A pesticide composition containing fenpyrazone

Abstract

The present invention provides a synergistic composition containing fenpyroxene. The composition contains fenpyroxene and compound 1, wherein compound 1 has the following structure: #imgabs0#Compound 1, wherein the weight ratio of fenpyroxene to compound 1 is 1:20-20:1, preferably 1:10-10:1, more preferably 10:1-1:1, and particularly preferably 10:1, 3:1, 2:1, and 1:1. Furthermore, the present invention provides a fenpyroxene IX crystal, which can solve the problem of instability in the performance of dispersible and suspending agents prepared by fenpyroxene and compound 1.

Description

Technical Field

[0001] The present invention relates to the field of pesticides, in particular to a pesticide composition containing fenpyroxene, and especially to a fenpyroxene IX crystal and a dispersible oil suspension containing the fenpyroxene IX crystal. Background Art

[0002] Topramezon is a herbicidal active substance of formula I and a tautomer of formula II:

[0003]

[0004] Benpyrazone is a benzoyl pyrazolone herbicide developed by BASF. It inhibits 4-hydroxyphenylpyruvate dioxidase (4-HPPD), an enzyme involved in plastoquinone biosynthesis, indirectly affecting carotenoid synthesis, thereby interfering with chloroplast synthesis and function, ultimately leading to severe bleaching. Sensitive weeds typically develop bleaching symptoms within 2-5 days of treatment, with symptoms most pronounced in the aboveground growth zones (growing points, internodes, leaves, and veins). Weed growth is also inhibited. Under light, chlorotic tissue necroses, and plants typically die 14 days after treatment. It is highly effective against weeds resistant to glyphosate, triazines, acetolactate synthase (ALS) inhibitors, and acetyl-CoA carboxylase (ACCase) inhibitors. It effectively controls major grass and broadleaf weeds in corn crops worldwide (it is less effective against sedge weeds). Benpyrazone offers a broad spectrum of activity, high compatibility, and safety for corn and subsequent crops.

[0005] Those skilled in the art are aware that different crystalline forms of the same active pesticide substance may sometimes exhibit different properties, such as differences in the following properties: solubility, vapor pressure, dissolution rate, stability towards phase transformation into another crystalline form, stability during grinding, suspension stability, optical and mechanical properties, hygroscopicity, crystal shape and size, filterability, density, melting point, decomposition stability, color and sometimes even chemical reactivity or biological activity.

[0006] Therefore, research on pesticide active substances has always been a focus of attention. Currently, BASF patents report the high-purity stable crystalline Form I of topramezone and four other forms (Forms II-V) as well as three crystalline solvates of topramezone (Forms VI-VIII). Domestic companies have also studied the crystals of fenpyrazone salts. Some XRD patterns of the above crystals are shown in the attached figure. Figure 2-9 .

[0007] Papanna (Beijing) Technology Co., Ltd. disclosed in CN116947749A a novel amide compound that exhibits excellent insecticidal effects. Compound 1 (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide):

[0008] Showed better results.

[0009] During the research process, the applicant unexpectedly discovered that the combination of fenpyraclostrobin and N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide has a good synergistic effect in the weed control process.

[0010] In addition, the applicant's research has also found that the dispersible suspending agent of the composition of fenpyrazone IX crystals and N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide does not cause the problem of fenpyrazone crystal precipitation in the dispersible suspending agent of the composition of fenpyrazone I crystals and N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide. Summary of the Invention

[0011] The present invention first provides a synergistic composition containing fenpyrazone, which contains fenpyrazone and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1). The structure of (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1) is as follows: The weight ratio of fenpyrad and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1) is 1:20-20:1, preferably 1:10-10:1.

[0012] The present invention also provides a fenpyroxene IX crystal, which shows all of the following reflections expressed as 2θ values ​​in an X-ray powder radiograph at 30°C and Cu-Ka radiation using Cu-Ka radiation (1.54178 Å): 8.5 ± 0.2°, 11.6 ± 0.2°, 15.8 ± 0.2°, 18.8 ± 0.2°, 19.2 ± 0.2°, 20.7 ± 0.2°, 21.2 ± 0.2°, 21.8 ± 0.2°, 28.1 ± 0.2° and 33.3 ± 0.2°.

