Composition containing carbosulfan, clothianidin and fludioxonil and application thereof

Abstract

The invention provides a composition containing carbosulfan, clothianidin and fludioxonil and application of the composition. The composition is prepared from carbosulfan, clothianidin and fludioxonil which serve as effective components. The effective components in the pesticide composition disclosed by the invention have a relatively good synergistic effect, and the pesticide composition has a very good application prospect.

Description

Technical Field

[0001] This invention relates to the field of pesticides, specifically to the application of a formulation containing a composition of carbofuran, thiamethoxam and fludioxonil, and the formulation containing the above composition in the prevention and control of plant diseases and pests. Background Technology

[0002] Carbosulfan, also known as Haoniandong or Anmiante, is a carbamate insecticide and acaricide with the chemical formula C. 20 H 32 N2O3S, CAS No. 55285-14-8, has the structural formula shown in Formula 1:

[0003]

[0004] Formula 1.

[0005] Pure carbofuran is a colorless or pale yellow oily liquid with a density of 1.1 ± 0.1 g / cm³ and a vapor pressure of 4.1 × 10⁻⁶. 4 Pa (25℃), sparingly soluble in water, readily soluble in organic solvents. Its oral LD50 in rats... 50 The dosage for male rats is 224 mg / kg, and for female rats it is 187 mg / kg, classifying it as a moderately toxic pesticide. This agent inhibits the activity of acetylcholinesterase and carboxylesterase, exhibiting contact and stomach poison effects against pests such as aphids, stem borers, and leafhoppers. It is characterized by strong penetration, low residue, and rapid action, and has low toxicity to natural enemies and beneficial organisms, making it a safe alternative to the highly toxic pesticide carbofuran. It is mainly used to control pests on crops such as citrus, cotton, and rice, and is highly effective in controlling various pests including rust mites, leaf miners, thrips, and sugarcane borers.

[0006] Thiamethoxam is the common name for the compound (E)-1-(2-chloro-1,3-thiazolylmethyl)-3-methyl-2-nitroguanidine; 1-(2-chloro-5-thiazolylmethyl)-3-methyl-2-nitroguanidine, with the English common name clothianidin. Its molecular formula is C6H8ClN5O2S, its relative molecular weight is 249.7, and its CAS number is 210880-92-5. Its structural formula is shown in Formula 2.

[0007]

[0008] Equation 2.

[0009] Thiamethoxam is a neonicotinoid insecticide, a novel, highly effective, safe, and selective insecticide. Its action is similar to that of nicotinic acetylcholine receptors, exhibiting contact, stomach poison, and systemic activity. It is mainly used on rice, vegetables, fruit trees, and other crops to control aphids, leafhoppers, thrips, planthoppers, and other pests belonging to the orders Hemiptera, Coleoptera, Diptera, and some Lepidoptera. It boasts advantages such as high efficiency, broad spectrum, low dosage, low toxicity, long-lasting effect, no phytotoxicity to crops, safe use, and no cross-resistance with conventional pesticides. It exhibits excellent systemic and penetrating effects, making it another alternative to highly toxic organophosphate pesticides. Its novel and unique structure, coupled with superior performance compared to traditional neonicotinoid insecticides, suggests it has the potential to become a globally recognized major insecticide.

[0010] Fludioxonil is a non-systemic fungicide that can be absorbed through plant tissues and inhibit the activity of mitogen-activated protein kinases in the osmotic signaling process. Fludioxonil is the common name for the compound 4-(2,2-difluoro-1,3-benzodioxane-4-yl)pyrrolo-3-onitrile, with the molecular formula C2. 12 H6F2N2O2, with a relative molecular weight of 248.2 and CAS number 131341-86-1, has the structural formula shown in Formula 3:

[0011]

[0012] Formula 3.

