Pesticide composition containing topramezone

Abstract

The invention provides a synergistic composition containing topramezone, the composition contains topramezone and a compound 1, the structure of the compound 1 is as follows: # imgabs0 # compound 1, and the weight ratio of topramezone to the compound 1 is (1: 20)-(20: 1), preferably (1: 10)-(10: 1), more preferably (10: 1)-(1: 1), especially preferably (10: 1), (3: 1), (2: 1) and (1: 1). In addition, the invention also provides a topramezone IX crystal, and the crystal can solve the problem that the performance of a dispersible suspending agent prepared from topramezone and the compound 1 is unstable.

Description

Technical Field

[0001] The invention relates to the field of pesticides, in particular to a pesticide composition containing fenpyroxil, and in particular to a fenpyroxil IX crystal and a dispersible oil suspension containing the fenpyroxil 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. The drug indirectly affects the synthesis of carotenoids by inhibiting 4-hydroxyphenylpyruvate dioxidase (4-HPPD) in the biosynthesis of plastoquinone, thereby interfering with the synthesis and function of chloroplasts and eventually leading to severe bleaching. Sensitive weeds usually show whitish symptoms within 2 to 5 days after treatment. The poisoning symptoms are most obvious in the aboveground growth area (growing point, internodes, leaves and veins), and the growth of weeds is also inhibited. Under light, the chlorotic tissue necroses and the plants usually die 14 days after treatment. It has a good control effect on weeds resistant to glyphosate, triazines, acetolactate synthase (ALS) inhibitors and acetyl-CoA carboxylase (ACCase) inhibitors, and can effectively control the main grass weeds and broadleaf weeds on corn crops worldwide (it has a poor effect on sedge weeds). Benpyrazone has the advantages of a wide spectrum of weed control, high activity, strong compatibility, and safety for corn and subsequent crops.

[0005] Those skilled in the art know that different crystalline forms of the same active pesticide substance may sometimes show different properties, such as differences in the following properties: solubility, vapor pressure, dissolution rate, stability to 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, the research on pesticide active substances has always been a focus of attention. At present, BASF's patent reports the stable crystal form I of topramezone and four other forms (crystal forms II-V) and three crystalline solvates of topramezone (crystal forms VI-VIII) obtained with high purity. Domestic companies have also studied the crystals of the salts of fenpyroxene. Some XRD diagrams of the above crystals are shown in the attached Figure 2-9 .

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

[0008] Shows better results.

[0009] The applicant unexpectedly discovered during the research process that the combination of fenpyrazone 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 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 will 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 fenpyroxene, the composition containing fenpyroxene and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1), wherein 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 fenpyroxil to (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 its X-ray powder radiogram at 30°C and Cu-Ka radiation using Cu-Ka radiation (1.54178A): 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 a fenpyroxetine IX crystal, which comprises the following steps:

[0014] A method for preparing the fenpyroxil 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 into 1-methyl-5-hydroxypyrazole under the conditions of an organic solvent, triethylamine and acetone cyanohydrin to obtain fenpyrazone;

[0017] Step 3, after the above reaction is complete, an acid is added to the system to neutralize the excess alkali, 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 fenpyroxil 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, fenpyrotone and compound 1 have a synergistic effect.

[0021] 2. The performance of the dispersible oil suspension prepared by the benomyl IX crystal and compound 1 is stable, which overcomes the problem of easy precipitation of benomyl in the dispersible oil suspension product prepared by the combination of compound 1 and other crystal forms of benomyl.

[0022] Instruction Manual

[0023] Figure 1 XRD spectrum of fenpyroxil Form IX

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

[0025] Figure 3 XRD spectrum of fenpyroxil Form Ⅰ

[0026] Figure 4 XRD spectrum of fenpyroxil crystal form II

[0027] Figure 5 XRD spectrum of fenpyroxil Form III

[0028] Figure 6 XRD spectrum of fenpyroxil Form IV

[0029] Figure 7 XRD spectrum of fenpyroxetine crystalline solvate Ⅶ-S

[0030] Figure 8 XRD spectrum of fenpyroxil Form Ⅷ

[0031] Fig. 9 XRD spectrum of fenpyroxil 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, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work 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 "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 be implemented without certain specific details. In certain embodiments, raw materials, methods, means, etc. well known to those skilled in the art are not described in detail to highlight the gist 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 benomyl 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 crystal.

