentazine, pyridaben, pyrimidifen, pyrimithan, clofentezine or rotenone; the acetyl-CoA carboxylase inhibitors are selected from the group consisting of spirodiclofen, spiromesifen, methylobarbital or spirotetramat; the mitochondrial electron transport complex (II) inhibitors are selected from the group consisting of cyanofenpham, ethyl azolcarbimide, butofenpyrad or pyraziflumid; the trifluoromethylsulphide acaricides are selected from the group consisting of bentioflumin, bisulflufen, sulfiflumin or flupentiofenox; the other pesticidal acaricides are selected from the group consisting of azadirachtin, dry ice, boric acid, sulfonyl fluoride, pyrimithan, Sulcofuron-sodium, amitraz or veratridine. The active ingredient A is selected from the group consisting of compound I, compound II or stereoisomers thereof, the active ingredient B is selected from etoxazole, the weight ratio of the two active ingredients being 30:1-1:30; preferably, the active ingredient A is selected from the group consisting of compound I, compound II or stereoisomers thereof, the active ingredient B is selected from veratridine; the weight ratio of the two active ingredients being 30:1-1:30; preferably, the active ingredient A is selected from the group consisting of compound I, compound II or stereoisomers thereof, the active ingredient B is selected from pyridaben; the weight ratio of the two active ingredients being 30:1-1:
30. The active ingredient A is selected from the group consisting of compound I, compound II or stereoisomers thereof, the active ingredient B is selected from propargite; the weight ratio of the two active ingredients being 1:
100. The active ingredient A is selected from the group consisting of compound I, compound II or stereoisomers thereof, the active ingredient B is selected from bifenazate; the weight ratio of the two active ingredients being 1:
15. 3. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, 4. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, 5. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, 6. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, The active ingredient A is selected from compound I, compound II or its stereoisomers, the active ingredient B is selected from spirodiclofen; the weight ratio of the two active ingredients is 1:
30.
7. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, The active ingredient A is selected from compound I, compound II or its stereoisomers, the active ingredient B is selected from ethyl (Z)-3-ethoxy-3-(2,4-dioxo-1-imidazolidin-4-yl)prop-2-enoate; the weight ratio of the two active ingredients is 1:
2.
8. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, The active ingredient A is selected from compound I, compound II or its stereoisomers, the active ingredient B is selected from ethyl (Z)-3-ethoxy-3-(2,4-dioxo-1-imidazolidin-4-yl)prop-2-enoate; the weight ratio of the two active ingredients is 1:
2.
9. The insecticidal and miticidal composition according to claim 1 or 2, characterized by, The active ingredient A is selected from compound I, compound II or its stereoisomers, the active ingredient B is selected from ethyl (Z)-3-ethoxy-3-(2,4-dioxo-1-imidazolidin-4-yl)prop-2-enoate; the weight ratio of the two active ingredients is 1:
2.
10. Use of a pesticidal composition according to claim 1 or 2, characterized in that The active ingredient A is selected from compound I, compound II or its stereoisomers, the active ingredient B is selected from ethyl (Z)-3-ethoxy-3-(2,4-dioxo-1-imidazolidin-4-yl)prop-2-enoate; the weight ratio of the two active ingredients is 1:
2. The composition is used for preparing an insecticide and acaricide for controlling agricultural pests or urban sanitary pests. The composition is used for preparing an insecticide and acaricide for controlling agricultural pests or urban sanitary pests.