[0013] Those skilled in the art know that the effects of pesticide mixtures are unpredictable, typically exhibiting antagonistic, additive, or synergistic effects. There are no prior art reports on mixtures of thiamethoxam, thiamethoxam, and fludioxonil. The inventors of this application, through research, discovered that mixing thiamethoxam, thiamethoxam, and fludioxonil has a good synergistic effect. Therefore, this invention was completed. Summary of the Invention

[0014] This invention provides a specific synergistic ternary pesticide composition, which consists of the active ingredients carbofuran, thiamethoxam, and fludioxonil. Preferably, the mass ratio of carbofuran, thiamethoxam, and fludioxonil is 24-8:8-24:0.5-4.

[0015] A second aspect of the present invention provides a pesticide composition comprising the pesticide composition described herein and a suitable pesticide adjuvant.

[0016] This invention also provides the application of the compositions and formulations of this invention in the prevention and control of plant diseases and pests. Detailed Implementation

[0017] The specific embodiments of the present invention will be further described in detail below with reference to the examples. To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "comprising" or its variations such as "including" or "comprising of," etc., will be understood to include the stated components or steps, without excluding other substances or steps.

[0018] Furthermore, to better illustrate the present invention, numerous specific details are provided in the following detailed embodiments. Those skilled in the art should understand that the present invention can be practiced without certain specific details. In some embodiments, materials, methods, and means well-known to those skilled in the art are not described in detail in order to highlight the spirit of the invention.

[0019] The content of this invention generally refers to the mass percentage.

[0020] The present invention first provides a pesticide composition comprising the active ingredients carbofuran, thiamethoxam and fludioxonil.

[0021] Preferably, the mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 24-8:8-24:0.5-4.

[0022] Preferably, the mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 24:8:0.5-4, and particularly preferred are 24:8:0.5, 24:8:1, 24:8:2, 24:8:3, or 24:8:4.

[0023] Preferably, the mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 8:8:0.5-4, and particularly preferably 8:8:0.5, 8:8:1, 8:8:2, 8:8:3, or 8:8:4.

[0024] Preferably, the mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 8:24:0.5-4, and particularly preferred are 8:24:0.5, 8:24:1, 8:24:2, 8:24:3, or 8:24:4.

[0025] This invention also provides a pesticide formulation prepared by comprising the pesticide composition described above and a suitable pesticide adjuvant. The combination and adjuvant of this invention can be formulated into suitable pesticide formulations.

[0026] The additives described in this invention include one or more of the following: emulsifiers, dispersants, wetting agents, penetrants, antifreeze agents, pH adjusters, defoamers, disintegrants, binders, film-forming agents, warning colors, solvents, fillers / carriers, etc.

[0027] Emulsifiers include, but are not limited to, fatty alcohol polyoxyethylene ether, nonylphenol polyoxyethylene ether, fatty amine polyoxyethylene ether, alkyl glycosides, agricultural emulsion series: agricultural emulsion 601#, agricultural emulsion 602#, agricultural emulsion 603#, agricultural emulsion 604#, agricultural emulsion 401#, agricultural emulsion 402#, agricultural emulsion 700#, agricultural emulsion 33#, agricultural emulsion 34#, agricultural emulsion 1601#, agricultural emulsion 1602#, etc., Tween series: Tween-20, Tween-40, Tween-60, Tween-65, Tween-80, Tween-85, etc., castor oil polyoxyethylene ether, polyoxyethylene oleate, ethylene oxide / propylene oxide co-ether, polyglycerol fatty acid ester, polyoxyethylene ether sulfate salt, polyoxyethylene ether phosphate salt, etc.

[0028] Dispersants include, but are not limited to, one or more of the following: nonionic comb copolymers, sodium succinate diester sulfonate, polycarboxylate, naphthalene or alkylnaphthalene formaldehyde condensate sulfonate, phosphate salts, polyoxyethylene polyether block copolymers, lignin sulfonates, fatty alcohol polyoxypropylene polyoxyethylene ether, polyoxyethylene ether sulfate salts, etc.