[0013] The present invention also provides a method for preparing fenpyrazone IX crystals, which comprises the following steps:

[0014] A method for preparing the fenpyrazone IX crystal according to claim 4, comprising the following steps:

[0015] Step 1: 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid is subjected to perchlorination to prepare 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride;

[0016] Step 2: adding the acyl chloride product obtained in step 1 dropwise to 1-methyl-5-hydroxypyrazole in the presence of an organic solvent, triethylamine, and acetone cyanohydrin to obtain fenpyrazone;

[0017] Step 3: After the above reaction is complete, acid is added to the system to neutralize the excess base, and then the temperature is raised to reflux for 1 hour, and the temperature is naturally lowered to room temperature and filtered to obtain a fenpyroxene solid;

[0018] Step 4: drying the fenpyrazone solid obtained in step 3 at 30-60° C. to obtain fenpyrazone crystal form IX.

[0019] Beneficial effects

[0020] 1. In the composition provided by the present invention, fenpyraclostrobin and compound 1 have a synergistic effect.

[0021] 2. The dispersible oil suspension concentrate prepared from the fenpyrazone IX crystals and compound 1 has stable performance, overcoming the problem of easy precipitation of fenpyrazone in the dispersible oil suspension concentrate product prepared from the combination of compound 1 and other fenpyrazone crystal forms.

[0022] Figures in the specification

[0023] Figure 1 XRD spectrum of fenpyrazone Form IX

[0024] Figure 2 XRD comparison spectra of fenpyrazone Form IX and Form Ⅰ

[0025] Figure 3 XRD spectrum of fenpyrazone Form Ⅰ

[0026] Figure 4 XRD spectrum of fenpyrazone Form II

[0027] Figure 5 XRD spectrum of fenpyrazone Form III

[0028] Figure 6 XRD spectrum of fenpyrazone Form IV

[0029] Figure 7 XRD spectrum of fenpyrazone crystal solvate VII-S

[0030] Figure 8 XRD spectrum of fenpyrazone Form VIII

[0031] Figure 9 XRD spectrum of fenpyrazone sodium salt crystal form DETAILED DESCRIPTION

[0032] In order to make the purpose, 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 part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention. Unless otherwise expressly stated, throughout the specification and claims, the term "including" or its variations such as "comprising" or "including" will be understood to include the stated components or steps, without excluding other material components or steps.

[0033] In addition, in order to better illustrate the present invention, numerous specific details are provided in the specific embodiments below. It should be understood by those skilled in the art that the present invention can also be implemented without certain specific details. In some embodiments, raw materials, methods, means, etc. well known to those skilled in the art are not described in detail in order to highlight the main purpose of the present invention.

[0034] The present invention first provides a synergistic composition containing fenpyrazone, which contains fenpyrazone and compound 1. The structure of compound 1 ((N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide)) is as follows: The weight ratio of fenpyrazone to compound 1 is 1:20-20:1, preferably 1:10-10:1, more preferably 10:1-1:1, and particularly preferably 10:1, 3:1, 2:1 and 1:1.

[0035] Preferably, the fenpyrazone in the above composition of the present invention is fenpyrazone IX crystals.

[0036] The present invention also provides a pesticide formulation comprising the above-mentioned pesticide composition and a pesticide-acceptable adjuvant. The adjuvant includes, but is not limited to, a solid carrier, a liquid carrier, a surfactant, and the like. Suitable adjuvants are added according to the requirements of the formulation.

[0037] The pesticide formulation of the present invention can be used in a suitable formulation form such as a suspension concentrate, emulsifiable concentrate, dispersible oil suspension concentrate, microcapsule, emulsion, water-dispersible powder, granule, dust, tablet, etc., and can be prepared by mixing the above-mentioned composition with at least one of a suitable inactive carrier and adjuvant in a suitable proportion as needed, followed by dissolving, separating, suspending, mixing, impregnating, adsorbing, or attaching the components.