[0036] The present invention also provides a pesticide formulation, which contains the above pesticide composition of the present invention and pesticide acceptable adjuvants. The adjuvants include solid carriers, liquid carriers, surfactants, etc., but are not limited thereto. Appropriate adjuvants are added according to the requirements of the dosage form.

[0037] The pesticide preparation of the present invention can be used in the form of a suitable formulation such as a suspension, emulsifiable concentrate, dispersible oil suspension, 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 an adjuvant in a suitable proportion as required, and then 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 meal, grain meal, wood meal, bark meal, sawdust, tobacco stem meal, walnut shell meal, 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.), silicon dioxide (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 powder (e.g., calcium carbonate, calcium phosphate), chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), and compost, which may 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 active ingredient compounds with the assistance of auxiliary agents.

[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 may be used alone or in the form of a mixture of two or more.

[0041] Examples of the auxiliary agent include the following auxiliary agents, which can be used alone or in combination of two or more depending on the purpose; however, no auxiliary agent may be used.

[0042] A surfactant may be used for the purpose of emulsifying, dispersing, solubilizing and / or wetting the active ingredient compound.

[0043] Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resin acid esters, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, alkyl aryl sulfonates, naphthalene sulfonates, lignin sulfonates, and higher alcohol sulfonates.

[0044] Auxiliary agents that can be used for the purpose of dispersion stabilization, adhesion 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 for the purpose of improving the fluidity 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. Defoamers such as silicone oils can also be used as adjuvants.

[0046] In addition, in order to enhance the stability of the composition to 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), BHA (butylated hydroxyanisole), bisphenol derivatives, and arylamines, such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, condensates of aminophenethyl ether and acetone, and benzophenone compounds.

[0047] The effective amount of the compound benzathine and compound 1 in the formula preparation is usually 0.5-20% by weight in powder, 5-50% by weight in emulsion, 10-90% by weight in water-dispersible powder, 0.1-20% by weight in granules, and 10-90% by weight in flow agents. On the other hand, the amount of the carrier in each formulation is usually 30-99% by weight in powder, 10-95% by weight in emulsion, 10-90% by weight in water-dispersible powder, 50-99% by weight in granules, and 5-90% by weight in flow agents. The amount of the above-mentioned adjuvant is usually 0.1-30% by weight in powder, 1-40% by weight in emulsion, 0.1-25% by weight in water-dispersible powder, 0.1-30% by weight in granules, and 0.1-40% by weight in flow agents.

[0048] The present invention also provides a fenpyroxil IX crystal, which shows all of the following reflections expressed as 2θ values ​​in its X-ray powder radiogram at 30°C and Cu-Ka radiation using Cu-Ka radiation (1.54178A): 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 a fenpyroxetine IX crystal, the steps of which are as follows:

[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 into 1-methyl-5-hydroxypyrazole under the conditions of an organic solvent, triethylamine and acetone cyanohydrin to obtain fenpyrazone;

[0052] Step 3, after the above reaction is complete, an acid is added to the system to neutralize the excess alkali, 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 fenpyroxil 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 is 0.1-5 times, preferably 0.5-2 times, 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 applied plants or ranges mainly include the following categories: fruits and vegetables, cucumber, loofah, watermelon, melon, pumpkin, hanging melon, spinach, celery, cabbage, cabbage, gourd, pepper, eggplant, tomato, onion, ginger, garlic, leek, lettuce, kidney bean, cowpea, broad bean, radish, carrot, potato, yam; cereals, wheat, barley, corn, rice, sorghum; fruit trees, apple, pear, banana, citrus, grape, litchi, mango; flowers, peony, rose, flamingo; oil crops, peanut, soybean, rape, sunflower, sesame; sugar crops, beet, sugarcane; other crops, such as strawberry, potato, sweet potato, tobacco and tea, etc.; the above-listed plants or ranges have no limiting effect on the application scope of the amide compounds of the present invention.

[0056] The technical solution of the present disclosure will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary illustrations 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 in 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, slowly drop 11.8 g of thionyl chloride, keep warm for one hour after the addition is complete, monitor the reaction to be complete, and obtain a 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride solution.

[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, slowly dropwise add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1, keep warm for 2 hours after the addition, monitor the reaction to be complete, and obtain a fenpyroxene reaction solution.