[0029] Wetting agents / penetrating agents, such as castor oil polyoxyethylene ether, EO / PO block copolymers: 500LQ, WINN 5503, etc., alkylphenol polyoxyethylene ethers: including NP, TX, OP series, etc., fatty alcohol ethers: including MOA series, isomeric alcohol ether 1300 series, penetrant JFC, emulsifier AEO, etc., fatty amine polyoxyethylene ethers: including AC-1800 series, AN-1800 series, AC-1200 series, etc., polyarylphenol polyoxyethylene ethers: including agricultural emulsion 600#, agricultural emulsion 400#, agricultural emulsion 33#, agricultural emulsion 34#, etc., alkyl glycosides: including C12-C14 alkyl glycosides, C8-C10 alkyl glycosides, C8-C14 alkyl glycosides, etc., sodium alkyl succinate sulfonate: including fast T, etc., polycyclic aromatic hydrocarbon formaldehyde condensate sulfonate or alkyl aromatic hydrocarbon sulfonate: including pull-opening powder BX, etc., one or more of the following, but not limited to: sodium salt of fatty alcohol ether sulfate AES, sodium dodecyl sulfate, sodium α-alkenyl sulfonate, etc.

[0030] Solvents include, but are not limited to, methanol, ethanol, acetone, toluene, solvent oil 200, solvent oil 150 (S-150), deionized water, etc.

[0031] Antifreeze agents include, but are not limited to, one or more of the following: ethylene glycol, propylene glycol, glycerol, diethylene glycol, ethylene glycol butyl ether, propylene glycol butyl ether, polyethylene glycol, urea, etc.

[0032] pH adjusters include, but are not limited to, one or more of the following: triethanolamine, ammonium sulfate, ammonium nitrate, ammonium chloride, hydrochloric acid, citric acid, and acetic acid.

[0033] Defoamers, such as silicone, C 8-10 fatty alcohols, C 10-20 One or more of saturated fatty acids (such as decanoic acid) and amides, silicone oils and silicone compounds, but not limited thereto.

[0034] Disintegrants include, but are not limited to, one or more of sodium carboxymethyl starch, croscarmellose sodium, croscarmellose cellulose, modified starch, croscarmellose polyvinylpyrrolidone, ammonium sulfate, sodium alginate, etc.

[0035] Binders include, but are not limited to, one or more of starch, xanthan gum, gelatin and gum arabic, sodium benzoate, magnesium aluminum silicate, povidone, sucrose, glucose, and dextrin.

[0036] The carrier / filler may be one or more of the following, but is not limited to: diatomaceous earth, attapulgite, bentonite, zeolite, sepiolite, kaolin, clay, silica, light calcium carbonate, starch, magnesium stearate, talc, granulated starch, ammonium sulfate, and sodium sulfate.

[0037] Film-forming agents include, for example, polyacrylate film-forming agent CMJ-002-03, but are not limited thereto.

[0038] Warning colors include, for example, pigment R2002S (produced by Decma (Tianjin) Pigment Chemical Co., Ltd.), but are not limited to this.

[0039] Preferably, the formulation of the present invention can be prepared as a seed treatment suspension, wherein the active ingredients, thiamethoxam, thiamethoxam and fludioxonil, account for 5% to 80% of the total weight of the formulation, preferably 10% to 50%.

[0040] The application of the compositions and formulations of the present invention in the prevention and control of plant diseases and pests, preferably, the plant disease is one of wheat sheath blight, root rot, anthracnose and stem base rot, particularly preferably wheat stem base rot; the pest is one of vegetable cabbage caterpillar, diamondback moth, rice planthopper, rice stem borer, cotton aphid or wheat wireworm; preferably, the pest is wheat wireworm.

[0041] The present invention will be further described in detail below with reference to embodiments.

[0042] Preparation Examples

[0043] Example 1: 17% Buthidimethalin·Thiamethoxam·Fluordioxonil Seed Treatment Suspension

[0044] A 17% carbofuran·thiamethoxam·fludioxonil seed treatment suspension was prepared by adding 8% carbofuran, 8% thiamethoxam, 1% fludioxonil, 3% nonionic comb copolymer, 2% EO / PO block copolymer, 2% castor oil polyoxyethylene ether, 0.2% xanthan gum, 0.1% sodium benzoate, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.2% silicone defoamer, 0.5% polyacrylate film-forming agent CMJ-002-03, 10% color paste R2002S, 1% triethanolamine, 3% S-150, and deionized water to 100% by weight.