[0038] The inactive carrier that can be used in the present invention may be solid or liquid, and examples thereof include, in particular, soybean flour, grain flour, wood flour, bark powder, sawdust, tobacco stem powder, walnut shell powder, bran, cellulose powder, residues after plant extraction, synthetic polymers such as powdered synthetic resins, clays (e.g., kaolin, bentonite, acid clay, etc.), talcs (e.g., talc, pyrophyllite, etc.), silica (e.g., diatomaceous earth, silica sand, mica, white carbon (also known as hydrous silica powder, hydrous silica powder called synthetic highly dispersible silicic acid, certain products containing calcium silicate as the main component)), activated carbon, sulfur powder, pumice, sintered diatomaceous earth, brick crushed material, fly ash, sand, inorganic mineral powders (e.g., calcium carbonate, calcium phosphate), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), and compost. These can be used alone or in the form of a mixture of two or more.

[0039] Examples of materials that can be used as inactive carriers in liquid form include materials that function as solvents and materials that do not function as solvents but can disperse the active ingredient compound with the assistance of an auxiliary agent.

[0040] Examples of inactive carriers include water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, ethylene glycol, etc.), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc.), ethers (e.g., diethyl ether, dioxane, cellosolve, diisopropyl ether, tetrahydrofuran, etc.), aliphatic hydrocarbons (e.g., kerosene, mineral oil, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent naphtha, alkylnaphthalene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, chlorobenzene, etc.), esters (e.g., ethyl acetate, butyl acetate, ethyl propionate, diisobutyl phthalate, dibutyl phthalate, dioctyl phthalate, etc.), amides (e.g., dimethylformamide, diethylformamide, dimethylacetamide, etc.), and nitriles (e.g., acetonitrile, etc.), which can be used alone or in the form of a mixture of two or more.

[0041] Examples of the adjuvant include the following adjuvants, which can be used alone or in combination of two or more depending on the purpose. However, no adjuvant may be used at all.

[0042] For the purpose of emulsification, dispersion, solubilization and / or wetting of the active ingredient compound, a surfactant may be used.

[0043] Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkylaryl sulfonates, naphthalenesulfonates, ligninsulfonates, and higher alcohol sulfonates.

[0044] Auxiliary agents that can be used for the purpose of stabilizing the dispersion, adhering and / or binding of the active ingredient compound include casein, gelatin, starch, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, turpentine, bran oil, bentonite, xanthan gum, and lignin sulfonate.

[0045] Examples of adjuvants that can be used to improve the flowability of solid products include waxes, stearates, and alkyl phosphates. Adjuvants such as naphthalenesulfonate condensation products or condensed phosphates can be used as suspending agents in suspensions. Defoaming agents such as silicone oil can also be used as adjuvants.

[0046] Furthermore, to enhance the stability of the composition against light, heat, oxidation, etc., a stabilizer may be added as needed to obtain a more stable composition. Examples of stabilizers include antioxidants, ultraviolet absorbers, phenol derivatives such as BHT (2,6-di-tert-butyl-4-methylphenol) and BHA (butylated hydroxyanisole), bisphenol derivatives, and arylamines such as phenyl-α-naphthylamine and phenyl-β-naphthylamine, condensates of aminophenethyl ether and acetone, and benzophenone compounds.

[0047] The effective amount of fenpyroxen and Compound 1 in the formulation is generally 0.5-20% by weight in powders, 5-50% by weight in emulsions, 10-90% by weight in water-dispersible powders, 0.1-20% by weight in granules, and 10-90% by weight in flowables. Meanwhile, the amount of carrier in each formulation is generally 30-99% by weight in powders, 10-95% by weight in emulsions, 10-90% by weight in water-dispersible powders, 50-99% by weight in granules, and 5-90% by weight in flowables. The amount of these adjuvants is generally 0.1-30% by weight in powders, 1-40% by weight in emulsions, 0.1-25% by weight in water-dispersible powders, 0.1-30% by weight in granules, and 0.1-40% by weight in flowables.

[0048] The present invention also provides a crystal of fenpyroxene IX, which shows all of the following reflections expressed as 2θ values ​​in an X-ray powder radiograph at 30°C and Cu-Ka radiation using Cu-Ka radiation (1.54178 Å): 8.5 ± 0.2°, 11.6 ± 0.2°, 15.8 ± 0.2°, 18.8 ± 0.2°, 19.2 ± 0.2°, 20.7 ± 0.2°, 21.2 ± 0.2°, 21.8 ± 0.2°, 28.1 ± 0.2° and 33.3 ± 0.2°.