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

[0063] Step 4: Dry the solid obtained in step 3 at 40° C. to obtain methamidoprop-ethyl 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, slowly drop 11.8 g of thionyl chloride, keep warm for one hour after the addition is complete, monitor the reaction to be complete, and obtain a 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride solution.

[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, slowly dropwise add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1, keep warm for 2 hours after the addition, monitor the reaction to be complete, and obtain a fenpyroxene reaction solution.

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

[0068] Step 4: Dry the solid obtained in step 3 at 60° C. to obtain phenoxyacetyl phthalide 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, slowly drop 11.8 g of thionyl chloride, keep warm for one hour after the addition is complete, monitor the reaction to be complete, and obtain a 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride solution.

[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, slowly dropwise add 3-(4,5-dihydro-3-isoxazolyl)-2-methyl-4-(methylsulfonyl)benzoyl chloride obtained in step 1, keep warm for 2 hours after the addition, monitor the reaction to be complete, and obtain a fenpyroxene reaction solution.

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

[0073] Step 4: Dry the solid obtained in step 3 at 40° C. to obtain methamidoprop-ethyl 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 fenpyroxetine IX crystals (98%), 5.1 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 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 fenpyroxetine I crystals (98%), 5.1 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 to 100 g of soybean oil methyl ester.

[0079] 3. Preparation stability test

[0080] The prepared Example 1 and Comparative Example 1 were placed in hot storage at 54°C and cold storage at 0°C for 14 days, and the contents of fenpyroxil were tested respectively. 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 Viscosity of preparation 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-ethyl IX crystal form of the present invention has excellent stability.

[0084] 4. Control effect of fenpyroxil and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) (Compound 1) on barnyard grass

[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 with a photoperiod of about 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 fenpyroxil and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide), applied alone or in combination.

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

[0088] The Colby 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 = observed efficacy of active ingredient A 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 benzathone IX on barnyardgrass

[0096]

[0097] As shown in Table 2, the mixture of fenpyroxil and compound 1 has a significant synergistic effect on barnyard grass, especially in the range of 10:1-1:1, it has a good synergistic effect, and more preferably, it shows a synergistic effect in the range of 10:1, 3:1, 2:1 and 1:1.

[0098] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A pesticide composition, characterized in that: Contains benzathone and (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide), wherein the weight ratio of benzathone to (N-(2-(3-chloro-5-(trifluoromethyl)pyridin-2-yl)ethyl)-4-(4-chlorophenoxy)-2-(trifluoromethyl)benzamide) 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.

2. The pesticide composition according to claim 1, characterized in that: The fenpyrazone is a fenpyrazone IX crystal, wherein the fenpyrazone IX crystal shows all of the following reflections expressed in 2θ values ​​in an X-ray powder radiogram at 30°C and Cu-Ka radiation: 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°.

3. A pesticide preparation, characterized in that: Contains the pesticide composition according to any one of claims 1 to 2 and a pesticide-acceptable adjuvant.

4. The pesticide formulation according to claim 3, characterized in that The pesticide preparation can be prepared into a suitable dosage form as required, preferably one of a suspension, emulsifiable concentrate, dispersible oil suspension, microcapsule, emulsion, water-dispersible powder, granule and dust.

5. A fenpyroxetine IX crystal, characterized in that: Its X-ray powder radiogram 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°.

6. A method for preparing the fenpyroxil IX crystal according to claim 4, comprising the following steps: 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; Step 2, adding the acyl chloride product obtained in step 1 dropwise into 1-methyl-5-hydroxypyrazole under the conditions of an organic solvent, triethylamine and acetone cyanohydrin to obtain fenpyrazone; Step 3, after the above reaction is complete, an acid is added to the system to neutralize the excess alkali, 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 fenpyroxil solid; Step 4: drying the fenpyrazone solid obtained in step 3 at 30-60° C. to obtain fenpyrazone crystal form IX.

7. The preparation method according to claim 6, characterized in that: The organic solvent is selected from one or more of dichloromethane, dichloroethane, chloroform and toluene, preferably dichloroethane or toluene.

8. The preparation method according to claim 6, characterized in that: The acid is hydrochloric acid, and the amount of the acid is 0.1-5 times, preferably 0.5-2 times, 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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