[0045] Example 2: 18% Buthidimethalin·Thiamethoxam·Fluordioxonil Seed Treatment Suspension

[0046] A seed treatment suspension of 18% carbofuran·thiamethoxam·fludioxonil was prepared by adding 8% carbofuran, 8% thiamethoxam, 2% fludioxonil, 4% nonionic comb copolymer, 1.5% EO / PO front copolymer, 2% castor oil polyoxyethylene ether, 0.2% xanthan gum, 0.1% sodium benzoate, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.2% silicone defoamer, 0.5% polyacrylate film-forming agent CMJ-002-03, 10% color paste R2002S, 1% triethanolamine, 3% S-150, and deionized water to 100% by weight.

[0047] Example 3: 33% Buthidimethoate·Thiamethoxam·Fluordioxonil Seed Treatment Suspension

[0048] A 33% carbofuran·thiamethoxam·fludioxonil seed treatment suspension was prepared by adding 24% carbofuran, 8% thiamethoxam, 1% fludioxonil, 2% polycarboxylate, 2% fatty alcohol polyoxypropylene polyoxyethylene ether, 3% castor oil polyoxyethylene ether, 0.1% xanthan gum, 0.1% sodium benzoate, 0.7% magnesium aluminum silicate, 5% ethylene glycol, 0.2% silicone defoamer, 0.5% polyacrylate film-forming agent CMJ-002-03, 10% color paste R2002S, 2% triethanolamine, 5% S-150, and deionized water to 100% by weight.

[0049] Example 4: 34% Buthidimethoate·Thiamethoxam·Fluordioxonil Seed Treatment Suspension

[0050] A 34% carbofuran·thiamethoxam·fludioxonil seed treatment suspension was prepared by adding 8% carbofuran, 24% thiamethoxam, 2% fludioxonil, 4% nonionic comb copolymer, 2% EO / PO front copolymer, 2% castor oil polyoxyethylene ether, 0.1% xanthan gum, 0.1% sodium benzoate, 0.5% magnesium aluminum silicate, 5% ethylene glycol, 0.2% silicone defoamer, 0.5% polyacrylate film-forming agent CMJ-002-03, 10% color paste R2002S, 1% triethanolamine, 3% S-150, and deionized water to 100% by weight.

[0051] II. Bioactivity Test

[0052] 1) Test reagents:

[0053] 92% Butylcarbamate technical grade: Produced by Shandong Huayang Pesticide & Chemical Group Co., Ltd. (PD20170190), available commercially:

[0054] 99% fludioxonil technical grade: produced by Jiangsu Hormone Research Institute Co., Ltd. (PD20172577), commercially available.

[0055] 98% Thiamethoxam technical grade: produced by Hebei Derui Chemical Co., Ltd. (PD20180848), purchased commercially.

[0056] II) Test Target

[0057] Wheat wireworm (Pleonomus canaliculatus) was artificially captured in the field as adults, and then raised in the laboratory to the third instar larvae for future use.

[0058] The pathogen causing wheat stem rot (Fusarium pseudograminearum): Diseased tissue was collected from the field, isolated, purified, and preserved on slant culture for later use in the laboratory.

[0059] III) Test Methods

[0060] 1. Activity assay of wheat wireworm (test standard: NY / T 1154.7-2006)

[0061] 1.1 Preparation of test materials

[0062] Adult insects were captured in the field and brought back to the laboratory for rearing. The adults were transferred to containers filled with sterilized and moisturized sandy loam soil (15%–20% moisture content), with a soil layer approximately 10 cm thick. The containers were sealed with mesh and reared at (25±1)℃. Wheat seedlings were inserted into the containers as feed, and the feed was changed every other day. Eggs were collected from the soil and placed in petri dishes filled with sterilized sandy loam soil (10%–20% moisture content) for development. After hatching, the newly hatched larvae were transferred to rearing boxes filled with sterilized sandy loam soil (10%–20% moisture content) and reared individually at 25℃±1℃. They were then reared with malt until the third instar for later use.