[0049] The present invention also provides a method for preparing fenpyrazone IX crystals, comprising the following steps:

[0050] Step 1: 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid is subjected to perchlorination to prepare 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride;

[0051] Step 2: adding the acyl chloride product obtained in step 1 dropwise to 1-methyl-5-hydroxypyrazole in the presence of an organic solvent, triethylamine, and acetone cyanohydrin to obtain fenpyrazone;

[0052] Step 3: After the above reaction is complete, acid is added to the system to neutralize the excess base, and then the temperature is raised to reflux for 1 hour, and the temperature is naturally lowered to room temperature and filtered to obtain a fenpyroxene solid;

[0053] Step 4: drying the fenpyrazone solid obtained in step 3 at 30-60° C. to obtain fenpyrazone crystal form IX.

[0054] In the above preparation method, the organic solvent is selected from one or more of dichloromethane, dichloroethane, chloroform, and toluene, preferably dichloroethane or toluene. The acid is hydrochloric acid, and the amount of the acid used is 0.1-5 times, preferably 0.5-2 times, the amount of [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1-pyrazol-4-yl)methanone.

[0055] The pesticide composition, pesticide preparation and benzathine IX crystal of the present invention have a wide range of applications, and the plants or ranges to which they are applied mainly include the following categories: fruits and vegetables, including cucumbers, loofahs, watermelons, melons, pumpkins, hanging melons, spinach, celery, cabbage, Chinese cabbage, gourds, peppers, eggplants, tomatoes, onions, ginger, garlic, leeks, lettuce, kidney beans, cowpeas, broad beans, radishes, carrots, potatoes, and yams; cereals, including wheat, barley, corn, rice, and sorghum; fruit trees, including apples, pears, bananas, citrus fruits, grapes, litchis, and mangoes; flowers, including peonies, roses, and anthuriums; oil crops, including peanuts, soybeans, rapeseed, sunflowers, and sesame seeds; sugar crops, including sugar beets and sugarcane; and other crops, such as strawberries, potatoes, sweet potatoes, tobacco, and tea. The plants or ranges listed above do not limit the scope of application of the amide compounds of the present invention.

[0056] The technical solutions of the present disclosure will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present disclosure and should not be construed as limiting the scope of protection of the present disclosure. All technologies implemented based on the above content of the present disclosure are included within the scope of protection intended by the present disclosure.

[0057] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0058] 1. Preparation Example

[0059] Example 1 Preparation of Form IX of Mefenacet

[0060] Step 1: Weigh 28.3 g of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid, add 100 g of dichloroethane and 0.5 g of DMF, raise the temperature to 70°C, and slowly add 11.8 g of thionyl chloride dropwise. After the addition is complete, keep the mixture warm for one hour and monitor the reaction to obtain a solution of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride.

[0061] Step 2: Weigh 9.8 g of 1-methyl-5-hydroxypyrazole, dissolve it in 100 g of dichloroethane, add 15 g of triethylamine and 1 g of acetone cyanohydrin, raise the temperature to 40 ° C, and slowly add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1 dropwise. After the addition is completed, keep warm for 2 hours and monitor the completion of the reaction to obtain a fenpyrotone reaction solution.

[0062] Step 3: Slowly add 73 g of hydrochloric acid dropwise to the fenpyroxene reaction solution obtained in step 2, then heat and reflux for one hour, slowly cool to room temperature, and filter.

[0063] Step 4: drying the solid obtained in step 3 at 40° C. to obtain fenpyrad-17-one in crystal form IX.

[0064] Example 2

[0065] Step 1: Weigh 28.3 g of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid, add 100 g of dichloroethane and 0.5 g of DMF, raise the temperature to 70°C, and slowly add 11.8 g of thionyl chloride dropwise. After the addition is complete, keep the mixture warm for one hour and monitor the reaction to obtain a solution of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride.

[0066] Step 2: Weigh 9.8 g of 1-methyl-5-hydroxypyrazole, dissolve it in 100 g of dichloroethane, add 15 g of triethylamine and 1 g of acetone cyanohydrin, raise the temperature to 40 ° C, and slowly add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1 dropwise. After the addition is completed, keep warm for 2 hours and monitor the completion of the reaction to obtain a fenpyrotone reaction solution.