[0063] 1.2 Chemical treatment

[0064] The assay was performed using the immersion method. Third-instar larvae of the wheat wireworm were immersed in the pesticide solution for 10 seconds, then removed. Excess pesticide was absorbed with filter paper, and each larva was transferred to a glass test tube containing fresh wheat seedlings. The tube opening was covered with a damp black cloth and placed in a constant-temperature rearing room at (25±1)℃ and a relative humidity of 60%–80%. Each treatment was repeated four times, with 30 larvae immersed in each replicate. A control group without the pesticide was also included.

[0065] 1.3 Survey

[0066] Investigate the mortality of test insects 72 hours after treatment (death criterion: the insect cannot move when touched with a brush), and record the total number of insects and the number of dead insects.

[0067] 1.4 Data Calculation Methods

[0068] Based on the survey data, the adjusted mortality rates for each treatment were calculated. The adjusted mortality rates were calculated according to equations (1) and (2), expressed as percentages (%), and the results were rounded to two decimal places.

[0069] ………………………………………(1)

[0070] Where: P1—mortality rate

[0071] K—Number of dead bugs

[0072] N—Total number of insects treated

[0073] …………………………………(2)

[0074] Where: P2—corrected mortality rate

[0075] P t —Handling Mortality

[0076] P0—Morale rate in the blank control group

[0077] If the control mortality rate is <5%, no correction is needed; if the control mortality rate is between 5% and 20%, correction should be made according to formula (7); if the control mortality rate is >20%, the experiment needs to be repeated.

[0078] 1.5 Test Results

[0079] This invention performs regression analysis based on the logarithmic values ​​of each drug concentration and the corresponding corrected mortality probability values, and uses DPS data processing software to analyze and calculate the LC of each drug. 50 LC 90 Equivalent values ​​and their 95% confidence limits and their co-toxicity coefficients were compared to assess synergistic effects.

[0080] This invention evaluates the synergistic effect of compounding according to Sun Yunpei's method, that is, the co-toxicity coefficient CTC≤80 shows an antagonistic effect, 80<CTC<120 shows an additive effect, and CTC≥120 shows a synergistic effect.

[0081] Table 1. Results of the combined toxicity assay of different mass ratios of carbofuran and thiamethoxam against wheat wireworm.

[0082]

[0083] Table 2. Results of combined toxicity assays of carbofuran and thiamethoxam 24:8 mixture with different ratios of fludioxonil against wheat wireworm.

[0084]

[0085] Table 3. Results of combined toxicity assays of thiamethoxam and thiamethoxam in an 8:8 ratio with different ratios of fludioxonil against wheat wireworm.

[0086]

[0087] Table 4. Results of combined toxicity assays of carbofuran and thiamethoxam 8:24 mixture with different ratios of fludioxonil against wheat wireworm.

[0088]

[0089] 2. Determination of the pathogen causing wheat stem rot (Experimental basis: NY / T 1156.6-2006)

[0090] 2.1 Preparation of test materials

[0091] The wheat stem rot pathogen was cultured on PDA medium for later use.

[0092] PDA culture medium, deionized water, glass rods, plastic pipette tips, petri dishes, punchers, inoculators, etc. are sterilized and ready for use.

[0093] 2.2 Chemical treatment

[0094] Under aseptic conditions, pre-melted and cooled sterile PDA medium (to approximately 50°C) was quantitatively added to a sterile streaked Erlenmeyer flask, leveling the medium with the streak line (60 mL). Then, 600 μL of the drug solution was sequentially added to each of the flasks, from lowest to highest concentration, and thoroughly mixed. The mixture was then poured into four equal petri dishes (Φ 9 cm) to create five concentration gradient plates. A blank control (without the drug) was also included.

[0095] 2.3 Inoculation and Culture

[0096] Select a uniformly growing strain for inoculation. Under aseptic conditions, use a 5mm diameter punch to cut a mycelial cake from the same circumference at the edge of the colony (ensuring that the tested pathogens are of the same age). Use an inoculator to inoculate the mycelial cake into the center of the drug-containing culture medium in a petri dish, with the mycelial side facing down. Cover the dish and incubate it upside down in the dark in an incubator at 25±1℃.