[0067] Step 3: Slowly add 54.5 g of hydrochloric acid dropwise to the fenpyroxene reaction solution obtained in step 2, then heat and reflux for one hour, slowly cool to room temperature, and filter.

[0068] Step 4: drying the solid obtained in step 3 at 60° C. to obtain fenpyrad-17-one in crystal form IX.

[0069] Example 3

[0070] Step 1: Weigh 28.3 g of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid, add 100 g of toluene and 0.5 g of DMF, raise the temperature to 70°C, and slowly add 11.8 g of thionyl chloride dropwise. After the addition is complete, keep the mixture warm for one hour and monitor the reaction to obtain a solution of 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride.

[0071] Step 2: Weigh 9.8 g of 1-methyl-5-hydroxypyrazole, dissolve it in 100 g of toluene, add 15 g of triethylamine and 1 g of acetone cyanohydrin, raise the temperature to 40 ° C, and slowly add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1 dropwise. After the addition is completed, keep warm for 2 hours and monitor the reaction to obtain a fenpyrotone reaction solution.

[0072] Step 3: Slowly add 73 g of hydrochloric acid dropwise to the fenpyroxene reaction solution obtained in step 2, then heat and reflux for one hour, slowly cool to room temperature, and filter.

[0073] Step 4: drying the solid obtained in step 3 at 40° C. to obtain fenpyrad-17-one in crystal form IX.

[0074] 2. Preparation Examples

[0075] Example 1 Preparation of 10% Mefenacet IX Crystals and Compound 1 ((N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide)) Dispersible Oil Suspension

[0076] Weigh 5.1 g of fenpyroxene IX crystals (98%), 15.1 g of compound 1, 6 g of styrylphenol polyoxyethylene ether, 4 g of fatty alcohol polyoxyethylene ether, 3 g of dodecylphenol polyoxyethylene ether, 2 g of organic bentonite, 1 g of white carbon black, and make up the amount to 100 g of soybean oil methyl ester.

[0077] Comparative Example 1 Preparation of 10% Mefenacet I Crystals and Compound 1 ((N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide)) Dispersible Oil Suspension

[0078] Weigh 5.1 g of benzothiazolin I crystals (98%), 15.1 g of compound 1, 6 g of styrylphenol polyoxyethylene ether, 4 g of fatty alcohol polyoxyethylene ether, 3 g of dodecylphenol polyoxyethylene ether, 2 g of organic bentonite, 1 g of white carbon black, and make up the amount to 100 g of soybean oil methyl ester.

[0079] 3. Preparation stability test

[0080] The prepared Example 1 and Control Example 1 were placed in hot storage at 54°C and cold storage at 0°C for 14 days, and the content of fenpyroxene was tested. The decomposition rate = (cold storage content - hot storage content) / cold storage content * 100%. The test results are shown in Table 1.

[0081] Table 1 Stability test

[0082] Crystal form Whether flocculation Preparation viscosity Decomposition rate% Ⅸ no 400 1 Ⅰ yes 950 10.5

[0083] As can be seen from Table 1, the dispersible oil suspension prepared using the methamidoprop-Isopropyl IX crystal form of the present invention has excellent stability.

[0084] 4. Control Effects of Benpyraclostrobin and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1) on Barnyardgrass

[0085] Seeds of barnyard grass were planted in plastic pots with a surface area of ​​100 square centimeters (cm2), and the plants were grown in a greenhouse for 7-36 days using a photoperiod of approximately 14 hours (h) maintained at 18°C ​​during the day and 17°C at night. Nutrients and water were added regularly, and overhead incandescent lamps were used to provide supplemental lighting when necessary. When the plants reached the 2nd to 3rd leaf stage, they were tested.

[0086] Treatments consisted of fenpyrad and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide), applied individually or in combination.

[0087] Treated plants and control plants were placed in the above-mentioned greenhouse and watered by irrigation to prevent washout of the test compound. After 10-15 days, the condition of the test plants was visually assessed compared to the control plants and scored on a scale of 0 to 100%, where 0 corresponds to no damage and 100 corresponds to complete kill.