[0097] 2.4 Survey

[0098] After 72 hours of incubation, mycelial growth was investigated, and colony diameters were measured using calipers. Each colony was measured vertically using a cross-sectional method, and the average value was used to calculate the inhibition rate.

[0099] 2.5 Data Calculation Methods

[0100] Based on the survey results, the inhibition rate of mycelial growth of *Strombus haematous* on each treatment concentration was calculated using formulas (3) and (4), expressed as a percentage (%), and the results were rounded to two decimal places. The relevant calculation formulas are as follows:

[0101] ………………………………………(3)

[0102] Where: D—colony growth diameter;

[0103] D1—colony diameter;

[0104] D2—Diameter of the mushroom cake.

[0105] ………………………………..(4)

[0106] In the formula: I—mycelial growth inhibition rate;

[0107] D0—Correlation diameter of the blank control;

[0108] D t —The diameter of colony growth after chemical treatment.

[0109] 2.6 Test Results

[0110] This invention performs regression analysis based on the logarithmic values ​​of each drug concentration and the corresponding inhibition rate probability values, and uses DPS data processing software to analyze and calculate the LC of each drug. 50 LC 90 Equivalent values ​​and their 95% confidence limits and their co-toxicity coefficients were compared to assess synergistic effects.

[0111] This invention evaluates the synergistic effect of compounding according to Sun Yunpei's method, that is, the co-toxicity coefficient CTC≤80 shows an antagonistic effect, 80<CTC<120 shows an additive effect, and CTC≥120 shows a synergistic effect.

[0112] Table 5. Results of combined toxicity assays of different ratios of carbofuran and thiamethoxam 24:8 mixture with fludioxonil against wheat stem rot.

[0113]

[0114] Table 6. Results of combined toxicity assays of different ratios of thiamethoxam and thiamethoxam (8:8 ratio) with fludioxonil against wheat stem rot.

[0115]

[0116] Table 7. Results of combined toxicity assays of different ratios of carbofuran and thiamethoxam (8:24 ratio) with fludioxonil against wheat stem rot.

[0117]

[0118] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A pesticide composition, characterized in that, It is composed of the active ingredients thiamethoxam, thiamethoxam and fludioxonil, wherein the mass ratio of thiamethoxam, thiamethoxam and fludioxonil is 24-8:8-24:0.5-4.

2. The pesticide composition according to claim 1, characterized in that, The mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 24:8:0.5-4, preferably 24:8:0.5, 24:8:1, 24:8:2, 24:8:3, or 24:8:

4.

3. The pesticide composition according to claim 1, characterized in that, The mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 8:8:0.5-4, preferably 8:8:0.5, 8:8:1, 8:8:2, 8:8:3, or 8:8:

4.

4. The pesticide composition according to claim 1, characterized in that, The mass ratio of thiamethoxam, thiamethoxam, and fludioxonil is 8:24:0.5-4, preferably 8:24:0.5, 8:24:1, 8:24:2, 8:24:3, or 8:24:

4.

5. A pesticide formulation, characterized in that, It contains the pesticide composition according to any one of claims 1-4 and a suitable pesticide adjuvant.

6. The formulation according to claim 5, characterized in that, The formulation is prepared into a suitable form for pesticides, preferably a seed treatment suspension.

7. The formulation according to claim 6, characterized in that, The active ingredients, thiamethoxam, thiamethoxam, and fludioxonil, account for 5% to 80% of the total weight of the formulation, preferably 10% to 50%.

8. The use of the composition according to any one of claims 1-4 or the preparation according to any one of claims 5-7 in the prevention and control of plant diseases and pests; preferably, the plant disease is one of wheat sheath blight, root rot, anthracnose and stem base rot, particularly preferably wheat stem base rot; preferably, the pest is one of cabbage caterpillar, diamondback moth, rice planthopper, rice stem borer, rice aphid, or wheat wireworm.

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