[0088] Colby's equation was used to determine the herbicidal response expected from a mixture (Colby, SR. Calculation of the synergistic and antagonistic response of herbicide combinations. Weeds 1967, 15, 20-22.).

[0089] The following equation is used to calculate the expected activity of a mixture containing two active ingredients, A and B:

[0090] Expected activity E0 = A + B - (A × B / 100)

[0091] A = Efficacy of active ingredient A observed at the same concentration as used in the mixture.

[0092] B = observed efficacy of active ingredient B at the same concentration as used in the mixture.

[0093] When the observed value E is greater than the theoretical value E0, it indicates a synergistic effect.

[0094] The test results are shown in Table 2.

[0095] Table 2 Indoor test data of compound 1 and fenpyraclostrobin IX on barnyardgrass

[0096]

[0097] As shown in Table 2, the mixture of fenpyraclostrobin and compound 1 has a significant synergistic effect on barnyard grass, especially in the range of 10:1-1:1, with a good synergistic effect. More preferably, a synergistic effect is exhibited at 10:1, 3:1, 2:1 and 1:1.

[0098] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A pesticide composition, characterized in that The invention is composed of fenpyrazone IX crystals and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide), wherein the weight ratio of fenpyrazone IX crystals to (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) is 10:1-1:

1.

2. The pesticide composition according to claim 1, characterized in that The weight ratios of the pyraclostrobin IX crystals and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) were 10:1, 3:1, 2:1, and 1:

1.

3. The pesticide composition according to claim 1 or 2, characterized in that The X-ray powder radiograph of the fenpyroxene IX crystals at 30° C. and Cu-Ka radiation showed all of the following reflections expressed as 2θ values: 8.5±0.2°, 11.6±0.2°, 15.8±0.2°, 18.8±0.2°, 19.2±0.2°, 20.7±0.2°, 21.2±0.2°, 21.8±0.2°, 28.1±0.2° and 33.3±0.2°.

4. A pesticide formulation, characterized in that Contains the pesticide composition according to any one of claims 1 to 3 and a pesticide-acceptable adjuvant.

5. The pesticide formulation according to claim 4, characterized in that The pesticide preparation can be prepared into a suitable dosage form as required.

6. The pesticide formulation according to claim 5, characterized in that The pesticide preparation can be prepared into one of a suspension concentrate, emulsifiable concentrate, dispersible oil suspension concentrate, microcapsule, emulsion, water-dispersible powder, granule and dust as required.

7. A method for preparing fenpyrazone IX crystals, comprising the following steps: Step 1: 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoic acid is chlorinated to prepare 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride; Step 2: adding the acyl chloride product obtained in step 1 dropwise to 1-methyl-5-hydroxypyrazole in the presence of an organic solvent, triethylamine, and acetone cyanohydrin to obtain fenpyrazone; Step 3: After the above reaction is complete, acid is added to the system to neutralize the excess base, and then the temperature is raised to reflux for 1 hour, and the temperature is naturally lowered to room temperature and filtered to obtain a fenpyroxene solid; Step 4: drying the fenpyrazone solid obtained in step 3 at 30-60° C. to obtain fenpyrazone IX crystals.

8. The fenpyrazone IX crystal prepared by the method according to claim 7, characterized in that: Its X-ray powder radiograph at 30°C and Cu-Ka radiation shows all of the following reflections expressed as 2θ values: 8.5±0.2°, 11.6±0.2°, 15.8±0.2°, 18.8±0.2°, 19.2±0.2°, 20.7±0.2°, 21.2±0.2°, 21.8±0.2°, 28.1±0.2° and 33.3±0.2°.

9. The method according to claim 7, characterized in that The organic solvent is selected from one or more of dichloromethane, dichloroethane, chloroform and toluene.

10. The method according to claim 9, characterized in that The organic solvent is selected from dichloroethane or toluene.

11. The method according to claim 7, characterized in that The acid is hydrochloric acid, and the amount of the acid is 0.1-5 times that of [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1-pyrazol-4-yl)methanone.

12. The method according to claim 11, characterized in that The amount of the acid used is 0.5-2 times that of [3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)phenyl]-(5-hydroxy-1-methyl-1-pyrazol-4-yl)methanone.

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